METHOD FOR MANUFACTURING LAYER-BUILT MATERIAL WITH SILICON DIOXIDE FILM CONTAINING ORGANIC COLORANT AND THE LAYER-BUILT MATERIAL MANUFACTURED THEREBY

PROCEDE DE FABRICATION D'UN MATERIAU COMPOSE DE PLUSIEURS COUCHES AVEC FILM DE DIOXIDE DE SILICIUM CONTENANT UN COLORANT ORGANIQUE ET MATERIAU AINSI FABRIQUE

English Abstract

A method for forming a silicon dioxide film
according to the present invention comprises steps of:
(i) contacting a substrate with processing solution
containing silicofluoric acid solution supersaturated
with silicon dioxide, and (ii) forming the silicon
dioxide film on the substrate; wherein organic
colorants) is/are introduced into the silicon dioxide
film by adding organic colorants) to the processing
solution. According to the present invention, a silicon
dioxide film containing organic colorant without defect
such as air bubbles, or undecomposed raw material.

Claims

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WHAT IS CLAIMED IS:


1. A method for forming a colored silicon
dioxide film comprising the steps of:
(i) contacting a substrate with processing
solution containing hydro silicofluoric acid solution
supersaturated with silicon dioxide, and
(ii) forming the silicon dioxide film on the
substrate;
wherein organic colorant(s) is/are introduced into the
silicon dioxide film by adding organic colorant(s) to
the processing solution.
2. The method according to Claim 1,
wherein the supersaturated solution used as the
processing solution is prepared by saturating an
aqueous solution of hydrosilicofluoric acid with
silicon dioxide, and adding an additive to the
saturated solution or heating the saturated solution,
thereby supersaturating the saturated solution, and
the organic colorant is added to the saturated or
supersaturated solution.
3. The method according to Claim 1 or 2,
wherein the silicon dioxide film is formed on the
substrate by immersing the substrate in the
supersaturated solution containing the organic
colorant, thereby depositing the silicon dioxide film
containing the organic colorant onto the substrate.
4. A method for coloring an organic
substrate comprising the steps of:
(i) forming on the organic substrate a
primary film by coating and curing at least one



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silicon compound selected from the group consisting of
organic silicon compound represented by general
formula (I)

R1n Si(R2)4-n (I)


hydrolyzate thereof and colloidal silica, wherein R1
designates an organic group containing a hydrocarbon
group having 1 through 6 carbon atoms, vinyl group,
methacryloxy group, epoxy group, amino group, mercapto
group, fluorine, or chlorine; R2 designates at least
one member selected from alkoxy group, alkoxyalkoxy
group, acetoxy group and chlorine; n designates 0
through 4; and
(ii) forming on the primary film of the
organic substrate a secondary film of silicon dioxide
containing an organic colorant by contacting the
primary film coated organic substrate with processing
solution prepared by adding an organic colorant to
hydrosilicofluoric acid solution supersaturated with
silicon dioxide.
5. A method for coloring an organic
substrate according to Claim 4 wherein said organic
silicon compound is comprised of at least one kind of
silicon compounds containing amino group represented
by general formula (II):


R3m Si(R4)4-m (II)


wherein R3 designates organic group
containing amino group, R4 designates alkoxy
group and m designates 1 or 2; and
at least one kind of silicon compounds represented by
general formula (III):





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R5 ~ Si(R6)4-~ (III)


wherein R5 designates organic group
containing hydrocarbon group having not more
than 2 carbon atoms or hydroxyl group, R6
designates alkoxyalkoxy group and L
designates 1 or 2;
wherein blend ratio between the total molar
concentration (A) of the silicon compound containing
amino group represented by the general formula (II)
and the total molar concentration (B) of the silicon
compound represented by the general formula (III)
satisfies the relationship of O~B/A<10.
6. A method for coloring an organic
substrate according to Claim 4 wherein said organic
silicon compound is comprised of silicon compounds
containing methacryloxy group represented by general
formula (IV)

R7Si(R8)3 (IV)

wherein R7 designates organic group
containing methacryloxy group and R8
designates either a kind or a plurality of
complex groups selected from the group
consisting of alkoxy group, alkoxyalkoxy
group, acetoxy group and chlorine; and
silicon compound represented by the general formula
(V)

Si(R9)4 (V)




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wherein R9 designates either a kind or a
plurality of complex groups selected from a
group consisting of alkoxy group,
alkoxyalkoxy group, acetoxy group and
chlorine;
wherein blend ratio between the weight (C) converted
into R7SiO3/2 from the silicon compound containing
methacryloxy represented by the general formula (IV)
and the weight (D) converted into SiO2 from the
hydrolyzed silicon compound represented by the general
formula (V) satisfies the relationship of 0.1<D/C.
7. A method of coloring an organic
substrate according to Claim 4, 5 or 6 wherein an
organic resin primer layer is formed over the surface
of said organic substrate prior to forming the primary
film.
8. A method for coloring an organic
substrate according to any of Claims 4 to 7 wherein
said hydrosilicofluoric acid solution supersaturated
with silicon dioxide is prepared by adding an additive
which reacts on fluorine ions such as boric acid,
ammonia water, metal elements having greater
ionization tendency than that of hydrogen, or metallic
halogenide, to a hydrosilicofluoric acid solution
saturated with dissolved silicon dioxide for
supersaturation with silicon dioxide.
9. A method for coloring an organic
substrate according to any of Claims 4 to 7 wherein
said hydrosilicofluoric acid solution supersaturated
with silicon dioxide is prepared by means of
supersaturation with silicon dioxide which is



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dissolved at a low temperature for saturation and
then, heated up to a high temperature.
10. A method for coloring an organic
substrate according to any of Claims 4 to 9 wherein
said organic colorant to be added to the
hydrosilicofluoric acid solution supersaturated with
silicon dioxide is provided in the form of a water
solution or dissolved in a water soluble organic
solvent.
11. A coloring method for acrylic resin
substrate comprising of the steps of:
(i) forming a primary film by coating and
curing an organic silicon compound on the acrylic
resin substrate; and
(ii) forming a secondary film of silicon
dioxide containing organic colorant on the primary
film by contacting the substrate with a
hydrosilicofluoric acid solution which is
supersaturated with silicon dioxide and contains a
dyestuff or pigment; wherein said primary film is
formed by coating and curing a mixture containing:
a silicon compound having methacryloxy group
represented by general formula (VI):

R11Si(R12)3 (VI)


wherein R11 designates organic group
containing methacryloxy group and R12
designates at least one member selected from
the group consisting of alkoxy group,
alkoxyalkoxy group, acetoxy group and
chlorine; and



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a hydrolyzate of a silicon compound
represented by formula (VII):

Si(R13)4 (VII)


wherein R13 designates at least one member
selected from the group consisting of alkoxy
group, alkoxyalkoxy group, acetoxy group and
chlorine;
wherein the mixture includes the silicon
compound (VI) and the hydrolyzate of the silicon
compound (VII) so that the ratio between the weight
(A) converted into R11SiO3/2 from the silicon compound
(VI) and the weight (B) converted into SiO2 from the
silicon compound (VII) satisfies the relationship of
0.1<B/A<0.5.
12. A method for coloring an acrylic resin
substrate according to Claim 11 wherein said acrylic
resin substrate has a number-average molecular weight
of not more than 80,000.
13. A method for coloring an acrylic resin
substrate according to Claim 11 or 12 wherein said
primary film is formed on a condition which forms 5 to
50 nm thickness film on a glass substrate if the
condition is applied thereto.
14. A method for coloring an acrylic resin
structure according to Claim 11, 12 or 13 wherein said
primary film is formed by application of a coating
liquid containing 0.3 to 3% by weight of the silicon
compound.
15. A method for coloring an acrylic resin
substrate according to any of Claims 11 to 14 wherein




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said hydrosilicofluoric acid solution supersaturated
with silicon dioxide is prepared by adding an additive
which is able to react with fluorine ions to a
hydrosilicofluoric acid solution saturated with
dissolved silicon dioxide for supersaturation with
silicon dioxide.
16. A method for coloring an acrylic resin
substrate according to any of Claims 11 to 14 wherein
said solution supersaturated with silicon dioxide is
provided by means of supersaturation with silicon
dioxide which is dissolved at a low temperature for
saturation and then, heated and kept at a high
temperature.
17. A method for coloring an acrylic resin
substrate according to any of Claims 11 to 14 wherein
said organic colorant to be added to the
hydrosilicofluoric acid solution supersaturated with
silicon dioxide is provided in the form of a water
solution or dissolved in a water soluble organic
solvent.
18. A coloring method for polycarbonate
substrate comprising the steps of:
(i) forming a primary film by coating and
curing an organic silicon compound on the
polycarbonate substrate; and
(ii) forming a secondary film of silicon
dioxide containing organic colorant on the primary
film by contacting the substrate with a
hydrosilicofluoric acid solution which is
supersaturated with silicon dioxide and contains a
dyestuff or pigment; wherein said primary film is
formed by coating and curing a mixture containing:


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at least one silicon compound selected from
the group consisting of a silicon compound and a
hydrolyzate thereof, the silicon compound being
represented by general formula (VIII):
R21 n Si (R22)4-n (VIII)
wherein R21 designates either hydrocarbon
group having not more than 2 carbon atoms or organic
group having not more than 3 carbon atoms containing
mercapto group or hydroxyl group, R22 designates at
least one member selected from the group consisting of
alkoxy group, alkoxyalkoxy group, acetoxy group and
chlorine, and n designates 0 or 1; and
a silicon compound containing amino group;
wherein the content of the silicon compound
containing amino group is not less than 0.2% by weight
and the concentration of total silicon compound is not
more than 5% by weight.
19. A method for coloring a polycarbonate
substrate according to Claim 18 wherein said primary
film is formed on a condition which forms of 5 to 100
nm thickness film on a glass substrate if the
condition is applied thereto.
20. A method for coloring a polycarbonate
substrate according to Claim 18 or 19 wherein one or
two of said silicon compound(s) containing amino group
is/are selected from a group consisting of
.gamma.-aminopropyltriethoxysilane, N-(.beta.-aminoethyl)-.gamma.-
aminopropyltrimethoxysilane and N- (.beta.-aminoethyl)-.gamma.-
aminopropyldimethoxysilane.



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21. A method for coloring a polycarbonate
substrate according to Claim 18, 19 or 20 wherein said
hydrosilicofluoric acid solution supersaturated with
silicon dioxide is prepared by adding an additive
which is able to react with fluorine ions to a
hydrosilicofluoric acid solution saturated with
dissolved silicon dioxide for supersaturation with
silicon dioxide.
22. A method for coloring a polycarbonate
substrate according to Claim 18, 19 or 20 wherein said
solution supersaturated with silicon dioxide is
provided by means of supersaturation with silicon
dioxide which is dissolved at a low temperature for
saturation and then, heated and kept at a high
temperature.
23. A method for coloring a polycarbonate
substrate according to any of Claims 18 to 22 wherein
said organic colorant to be added to the
hydrosilicofluoric acid solution supersaturated with
silicon dioxide is provided in the form of a water
solution or dissolved in a water soluable organic
solvent.
24. A colored product comprising a
substrate and a colored layer formed on said
substrate, said colored layer being a silicon dioxide
film containing an organic colorant formed by a
process which comprises bringing said substrate into
contact with an aqueous solution of hydrosilicofluoric
acid supersaturated with silicon dioxide and
containing the organic colorant, thereby depositing
said silicon dioxide film containing the organic
colorant onto said substrate.


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25. The colored product of Claim 24,
wherein said organic colorant is a water-soluble or
water-dispersible dyestuff or pigment.
26. The colored product of Claim 24 or 25,
wherein said substrate is a member selected from the
group consisting of a particulate material, a
transparent material, a metallic material and a
plastic material.
27. The colored product of Claim 24 or 25,
wherein said substrate is a particulate material
selected from the group consisting of an inorganic
powder, an organic powder, a powder of a thermoplastic
or thermosetting resin and glass particles.
28. The colored product of Claim 24 or 25,
wherein said substrate is a glass sheet, and said
colored layer is formed on at least one surface of
said substrate.
29. The colored product of Claim 28,
wherein said glass sheet is a member selected from the
group consisting of a flat glass sheet, a glass sheet
having an uneven surface, a figured glass, and a glass
sheet having a roughed surface formed by chemical
etching or mechanical grinding.
30. The colored product of Claim 24 or 25,
wherein said substrate is a cover glass for use in
watches and clocks, and said colored layer is formed
on at least one surface of said substrate.
31. The colored product of Claim 24 or 25,
wherein said substrate is a transparent sheet and said
colored layer is composed of red fine stripes, green
fine stripes and blue fine stripes arranged in a
repeated pattern of the red stripe, green stripe and


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blue stripe, and which is suitable as a color filter
for use in a display device.
32. The colored product of Claim 31,
wherein said transparent sheet is a glass sheet.
33. The colored product of Claim 24 or 25,
wherein said substrate is a transparent sheet, and
which includes a metal film formed on said colored
layer.
34. The colored product of Claim 33,
wherein said transparent sheet is a glass or plastic
sheet of a flat, convex or concave shape.
35. The colored product of Claim 33 or 34,
wherein said colored layer formed between said
transparent sheet and said metal film is in the form
of a letter, a figure or a pattern.
36. The colored product of Claim 24 or 25,
wherein said substrate is a metallic material having a
film of an inorganic compound on which said colored
layer is formed.
37. The colored product of Claim 36,
wherein said metallic material is a non-metallic
material having a metallic layer on its surface.
38. The colored product of Claim 36 or 37,
wherein said inorganic compound is a member selected
from the group consisting of a metal oxide and an
inorganic compound containing silicon.
39. The colored product of Claim 36, 37 or
38, wherein said film of inorganic compound is a film
of a composite material composed of an organic



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compound and an inorganic compound dispersed in said
organic compound.
40. The colored product of Claim 24 or 25,
wherein said substrate is a plastic material having a
film of a silicon compound selected from the group
consisting of an organic silicon compound of the
formula (I)
R1 n Si(R2)4-n (I)
wherein R1 is an organic group containing a
group selected from a hydrocarbon group having 1 to 6
carbon atoms, vinyl group, methacryloyoxy group, epoxy
group, amino group, mercapto group, fluorine and
chlorine, and R2 is the same or different and each is
an alkoxy group, an alkoxyalkoxy group, acetoxy group
or chlorine, and n is 0 or an integer of 1 to 4; a
hydrolyzate of the silicon compound (I); and colloidal
silica.

Description

- 1 -
METHOD FOR MANUFACTURING LAYER-BUILT MATERIAL WITH
SILICON DIOXIDE FILM CONTAINING ORGANIC COLORANT
AND THE LAYER-BUILT MATERIAL MANUFACTURED THEREBY
BACKGROUND OF THE INVENTION
The present invention relates to a method of
manufacturing a layer-built material in which a silicon
dioxide film containing an organic colorant is formed on
a substrate, and to the layer-built material manufactured
thereby.
As a means for acquiring a material having new
functional feature, it is already attempted to introduce
ari organic colorant to a silicon dioxide film. However,
organic colorants are easily decomposed when being
exposed to high temperatures and, therefore, a so-called
sol-gel method is the only method conventionally
practiced for producing such material featuring new
functional characteristic. Typically a technical paper
1S "J. Non-Crys. Solids, 74 (1985), 395" refers to this
method in which a fluorescent organic colorant is
introduced to silicon dioxide film. This prior art
reports to have merely produced a porous film containing
organic colorant. Another technical paper "Ceramics, 21,
No. 2, 1986, 111" proposes the doping of organic
molecules into non-crystal quartz by sol-gel method. It
is reported that residual impurities, distortion, defects
and the like are present in the structure of the produced
glass.
Any of those prior arts use the sol-gel method,
and as a result, in order to securely fix the film to the
substrate, heating must be executed in the final stage of
the production process. However, since the film on the
substrate cannot be heated at such a high temperature as
3a causing the organic colorant to decompose, the resultant
film unavoidably becomes porous. Furthermore, organic
colorants easily decomposable by heating at a low
temperature cannot be used in this method. Heating which
is obliged to conduct at a low temperature raises further



- 2 -
problems inherent to the sol-gel method, for example,
generation of residual impurities in the structure of
film such as some amounts of undecomposed raw material
and organic solvent. These prior arts cited above
commonly involves another problem of expensive cost of
film because expensive metal alkoxide is used as the
starting material. Furthermore, dip--coating employed by
those prior arts cannot effectively be applied to
substrates having complex form.
The primary abject of the invention is to
provide a novel method of manufacturing a silicon dioxide
film containing an organic colorant which is perfectly
free from those defects inherent to any conventional
method of manufacturing silicon dioxide film containing
organic colorant.
The term "organic colorant" as used herein
means a concept broad enough to include those capable of
developing color by any effective treatment.
The first embodiment of the invention relates
to a method of dyeing a molded organic material. More
particularly, it relates to a method of forming a colored
layer featuring surpassing chemical and mechanical
durability on the surface of molded organic material
shaped in those forms such as plane sheet, film, rod,
tube, sphere, fiber, web, and a variety of processed
forms.
Conventionally, the molded organic material is
colored merely by adding colorant to the organic material
in the course of synthesizing the moldable material. For
example, when coloring moldable resin, any of those
colorants such as inorganic pigment, or organic pigment,
or dyestuff, is blended with resin, and then pasted,
uniformly dispersed in the resin, which is then
polymerized and cured before eventually being molded:
However, the method of blending colorant with moldable
organic material is subject to-restriction against
molding temperature of resin, polymerizing and curing




~~~~~3~~
- 3 -
condition, and crosslinking condition caused by weak heat
resistivity of the organic colorant and has a problem
against the weatherability in exposure to air and
water. T_n addition, there is a certain limit caused by
inability to locally color on the moldable object.
To dispose of those problems, in addition to
the method of blending colorant with moldable organic
material. mentioned above, conventionally, either printing
or dyeing process is used for coloring on the surface of
the moldable organic material. Printing is performed by
causing color ink composed of either inorganic pigment,
or organic pigment, or dyestuff, to be absorbed into the
moldable organic material. Printing process locally
colors the molded substrate, and in addition, there are a
variety of kinds of colors available for coloring the
molded substrate. However, adhesive strength of colorant
contained in ink for molded substrate having smooth
surface is weak, so that ink film often exfoliates.
Furthermore, since the surface of molded substrate does
not absorb ink vehicle, it is necessary that vaporization
of organic solvent is promoted by heating: Nevertheless,
since heating process at a high temperature cannot be
applied, organic solvent may remain on the printed
surface to result in the occurrence of odor and blocking
(i.e., adhesion of the printed substrates).
On the other hand, dyeing is mainly used for
coloring fibers by causing colorant mainly consisting of
dyestuff to be absorbed into fibers. In case of dyeing
fibers, in order to promote the bonding force between
dyestuff and fibers, it is necessary to carefully select
dyestuff, auxiliary agents; and paragenic ion and the
like in accordance with fibers; so that dyeing process
becomes extremely complex.
Furthermore, printing and dyeing have common
problems. Colorant is directly exposed to external
atmosphere, and as a result, oxygen and moisture in
atmosphere easily causes oxidation and hydrolysis to
occur. In addition, rendering symptom may also be


generated due to presence of water, organic solvent, and
a variety of chemicals. Also, dyed fibers may
mechanically be worn or damaged, so that local
degradation of the colored effect or local discoloration
often occurs.
The primary object of the first embodiment of
the invention is to fully eliminate those defects
inherent to the printing and dyeing processes mentioned
above by providing an improved coloring or dyeing method
which is capable of securely forming a colored layer on
the surface of the molded organic substrate and features
surpassing chemical and mechanical durability.
More particularly, the invented method
dispenses with the condition of causing the colorant to
be exposed to the external atmosphere directly while
either the printing or the dyeing is underway, and the
invented method prevents the colorant from reacting water
and organic solvent by virtue of the protective effect of
silicon dioxide film, thus securely promoting the
weatherability of the colored layer. Furthermore, by
virtue of surpassing durability of silicon dioxide
against wear, the durability against mechanical wear is
also promoted. Since the improved method of the first
embodiment of invention provides organic silicon compound
(coupling agent) between silicon dioxide containing
colorant and the molded organic substrate, the bonding
force between the colored layer and the molded organic
substrate is intensified.
As is clear from the above description, the
object of the first embodiment of the invention is to
provide a colored layer which has extremely intense
bonding force on the surface of the molded organic
substrate and the chemically and mechanically stable
resistivity by initially forming a film of organic
silicon compound (coupling agent) before eventually
generating silicon dioxide film containing colorant.
The second embodiment o~ the invention relates



2 ~i ::~: ~ ~~
- 5 -
to a method of coloring acrylic resin molded substrate.
More particularly, it relates to a method of forming a
chemically and mechanically durable colored layer on the
surface of the molded acrylic resin shaped in those forms
such as plane sheet, film sheet, rod, tube, sphere,
fiber, web, and a variety of processed forms.
Conventionally, colorant is added to the molded
acrylic resin in the course of synthesizing the moldable
material. For example, when coloring molded resinous
material, any of those coloring agents such as inorganic
pigment or organic pigment, or dyestuff, is blended with
resin, which is then pasted, and then uniformly dispersed
in the resin material, which is then polymerized and
cured before eventually being molded. However, the
method of blending colorant with moldable acrylic resin
is subject to restriction against molding temperature of
resin, polymerizing and curing condition and crosslinking
condition caused by weak heat resistivity of the organic
colorant, and has a problem against the~weatherability in
exposure to air and caater. In addition, there is a
certain limit when using colorant caused by inability to
locally develop color on the moldable material.
To dispose of those problems, in addiEion to
the method of blending colorant with moldable acrylic
resin mentioned above, conventionally, either printing or
dyeing process is widely used for coloring on the surface
of the moldable acrylic resin. Printing is performed by
causing color ink composed of either inorganic pigment or
organic pigment, or dyestuff, to be absorbed into the
moldable organic material surface. Printing allows the
molded substrate to be colored locally, and in addition,
there are a variety of kinds of colors available for
coloring. However, adhesive strength of cplorant
contained in ink for molded substrate having smooth
surface is weak, so that ink film often exfoliates.
Furthermore,. since the surface of the rnolded resin does
not absorb ink vehicle, it is necessary that
vapourization of solvent is promoted by the heating.




2~~~~~
- 6 -
Nevertheless, since the heating process at a high
temperature cannot be applied, organic solvent may remain
op the printed surface to result in the occurrence of
odor and blocking (i.e., adhesion of the printed
substrates).
On the other hand, dyeing is mainly used for
coloring fibers by causing colorant mainly consisting of
dyestuff to be absorbed into fibers. When dyeing fibers,
in order to promote the bonding force between dyestuff
and fibers, it is necessary to carefully select dyestuff,
auxiliary agents, and paragenic ion, and the like in
accordance with fibers, so that dyeing process becomes
extremely complex.
Furthermore, printing and dyeing have common
problems. Colorant is directly exposed to external
atmosphere, and as a result, oxygen and moisture in
atmosphere easily causes oxidation and hydrolysis to
occur. In addition, rendering symptom may also be
generated due to presence of water, organic solvent, and
a variety of chemicals. Also, dyed fibers may
mechanically be worn or damaged, so that local
degradation of the colored effect or local discoloration
often occur.
The object of the second embodiment of the
invention is to fully eliminate those defects inherent to
the printing and dyeing processes mentioned above by
providing an improved coloring or dyeing method which is
capable of securely forming colored layer on the surface
of molded acrylic resin and features surpassing chemical
and mechanical durability. '_
More particularly, the invented method
dispenses with the condition of causing the colorant to
be exposed to the external atmosphere directly while
either the printing or the dyeing process is underway,
and the invented method prevents the colorant from
reacting water and organic solvent by virtue of the
protective effect of silicon dioxide film, thus securely
promoting the weatherability of the colored layer.




Furthermore, by virtue of surpassing durability of
silicon dioxide against wear, the durability against
mechanical wear is also promoted. Since the improved
method provides organic silicon compound (coupling agent)
between silicon dioxide containing colorant and the
molded acrylic resin, the bonding force between the
colored layer and the molded acrylic resin is
intensified.
As is clear from the above description, the
object of the second embodiment of the invention is to
provide a colored layer which has extremely intense
bonding force on the surface of the molded acrylic resin
and the chemically and mechanically stable resistivity
against wear by initially forming a film of organic
silicon compound (coupling agent) before eventually
generating silicon dioxide film containing colorant.
The third embodiment of the invention relates
to a method of coloring polycarbonate resin molded
substrates. More particularly, it relates to the method
of forming a chemically and mechanically durable colored
layer on the surface of the molded polycarbonate resin
shaped in those forms like plane sheet, film, rod, tube,
sphere, fiber, web, and a variety of processed forms.
Conventionally, colorant is added to the molded
polycarbonate resin in the course of synthesizing the
moldable material. For example, when coloring molded
resinous material, any of those coloring agents like
inorganic pigment or organic pigment, or dyestuff, is
blended with resin, which is then pasted, and then
uniformly dispersed in the resin material, which is then
polymerized and cured before eventually being molded.
However, the method of blending colorant with moldable
polycarbonate resin is subject to restriction against
molding temperature of resin, polymerizing and curing
condition, and crosslinking,condition caused by weak heat
resistivity of the organic colorant, and has a problem
against the weatherability in exposure to air and




water. In addition, there is a certain limit when using
colorant caused by inability to locally develop color on
the moldable material.
To dispose of those problems, in addition to
the method of blending colorant with moldable
polycarbonate resin mentioned above, conventionally,
either printing or dyeing process is widely used for
developing color on the surface of the moldable
polycarbonate resin. Printing is performed by causing
color ink composed of either inorganic pigment, organic
pigment, or dyestuff, to be absorbed into the moldable
organic material surface. Printing allows the molded
substrate to be colored locally, and in addition, there
are a variety of kinds of colors available for
coloring. However, adhesion strength of colorant
contained in ink for mold substrate having smooth surface
is weak, so that ink film often exfoliates. Furthermore,
since the surface of the molded resin does not absorb ink
vehicle, it is necessary that vapourization of solvent be
promoted by the heating. Nevertheless, since the heating
process at a high temperature cannot be applied, organic
solvent may remain on the printed surface to result in
the occurrence of odor and blocking (i.e., adhesion of
the printed substrates).
On the other hand, dyeing is mainly used for
coloring fibers by causing colorant mainly consisting of
dyestuff to be absorbed into fibers. When dyeing fibers,
in order to promote the bonding force between dyestuff
and fibers, it is necessary to carefully select dyestuff,
auxiliary agents, and paragenic ion, and the like in
accordance with fibers, so that dyeing process becomes
extremely complex.
Furthermore; printing and dyeing have common
problems.' Colorant is directly exposed to external
atmosphere, and as a result, oxygen and moisture in
atmosphere easily causes oxidation and hydrolysis to
occur. In addition, rendering symptom may also be
generated due to presence of wa er, organic solvent, and




a variety of chemicals. Also, dyed fibers may
mechanically be worn or damaged, so that local
degradation of the colored effect or local discoloration
often occurs.
The object of the third embodiment of the
invention is to fully eliminate those defects inherent to
the printing and dyeing processes mentioned above by
providing an improved coloring or dyeing method which is
capable of securely forming colored layer on the surface
of molded polycarbonate resin and features surpassing
chemical and mechanical durability.
More particularly, the invented method
dispenses with the condition of causing the colorant to
be exposed to the external atmosphere directly while
either the printing or the dyeing is underway, and the
invented method prevents the colorant from reacting water
and organic solvent by virtue of the protective effect of
silicon dioxide film, thus securely promoting the
weatherability of the colored layer. Furthermore, by
virtue of surpassing durability of silicon dioxide
against wear, the durability against mechanical wear is
also promoted. Since the improved method of the third
embodiment of the invention provides organic silicon
compound (coupling agent) between silicon dioxide
containing colorant and the molded polycarbonate resin,
the bonding force between the colored layer and the
molded polycarbonate resin is intensified.
As is clear from the above description, the
object of the third embodiment of the invention is to '
provide a colored layer which has extremely intense
bonding force on the surface of the molded polycarbonate
resin and the chemically and mechanically stable
resistivity against wear by initially forming a film of
organic silicon compound (coupling agent) before
eventually generating silicon dioxide film containing
colorant.
The fourth embodiment of the invention relates




- l0 -
BSI ~fi.f~-f'
to coloring pigments which form a colored layer on the
surface of pulverulent body. More particularly, it
relates to a coloring pigments which form silicon dioxide
film containing organic colorant on the surface of
pulverulent body and features surpassing chemical and
mechanical durability.
Today, important role of pigment sharply
increases as versatile colorant for the production of
paint, printing ink, cosmetics, synthetic resin, and
conventional goods in a variety of fields.
Pigment consists of inorganic pigment made from
inorganic material and organic pigment made from organic
material. Most of inorganic pigments are chemically
stable and harmless, which are extensively used for the
production of paint, printing ink, cosmetics, and
construction materials.
On the other hand, only limited kinds of
inorganic pigments are available today. zn particular,
the inorganic pigment lacks in the color brilliancy. As
a result, in many cases, organic pigments are unavoidably
used for the production of those fields of goods
critically requiring color characteristic, for example,
makeup cosmetics including lip stick and nail enamel for
the point makeup, or image printing ink. Although
organic pigments feature a wide variety of the kinds of
color and brilliancy of color, majority of them are based
on tarry ingredient. Because of potential hazard against
human health like skin disease, carcinogenic potential,
or mutation, strict regulation is legahly applied to the
use of organic pigments. And therefore, there is
substantial restriction over the use of organic pigments
today.
To deal with those problems cited above, a wide
variety of attempts such as coating the surface of
organic pigment completely with inorganic material and
sealing organic pigment inside of extremely fine
inorganic capsules were tried. Nevertheless, in strict .
sense, such protective layer made from inorganicvmaterial


11 -
consists of crusted structure composed of porous or
extremely fine colloid, so that the protective layer
cited above cannot fully prevent organic pigment from
coming into contact with water, solvent, and oxygen.
More particularly, there is no practical means
to safely materialize such chemically stable pigments
featuring a caide variety of available colors and color
brilliancy.
The object of the fourth embodiment of the
invention is to fully solve those problems inherent to
conventional coloring pigments by forming silicon dioxide
film containing organic colorant all over the surface of
inorganic or organic pulverulent body so that stability
and safety of this film comparable to those of inorganic
pigments can be achieved while securing abundant kinds
and brilliancy of colors characteristic of organic
pigments.
The fifth embodiment of the invention relates
to a color filter necessary for a light-receptive display
device like liquid crystal display (LCD). More
particularly, it relates to a.color filter which features
surpassing chemical and mechanical durability and is
provided with the color layers of red, green, and blue
composed of silicon dioxide film containing organic
colorant.
As a result of significant development achieved
in the information/communication fields, display device
shares extremely important roles. Accordingly, there are
a variety of sophisticated demands on the display
technique to materialize light weight, slim'structure,
wider area, coloration, and finer image for the display
device. In particular, there is a growing expectation on
the LCD which has achieved significant technological
progress in late years. Above all, there i.s an ardent
expectation on the liquid crystal color display like a
color TV for example. To suffice the demand; a variety
of arts related to the color liquid crystal display have




- 12 -
already been proposed.
Today, majority of the colored liquid crystal
display devices incorporate color filters which at
regular intervals set fine color layers of red (R), green
(G), and blue (B) in the order of RGB, RGB ... . In
order to select any of these RGB colors at a specific
display position, shutter function of liquid crystals
operating in correspondence with extremely fine areas of
the RGB colors is used.
At present, some methods have been tried for
the production of the color filter cited above. One of
these methods directly coats the three-color inks over
the surface of glass by applying the offset or screen
printing process for each color fox three rounds.
Despite of simple process, precision of the printed
pattern is critical problem. Furthermore, ink thickness
becomes thick in the portion where these three-color inks
are superimposed. As a result, the ink. surface easily
generates concaves and convexes. To level off the
surface, leveling operation is necessary. Normally,
surface smoothening operation is necessarily performed by
coating, for example, polyimide resin film over the
surface coated with R, G, and B inks. Conventionally,
printing ink is composed of the blend of organic solvent
like "cellosolve" and colorant like organic colorant and
pigment. Also, leveling agent is composed of organic
material. After completing the smoothening operation,
transparent electrodes composed of indium oxide/zinc
indium (ITO), film, for example, are provided under
3~ vacuum condition. While forming, his film, organic
material arises problems such as long time pressure
reduction operation caused by discharge gas from the
material, and difficulty of obtaining satisfactory ITO
film. To dispose of this problem, there is another
method which initially forms silicon dioxide film on the
surface of the leveling agent by applying sputtering
process before eventually generating the ITO film.
The secondary method coats photopolymer




rr
- 13 -
containing organic colorant over the ink surface by
applying photoresist process. For example, ink surface
is initially masked by the photoresist process except for
the red-ink portion, and then, photopolymer containing
red colorant is coated over the red segment, and finally,
photopolymer is optically cured before a red filter is
eventually formed. Next, masking agent is removed, and
then, by repeating those sequential processes against the
green and blue segments as is done for the red segment
before a color filter is eventually produced.
The above method involves a number of processes
because delicate operation like the photoresist process
must be performed repeatedly with much care. On the
other hand, advantage of this method is that extremely
precise pattern is obtained. However, even when applying
this method with the photoresist process, the surface of
the colorant applied to the red, green, and blue
components becomes unlevel to a certain extent, so that,
after executing this method, the leveling process is
required. Furthermore, as was done for the printing
process, since the photopolymer and the leveling agent
are respectively composed of organic material, after
completing the leveling process, it is necessary that
silicon dioxide film is formed in the final stage.
~'he third method preliminarily forms patterned
ITO film on the transparent substrate in correspondence
with the red, green and blue components, and then
immerses the substrate in aqueous solution containing
dispersed organic pigments. Next, DC voltage is supplied
between opposite electrodes like graphite electrodes and
the red segment on the surface of the substrate in the
aqueous solution to allow only the red organic pigment
(having colloidal electric charge in this solution) to be
laid on the surface of the red segment. Next, green
organic pigment is laid on the surface of the ITO film of
green segment by supplying-DC voltage between those
opposite electrodes and the ITO film of the green segment
in aqueous solution containing dispersed green organic



~,~:~~ ~°~~~
- 14 -
pigment. These serial processes are also executed
against the blue segment. Even in this method, after
completing those sequential processes mentioned above, it
is necessary that the leveling process is performed
before eventually forming the silicon dioxide film as was
done for the first and second methods mentioned earlier.
As is clear from the above description, any of
those methods attempted needs to individually perform
coating processes for the red, green, and blue segments,
and yet, since the leveling process for leveling uneven
thickness of film after completing the coating process
solely uses organic material like organic colorant and
organic leveling agent, any of those methods cited the
above needs to form silicon dioxide film in order to
restrain discharge of gas in presence of vaccum. Above
all, too many steps and the complexity of these processes
are critical problems to solve for reducing the
production cost. Thus, an early renovation of these
methods cited the above is urged today.
The fifth embodiment of the invention has been
achieved to fully solve those problems related to color
filters. The object of the fifth embodiment of the
invention is to dispense with the process for forming
silicon dioxide film thus far needed for restraining
discharge of gas under vacuum condition and also
eliminate the leveling process by providing a novel means '
for forming silicon dioxide film containing organic
colorant.
The sixth embodiment of the invention relates
to a colored mirror composed of a colored layer which is
formed on the surface of a transparent substrate. More
particularly, it relates to a colored mirror featuring
surpassing durability against chemical and mechanical
wear, where the colored mirror is composed of silicon
dioxide film containing organic colorant on the surface
of a transparent substrate.
From those old days, there is a constant demand


~~_~. ~ ~~v
- 15 -
for such a colored mirror to enhance the decorative
effect. Recently, there is an idea of applying the
colored mirror to the filter mirror by availing of the
effect of the increase and decrease of reflection rate in
the specific wave length band shown in the spectrum of
the colored mirror.
When using the colored mirror for decorative
purpose, coloration is performed by either coloring the
transparent substrate itself or forming the colored layer
on the transparent substrate. rn the method, basically,
coloration of the transparent substrate is performed by
blending colorant with the substrate material, although
there is difference in the colored effect depending on
the kinds of material available for the substrate. For
example, trial coloration of glass substrate was executed
by blending inorganic colorant with the substrate
material while the glass production process was
underway. Also, trial coloration of plastic substrate
was executed by blending colorant such as organic
dyestuff or organic pigment with resinous material while
the plastic molding process was undexway.
Nevertheless, there were a variety of
restrictive factors in the coloration of glass substrate
using inorganic colorant, where the restrictive factors
were found in the limited kinds of colors for use,
absence of color brilliancy, inability of coloration
against part of the substrate, etc. On the other hand,
although there are a wide variety of colors having
satisfactory brilliancy available for coloring resinous
material containing organic colorant, the colored plastic
substrate still has problem common to organic materials,
where the problem is found in the shortage of chemical
durability against water and oxygen which respectively
infiltrate into the plastic substrate , shortage of
physical durability against ultraviolet rays, and
inability to implement local decoration. As a result,
like the coloration of glass substrate; there is
substantial restriction over the application of the



- 16 -
method of coloring plastic substrate.
To dispose of this problem, a method of forming
metallic film over the colored layer preliminarily formed
on the surface of the transparent substrate has widely
been introduced. Although this method allows local
coloration, like the case of coloring the glass substrate
mentioned above, there is a certain limit in the kinds
and brilliancy of available colors. (When producing
glass substrate, generally, colored layer is formed with
inorganic colorant like the case of providing colored
luster.) As a result, trials are still underway fox
forming organic colored layer over the surface of plastic
substrate. Nevertheless, since organic colorant is
present in the surface layer of plastic substrate,
durability and weatherability are more critical problems
than the coloration of the plastic substrate itself.
Furthermore, the filter mirror generally
requires not less than three layers, so that it arises
such problems as difficulty of applying to large scale
substrates because of troublesome film thickness control
and high production cost brought by many production
steps.
The sixth embodiment of the invention has been
achieved to fully solve those problems related to the
conventional colored mirrors. The object of the sixth
embodiment of the invention is to provide a novel colored
mirror featuring extremely high durability and
weatherability, availability of a wide variety of colors,
brilliancy of colors, and the local coloration
capability, by providing novel silicon dioxide film
containing organic colorant on the surface of transparent
substrate.
The seventh embodiment of the invention relates
to a glass composed of colored layer coated on a glass
substrate having unlevel surface. More particularly, it
relates to a colored glass having enhanced decorative
function by forming novel silicon dioxide film containing




s f.
- 17 -
organic colorant on the unlevel surface of the glass
substrate.
In order to promote decorative function of
glass, template glass having figurative patterned unlevel
surface has been used since old days. Furthermore, in
order to promote glare-proof effect and restrain
transparency of glass, an art of roughing the glass
surface has widely been made available. For example,
ground glass having the surface ground with a metallic
brush is exemplified. In addition, there is such an art
of roughing the glass surface by applying sand-blast
process and an art of etching the glass surface by
applying a sort of hydrofluoric acid solution. Tn this
way, glass having unlevel surface is widely used for a
variety of purposes like for decoration, restraining
transparency, and for achieving glaze-proof effect.
Recently, a variety of trials are actively
carried on to promote decorative effect and appearance by
coloring those kinds of glass mentioned above so that
more comfortable living space can be materialized.
Mainly, two methods are experimentally performed to color
glass having unlevel surface. One is an art which varies
the composition of glass before being colored. For
example, oxide composed of transition metal like cobalt,
nickel, iron, or chrome, is added to glass material so
that the glass material can be colored by the ionized
effect of those metallic elements mentioned the above.
While the colored glass material still remains in the
softened state during molding; a pattern on the glass '
surface is engraved using a roll bearing figurative
unlevel pattern before eventually producing template
glass. Nevertheless, only those cold colors including
blue, green, yellow, and gray can be used for developing
color when applying the above method. Furthermore, there
are only limited kinds of colors available for this
method. Above all, since glass material containing
colorant is dissolved in the glass furnace, this method
is not suited for producing a variety of kinds of colored




~;
- 18 -
glass in small production lots. To dispose of these
problems, another method was tried for forming
transparent layer on unlevel surface of glass. A thermal
discomposition method, as is typically represented by
luster for example, wherein the glass initially coated
with organic solvent solution containing organic metal
compound and precious metal compound, and then applied
heat treatment between 450°C and 550°C. A still another
method was also attempted by initially coating paste
containing precious metal compound of gold, silver, and
copper on the plane glass, followed by thermal treatment
between 500°C and 600°C, and impregnation of precious
metal elements into glass by ion-exchange process before
eventually developing color.
Any of those methods cited above utilizes color
development of metallic colloid. Thermal decomposition
method causes precious metal colloid to,be generated in
metal oxide, whereas ion-exchange method causes precious
metal colloid to be generated on the glass surface
layer. Nevertheless, any of these methods merely uses
limited kinds of colors effective for development, and
yet, only those cold colors cited above are applicable.
Above all, a critical problem of any of these methods
like spraying or immersing process is that colored layer
having uniform thickness cannot be formed because of the
unlevel glass surface. Tn other words, any of these
methods cannot practically be used because the colored
effect is significantly uneven.
The seventh embodiment of the invention has
been achieved to fully solve those problems inherent to
the art of calored glass having unlevel Surface. The
object of the seventh embodiment of the invention is to
provide such colored glass free from those problems '
mentioned the above, where the colored glass provided by
the seventh embodiment of the invention has Chemically
and mechanically stable colored layer by applying a wide
variety of available colors and brilliancy of these
colors characteristic of organic colorant by allowing



~~~. 9 a~~
- 19 -
novel silicon dioxide film containing organic colorant to
stably be formed on the glass surface.
The eighth embodiment of the invention relates
to metallic substrate which is complete with coloration
process. More particularly, it relates to such metallic
substrate which is provided with colored layer featuring
surpassing durability and decorative effect by forming
novel silicon dioxide film containing organic colorant an
its surface.
To enhance decorative effect of any metallic
substrate, conventionally, colored layer has been formed
on its surface since old days. For example, the chemical
coloration process represented by the black-dyeing method
immerses the metallic substrate in aqueous solution
containing potassium sulfide or potassium persulfate for
sulfuration or oxidation of the metallic surface so that
the blackening characteristic of the sulfurated or
oxidized layer can be used: This method is applicable to
such metallic substance like copper, iron, and
aluminium. However, this method is not always widely
applicable, and yet, only black is available fox
development. To compensate for this, anode oxidation
method is widely applied today, which is effective for
such metal like stainless steel that cannot be colored
merely by applying chemical coloration process. Anode
treatment of aluminium is the typical example of the
anode oxidation method, where aluminium can be colored by
contacting the aluminium with solvent containing organic
dyestuff, although the oxidized layer formed is porous
and colorless.
In addition, although porous colored layer can
be formed on theasurface of metallic substrate by
treatment with phosphate or chromate; only limited number
of the kinds of color are applicable, and therefore, only
organic dyestuffs are unavoidably used. However,
coloring the metal substrate with porous layer,
containing colorant, formed by anode oxidation process or




r ~r
~~~~z~~
- 20 -
chemical treatment has drawbacks°.
most of the formed layers are opaque so that metal
surface becomes invisible;
coloring process is complex since sealing process for
pinholes is required after impregnating these pinholes
with dyestuff; and
dyestuffs are easily disgraded and discolored by water
infiltrating through sealing wall. In addition, metallic
substrates which can be applied to by the above-mentioned
treatment are limited. As a result, it is difficult to
adopt the above=mentioned method as a universal method.
To replace those methods cited above, another
method was also tried. This method colors the metal
surface by generating eutectoid of metallic particles and
molecules of organic and inorganic pigments by applying
dispersion plating process. Also in this case, there is
a restriction in practical application since the coated
layer becomes too thick for the metal surface to be seen, .
and insufficient acidproof of the eutoctoid-applied
metallic particle.
As mentioned above, although it was the
important target for the concerned to properly coat the
metal surface with optional colors during the past years,
actually, there was no art that could satisfy this
requirement because of a variety of problems in the kinds
of available colors, kinds of usable metals, and the
durability of colored layer.
The object of the eighth embodiment of the
invention is to provide novel metallic substrate which
fully solves those problems found in any of these prior
arts.
The ninth embodiment of the invention relates
to a glass covering clock sand/or wrist watches. More
particularly, it relates to a colored glass covering
clocks and/or wrist watches, which features provision of
sufficiently strengthened glass covering with transparent
layer on the surface.



- 21 -
To enhance decorative function of clocks and
wrist watches, a variety of trials were carried out for
coloring the covering glass since old days. One of these
methods is to blend the glass material with oxide of
transition metal like cobalt, nickel, iron, and chrome so
that glass material can be colored by ionized effect of
these metallic elements. Nevertheless, this method can
merely use those limited kinds of cold colors including
blue, green, yellow, and gray for development, and yet,
there are only limited kinds of colors available for this
method. In particular, since glass material containing
colorant is dissolved in the glass furnace, this method
is not suited for producing a variety of kinds of
clock/watch covering glass in small production lots. To
dispose of this problem, another method was tried, in
which initially transparent colored layer on plane glass
was formed, and then, thermal treatment was applied
before eventually performing molding process. To form a
colored layer, as typically shown by luster, thermal
decomposition method wherein a plane glass is coated with
organic solvent solution containing organic metal
compound and precious metal compound, and then they are
applied with thermal treatment between 450°C and 550°C.
Another method was also tried, which initially coated the
plane glass with paste containing precious metal compound
like gold, silver, or copper, and then it was applied
with thermal treatment between 500°C and 600°C, and then
precious metal element was impregnated into the glass by
applying ion-exchange process before eventually
developing color.
Any of those preceding methods effectively uses
color development of metallic colloid. The thermal
decomposition method allows generation of precious metal
colloid in metal oxide, whereas the ion-exchange method
allows generation of precious metal colloid in the glass
surface Layer. Nevertheless, when applying either of
these methods, only limited kinds of colors are available
for the color development, and yet, only those cold



~~1~ ~~~~3
- 22 -
colors cited above are available. In particular, any of
these preceding methods has a critical problem, that is,
chemical strengthening for covering glass cannot be
applied to those method.
More particularly, when executing any of those
methods cited above, the covering glass is chemically
strengthened by being immersed in the heated nitrate
solution containing K+ so that Na+ can be exchanged with
K+ in the nitrate solution. However, the colored layer
which was colored by preliminarily applying either the
thermal decomposition method or the ion-exchange method
against the glass surface disturbed the transfer of the
Na+ and K*, so that it was not possible for these methods
to properly exchange ion for chemically strengthening the
glass surface. To dispose of this defect, trials were
executed far coloring glass surface chemically
strengthened. However, since the strength was lowered by
the thermal treatment executed for the coloring process,
the method were not practically adopted. .
A still another trial wherein organic solvent
containing organic colorant i~ coated with the chemically
strengthened glass, for example, the sol-gel method was
tried. Nevertheless, the trial failed to evenly form
colored layer having uniform thickness on a variety of
shapes of the covering glass. Namely, depending on the '
shape of the covering glass, the colored effect was
uneven, and yet, organic colorant proved to be poor in
the durability.
As mentioned above, it was quite difficult for
any conventional art to properly form durable color layer
under a low temperature by chemically strengthening the
covering glass having various shape without sacrificing
own strength of the colored layer.
The object of the ninth embodiment of the
invention is to provide a novel covering glass free from
those technical problems mentioned above.
SUMMARY'OF THE INVENTION




_ 23 _ ~~~~~~~~a
During the past many years, inventors followed
up study on the introduction of an organic colorant into
a silicon dioxide film. The inventors have discovered
that in a process for forming an extremely dense silicon
dioxide film on a substrate wherein the substrate is
contacted caith a processing solution, namely a
hydrosilicofluoric acid solution supersaturated with
silicon dioxide, addition of an organic colorant into the
processing soluticn provides a silicon dioxide film
containing organic colorant, thus the inventors have
achieved the invention. The present invention comprises
the first step to supersaturate a hydrosilicofluoric acid
solution with silicon dioxide; the second step to add an
organic colorant to the solution, and the third step to
form a silicon dioxide film containing organic colorant
on the substrate.
In the first step, the processing solution is
prepared by making a hydrosilicofluoric acid solution
containing silicon dioxide in a supersaturated state.
The method of preparing this solution is not limited to
one specific method, but a variety of conventional
methods can be adopted, for example, like addition of
H3B03, aluminium, A1(OH)3 to the above solution, or
heating the above solution, or the like.
In the second step, an organic colorant is
added to the prepared solution. Normally, the organic
colorant is added to the solution after being dissolved
or dispersed in water or a water-miscible solvent such as
methanol or ethanol. Also, the organic colorant can
directly be added to the solution. Table l designates
concrete examples of the organic colorant that can be
introduced into the silicon dioxide film. The second
step can be included in the-first step.



sR a~ r;.~,~.,
_~ Lv 4~ '~3 .~
- 2~1
Table 1
Name of organic colorant Name of manufacturer
MALACHITE GREEN
VICTORIA BLUE BH
VICTORIA PURE BLUE BOH
METHYL VIOLET PURE SP
CATHILON RED T-BLH
CATHILON RED GTLH
CATHILON BLUE T-BLH HODOGAYA CHEMICAL CO., LTD.
CATHILON YELLOW T-RLH
CATHILON YELLOW 7GLH
CATHILON BRILLIANT lOGFH
CATHILON BLACK MH
CATHILON BLACK CD-BLH
CATHILON BLACK SH
ALIZARINE ASTROL
RHODAMINE 6G
RHODAMINE B
SULFORHODAMINE B
ACRDINE RED TOKYO KASEI KABUSHIKI KAISHA
FLUORESCEIN
2,5-diphenyloxazol
1,4-bis[2-(5-phenyl-
oxazolyl)]benzene
continued -




.2 ~ ~3 i_t 'L'
- 25 -
- continued -


Name of organic colorant Name of manufacturer


KAYACYL YELLOW GG


KAYACYL RHODAMINE FB


BLUE 5P


RED 21P NIPPON KAYAKU CO., LTD.


RED 3P


GREEN lOP


TG-21



NK-125


NK-78


NK-123 NIPPON KANKO SHIKISO


NK-863 KENKYUSHO


NK-1144


NK-1331


COUMARINE 504
COUMARINE 521
COUMARINE 523
COUMARINE 525 EXCITON CHEMICAL CO., LTD.
COUMARINE 535
COUMARINE 540
FLUOROL 555
RHODAMINE 123
RHODAMINE llo '
RHODAMINE 110 Kodak
RHODAMINE 19
COUMARINE 6
PSD-HR Nippon Soda Co., Ltd:
PSD-0
- continued -



- 26 -
- continued -
Name of organic colorant Name of manufacturer
DIACELLITON FAST RED R MITSUBISHI CHEMICAL
INDUSTRIES LTD.
TPP DOJIN KAGAKU KENKYUSHO
2-(1-naphthyl)-5- Lancaster Synthesis Co., Ltd.
phenyloxazol
From another point of view, the colorants shown
in Table 1 are classified as follows:
(1) triphenylmethane colorants: MALACHITE GREEN and the
like
(2) oxazol colorants: 2,5-diphenyloxazol and the like
(3) xanthene colorants: RHODAMINE 6G and the like
(4) fluoran colorants: PSD-HR and the like
(5) cyanine colorants: NK-125 and the lik a
(6) coumarine colorants: COUMARINE 504 and the like
(7) porphyrin colorants: TPP and the like
And therefore, other colorants belonging to any
of the above classes can be effectively used as organic
colorant.
Further, colorants which have substituents or
basic atom (i.e., nitrogen) in their skeleton can be
generally adoptable.
In the third step, a substrate is brought into
contact with the processing solution. Although contact
is achieved ~y allowing the prepared solution to flow
down on the surface ofsubstrate; it is simple and is
preferable that the substrate is immersed in the
processing solution stored in a bath because an uniform
film of silicon dioxide containing organic colorant can
easily be formed on the surface of substrate even if it



- 27 -
has extremely complex configuration.
Tt is enough that the temperature of the
processing solution is held at the room temperature when
immersing the substrate in the solution. Although the
maximum temperature of the solution is not clearly
defined, it is preferable that the temperature does not
exceed about 35°C. It is useless to thoughtlessly raise
the temperature of the solution because the added organic
colorant may be decomposed.
In contrast with the film formed by applying a
conventional sol-gel method, the silicon dioxide film
containing organic colorant formed by execution of the
serial steps mentioned above is extremely dense without
allowing presence of film defects such as foam or
bubbles.
The present invention performs the formation of
silicon dioxide film containing organic colorant in a
uniform processing solution. Since the'reaction for the
formation of the above film goes on at the room
temperature, the organic colorant in the solution is
uniformly introduced into the film without being
decomposed at all.
Since the produced film is extremely dense and
firmly adheres to the substrate,aven if it has smooth
surface, no thermal treatment is reguired. The film is
formed on the substrate by precipitation of silicon
dioxide from the supersaturated solution, and as a
result, the silicon dioxide film containing organic
colorant obtained by the invention is perfectly free from
impurities like undecomposed raw material or solvent.
The starting raw material used in the invention is
extremely inexpensive and dispenses with thermal
treatment at a high temperature, thus minimizing the film
production cost. Furthermore, since the applicable
materials are subject to reaction in the uniform
solution, satisfactory silicon dioxide film containing
organic colorant with uniform thickness can be formed on
substrates including those which have extremely complex




configuration.
First Embodiment
The method of dyeing molded organic substrate
S concerning the first embodiment of the present invention
is composed of those sequential processes described
below.
The primary film is formed on the molded
organic substrate by coating and curing at least one kind
of silicon compound selected from a group consisting of
organic silicon compounds represented by a general
formula (I):
RlnSi (R2) 4,n.
the hydrolyzates thereof, and colloidal silica. Next,
the molded organic substrate bonded with the primary film
is contacted with the processing solution which is
composed of hydrosilicofluoric acid solution,
supersaturated with silicon dioxide, added an organic
colorant such as an organic dyestuff or pigment before
eventually forming the silicon dioxide film containing
organic colorant on the surface of the molded organic
substrate coated with the primary film., In the above
general formula (I), R1 designates an organic group
containing hydrocarbon group haring l through 6 of carbon
number, vinyl group, methacryloxy group, epoxy group,
amino group, melcapto group, fluorine or chlorine; R2
designates either a single number ar a plurality of bond
groups selected from a group consisting of alkoxy group,
alkoxyalkoxy group, acetoxy group and chlori.n~; n ,:
designates 0 through 4.
Those molded substrates made from organic
material used for the first embodiment of'the invent~.on
include a variety of molded resinous materials such as
thermoplastic resins represented by polyvinyl chloride,
polystylene, polycarbonate, polymethyl me~hacry~:ate,
polyamide. polyacetal; polybutylene terephthala~e,:and
polyphenylene oxide; and those thermosetting reins
represented by polydiethyleneglycolbisallyl carbonate,



.'! x:J ~:3 ?.~
- 29 -
and phenol resin; furthermore, the first embodiment of
the invention is also applicable to cellulosic materials
such as pulp, paper, fibers, protein fibers, and
synthetic fibers represented by nylon, vinylon,
polyacrylonitrile, polyethylene and triacetate. Although
there is no limitation to the shape of the molded
substrates for the first embodiment being applied, the
shapes generally adopted are plate, film, rod, tube,
sphere, pulverulent body, fiber, web, and a variety of
processed forms.
As to the typical example of organic silicon
compounds represented by the general formula (I);
tetramethylsilane, trimethylmethoxysilane, dimethyl-
dimethoxysilane, methyltrimethoxysilane,
tetraethoxysilane, phenyltrimethoxysilane,
phenylmethyldimethoxysilane, vinyltriethoxysilane, vinyl-
tris(B-methoxyethoxy)silane, vinyltriacetoxysilane, Y-
methacryloxypropyltrimethoxysilane, Y-aminopropyl-
triethoxysilane, N-(s-aminoethyl)
aminopropyltrimethoxysilane, N-bis(s-hydroxylethyl)-Y-
aminopropyltriethoxysilane, N-(s-aminoethyl)-y-
aminopropyl(methyl)dimethoxysilane, y-melcaptopropyl-
trimethoxysilane, 3,3,3 - trifluoropropyltrimethoxy-
silane, y-glycidoxypropyltrimethoxysilane, s-(3,4 -
epoxycyclohexyl)ethyltrimethoxysilane,
methyltrichlorosilane, dimethyldichlorosilane,
trimethylchlorosilane, and tetrachlorosilane axe
exemplified.
The primary film is formed on the molded
organic substrate by applying at least one kind of
material selected from a group consisting of the silicon
compounds represented by the general formula (I), the
hydrolyzate thereof and colloidal silica. In this case,
before forming the primary film; if the primer layer of
organic resin is provided on the surface of the molded
organic substrate, adhesive strength of the primary film
against the substrate is significantly promoted. There
is no limitation to the material for the primer layer




'3 ~ ~ 'J
- 30 -
provided that it has sufficient adhesive strength against
the substrate. As the material for the primer layer,
denatured polyolefin, acrylic, polyester, polyurethane,
polyvinyl alcohol, vinyl acetate, vinyl chloride, phenol,
epoxy, or copolymer of these can be adopted.
To promote the adhesive strength of the primer
layer composed of any of those organic resin cited above,
before forming the primary layer, the organic substrate .
surface may be provided with hydrophillic property by
preliminarily treating the organic substrate surface with
corona treatment, plasma treatment, saponification
treatment, or by radiation of ultraviolet rays.
The primary layer can easily be formed by
initially coating the substrate surface with selected
resinous material cited above by any convenient means
such as spraying, dipping or brushing before curing it by
applying heat, ultraviolet rays, or electron beam.
It is preferable for the first embodiment of
the present invention that the thickness of primer layer
is in the range of about 0.05 to about 10 um.
As zs mentioned above, in the first embodiment
of the present invention, preferably forming film of the
primer layer, thereafter the primary film is formed by
curing organic silicon compound.
Considering the adhesive strength between the
formed primary layer and the silicon dioxide film
containing colorant to be formed on the primary layer, it
is preferable that organic silicon compound is used in
the state of mixture which satisfies the following
condition (a) or (b).
(a) At least a kind of silicon compound
containing amino group represented'by a general formula
(II) and at least a kind of silicon compound represented
by a general formula (III) so that the blend ratio
between the total molar concentration (A) of the above
silicon compound containing the amino group represented
by the general formula (zI) end he total molar
concentration (B) of the silicon cAmpound represented by




- 31
the general formula (III) satisfies the relationship of
OSB/A<10.
R3mSi(R4)4_m (II)
R5~Si(RS)4_Q (III)
cahere R3 designates an organic group containing amino
group; R4 designates an alkoxy group, R5 designate an
organic group containing hydrocarbon group having not
more than 2 of the carbon mumber such as methyl group, or
vinyl group, or hydroxyl group; and R5 designates an
alkoxyalkoxy group; m designates 1 or 2; and ~, designates
0 or 1, respectively.
(b) Silicon compound containing methacryloxy
group represented by a general formula (IV) and the
hydrolyzed silicon compound represented~by a general
formula (V) so that the ratio between the weight (C)
converted into R?Si0 3/2 from the silicon compound
containing methacryloxy group represented by a general
formula (IV) and the weight (D) converted into Si02 from
the hydrolyzed silicon compound represented by the
general formula (V) satisfies the relationship of
0.1<D/C.
R~Si(R8)3 (IV)
Si(R9)4 (V)
where R~ designates an organic group containing
methacryloxy group; R$ and R9 respectively designate
either a kind or a plurality of complex groups selected
from the group consisting of alkoxy group', alkoxyalkoxy
group, acetoxy group and chlorine.
The hydrolyzed silicon compound represented by
the general formula (I) contains such compounds a5 part
or the whole of the alkoxy group, or alkoxyalkoxy group,
acyloxy group or chlorine, is/are substituted by hydroxyl
group and such compound as part of the substituted




hydroxyl groups bound together themselves naturally.
These hydrolyzates can be generated by hydrolyzating
those compounds mentioned above in presence of acid in
the blended solvent composed of water and alcohol for
example. As to methods for forming the primary film, any
of those method may be used, which include the wet method
wherein organic resinous material are applied to the
substrate and thereafter they are cured by applying heat,
ultraviolet rays, or electron beam and the dry methods
including vacuum deposition, ion-plating, sputtering, or
plasma polymerization. Nevertheless, in order to form
the primary film on the organic substrate of large scale
or arbitrary shapes, the wet method is preferable.
In this case, it is desirable that the
thickness of the primary film is adjusted in a range from
10 nm to 100 nm. If less than 10 nm of the film
thickness is provided, adhesive strength of the silicon
dioxide film containing organic colorant to be formed
later on becomes too weak. Conversely, if more than 100
nm of the film thickness is provided, the primary film
itself becomes liable to lose transparency caused by
milky color generated in the film.
As is mentioned above, in the first embodiment
of the present invention, the organic molded substrate is
colored by forming silicon dioxide film containing
organic colorant on the surface of the organic molded
substrate after the substrate is contacted with
processing solution which is prepared by adding organic
colorant such as dyestuff or pigment into ..
hydrosilicofluoric acid solution supersaturated wi h
silicon dioxide.
The hydrosilicofluoric acid solution
supersaturated with silicon dioxide can be prepared by
adding additive reacting fluorine ion such as boric acid,
aqueous ammonia. metal composed of elements having the
ionization tendency greater than that of hydrogen or
metal halide, to the hydrosilicofluoric said solutzon in
which silicon dioxide dissolved and'saturated. Likewise,




- 33 -
as shown in Japanese Laid-Open Patent Publication No. 61-
281047 of 1986, the above hydrosilicofluoric acid
solution supersaturated with silicon dioxide can be
prepared by raising temperature of the hydrosilicofluoric
acid solution saturated with silicon dioxide.
The organic colorant can directly be added to
the hydrosilicofluoric acid solution saturated or
supersaturated with silicon dioxide. Also, the organic
colorant can preliminarily be dissolved in water before
being added to the hydrosilicofluoric acid solution.
Furthermore, insoluble organic colorants can also be
added to the hydrosilicofluoric acid solution by
preliminarily being dissolved in water-soluble organic
solvent.
It is preferable that concentration of
hydrosilicofluoric acid is in the range from 1.5 mol/L to
3.5 mol/L.
Examples of these organic colorants are as
follows: Dyestuffs such as KAYACYL YELLOW GG (a product
of NIPPN KAYAKU CO., LTD.), MALACHITE GREEN (a product of
HODOGAYA CHEMICAL CO., LTD.), ARIZARINE ASTROL (a product
of TOKYO KASEI K.K.), METHYL VIOLET PURE SP (a product of
HODOGAYA CHEMICAL CO:, LTD.), RED 21P,(a product of
NIPPON KAYAKU CO., LTD.), KAYACYL RHODAMINE FB (a product
of NIPPON KAYAKU CO., LTD.), VICTORIA PURE BLUE;BOH (a
product of HODOGAYA CHEMICAL CO., LTD.), BLUE 5P (a
product of NIPPON KAYAKU CO:, LTD:), RED 3P (a product of
NIPPON KAYAKU CO., LTD.), VICTORIA BLUE BH (a product of
HODOGAYA CHEMICAL CO., LTD.), and GREEN lOP (a product of
NIPPON KAYAKU CO., LTD.). Disperse pigment such as
DIACELLITON FAST RED (a product of MITSUBISHI CHEMICAL
INDUSTRIES, LTD:). Laser'colorant such as ACi2DTNE RED,
FLUORESCEIN, RHODAMINE B, RHODAMINE 6G, RHODAMINE 19,
RHODAMINE 110, RHQDAMINE 116, RHODAMINE 123,
SULFORHODAMINE B and COUMARINE 6:
In this specification, .the term "laser
colorant" means a colorant developing a color by means of
laser radiation.




Silicon dioxide film containing organic
colorant can properly be formed on the surface of the
organic substrate by contacting the organic substrate
coated with the primary film with the processing solution
prepared in the above-mentioned manner. This
functionally materializes dyeing and coloration.
As to the method in which the substrate is
contacted with processing solution, it is simple and
preferable that the substrate is immersed in a bath in
which the processing solution is filled although the
substrate may be contacted with the processing solution
by flowing the solution on the surface of the substrate
because satisfactory silicon dioxide film having
uniformly dispersed organic colorant can be formed on the
entire surface of the substrate even if it had extremely
complex configuration.
The temperature of the processing solution is
enough around the room temperature at the time of contact
with the substrate. Although there is no clear upper
limit for the temperature of processing solution, the
upper limit is preferably about 35°C. It is useless to
thoughtlessly raise temperature of the processing
solution because the added organic colorant may be
decomposed.
Since organic colorant is uniformly dispersed
in the processing solution, it is possible for the first
embodiment of the invention to easily form silicon
dioxide film containing uniformly dispersed organic
colorant. Since the reaction for the formation of
silicon dioxide film goes on ih the vicinity of the room
temperature, the organic colorant in the solution is
uniformly introduced into the film without being
decomposed: In addition, since the silicon dioxide film
is extremely dense and firmly adheres'to the substrate,
no thermal treatment is required:- Since the film
formation is implemented by precipitation from the
supersaturated solutions the'silicon dioxide. film
containing organic colorant is almost free from




_ 35 _ ~~ ~ ~~ ~"r~
impurities like undecomposed raw material or solvent. In
addition, since the starting raw material used for the
first embodiment of the present invention is extremely
inexpensive, and yet, it requires no thermal treatment at
a high temperature, the film production cost can be
minimized. Furthermore, since the reaction for the
formation of the silicon dioxide film is carried on in
the solution containing uniformly dispersed organic
colorant, the first embodiment of the present invention
can securely provide satisfactory silicon dioxide film
containing organic colorant having uniform thickness all
over the substrate surface even though it had extremely
complex configuration.
Second Embodiment
The second embodiment of the present invention
is a method for coloring a molded acrylic resin substrate
by applying the method far manufacturing the molded
acrylic resin substrate coated with silicon dioxide film
proposed by 3apanese Laid-Open Patent Publication Noo 1-
101339 of 1989. Concretely, the second embodiment of the
present invention relates to a method for manufacturing
the molded acrylic resin substrate coated with silicon
dioxide, wherein the primary film is initially generated
by coating and curing organic silicon compound on the
molded acrylic substrate and then the molded acrylic
substrate coated with the primary film formed by
contacting the substrate with the processing solution
formed by adding organic colorant such as dyestuff or
pigment to the hydrosilicofluoric acid solution
supersaturated with silicon dioxide so that the'silicon
dioxide film containing organic colorant can eventually
be formed on the primary film.
. The essential point of the second embodiment of
the present inventionis'thats a method of manufacturing
acrylic resin molded substrate'coated with silicon
dioxide containing organic colorant, wherein mixture
which includes silicon compound havzng a methacryloxy




- 36 -
group represented by a general formula (VI) and the
hydrolyzate of silicon compound represented by a general
formula (VII) so that the ratio between the weight (A)
converted into R11Si0 3/2 from the silicon compound
containing the methacryloxy group represented by the
general formula (VI) and the weight (B) converted into
Si02 from the silicon compound represented by the general
formula (VTI) satisfies the relationship of 0.1<B/A<0.5
is coated and cured.
RllSi(R12)3 (VI)
Si(R13)4 (VII)
where R11 designates an organic group containing
methacryloxy group, R12 and R13 respectively designate
either a kind or a plurality of bound groups selected
from a group consisting of alkoxy group, alkoxyalkoxy
group, acetoxy group and chlorine.
When the surface of the molded plastic
substrate is directly coated with silicon dioxide
containing the organic colorant by precipitation process,
a film having poor adhesive ability and uneven thickness
is only obtained caused by poor reactivity and wetting
property between the hydrosilicofluoric acid solution and
the plastic substrate. On the other hand, if the molded
plastic substrate is preliminarily coated with organic
silicon compound, which is properly cured, the silanol
group on the surface provides bonding property with the
silicon component in the hydrosilicofluoric acid
solution, so that adhesive strength and unevenness of the
silicon dioxide film containing organic colorant obtained
by the precipitation process can be improved.
Nevertheless, when the primary film having
thickness of not more than 2 or 3 hundreds ~ is formed by
means of coating and curing organic silicon compound, in
order to produce silicon dioxide film containing organic
colorant having uniform thickness and sufficient adhesive
strength by precipitation process, it is necessary to
select organic silicon compound in accordance with kinds
of plastic.



~a
~,~~.a
37 _
Inventors earnestly studied on the organic
silicon compound available for the formation of the
primary film suited for the molded acrylic substrate, and
finally discovered that the mixture of silicon compound
containing methacryloxy group represented by the general
formula (VI) and the hydrolyzate of silicon compound
represented by the general formula (VII) was optimal
under a specific ratio.
The second embodiment of the present invention
is described below. To materialize the second
embodiment, among silicon compounds containing
methacryloxy group represented by the general formula
(VI) usable for the formation of the primary film, it is
preferable that y-methacryloxypropyltrimethoxysilane is
used. As silicon compounds represented by the general
formula (VII), tetraethoxysilane is exemplified, and as
the hydrolyzates include the followings: part or the
whole of alkoxy groups, or alkoxyalkoxy groups, acyloxy
group, or chlorine of silicon compound is/are substituted
by hydroxyl groups, and part of the substituted hydroxyl
groups being condensated themselve naturally. The
hydrolyzate can easily be generated by hydrolyzing those
silicon compounds cited above in the blended solvent such
as water and alcohol mixture in presence of acid.
Either one kind or a plural kinds of silicon
compounds containing methacryloxy group represented by
the general formula (VI) may be used. Likewise, either a
kind or a plural kinds of silicon compounds represented
by the general formula (VII) may also be used.
In the second embodiment mixing ratio of
silicon compound containing methacryloxy group
represented by the general formula (VI) and the -
hydrolyzate of silicon compound represented by the
general formula (VII) is set so that the ratio between
the weight (A) converted into R11Si0 3/x from the silicon
compound containing methacryloxy group represented by the
general formula (VI) and the weight (B) converted'into
Si02 from the silicon compound repxesented-by the general




- 38 -
formula (VII) satisfies the relationship of 0.1<B/A<0.5.
The adhesive strength of silicon dioxide film
containing organic colorant produced by the precipitation
process is greatly affected by the mean molecular weight
of acrylic resin of the molded acrylic resin substrate to
be coated with film and also by the blend ratio B/A of
the above silicon compounds.
In the second embodiment of the present
invention, in order to form silicon dioxide film
containing organic colorant featuring strong adhesive
strength, it is preferable that the mean molecular weight
of the applicable acrylic substrate is not more than
80,000 and yet, it is necessary that the mixing ratio A/B
of the above silicon compound satisfies the relationship
of 0.1<B/A.
Among methods which form the primary film by
coating and curing the blend of silicon compound on the
molded acrylic resin substrate, immersion method is most
preferable, which uses such coating solution prepared by
dissolving the blend of the above silicon compounds in a
variety of available solvents.
It is desirable that the primary film is formed
by selecting such coating conditions such as
concentration of the silicon compound in the coating
solution and the pull up speed so ws to form film on a
glass substrate (for example, a conventional plate glass
or soda-lime glass) from 5 to 50nm of the film thickness,
preferably from 10 to 30nm of the film thickness if the
conditions are applied thereto.
More particularly, if the primary film is
formed under the condition allowing the formation of film
having around 50 nm of thickness, even though the
substrate had uneven surface having sub-micron concaves
and convexes, uniform film following to the configuration
of the substrate can be formed on the substrate.
Conversely, if the primary film is formed under the
condition to cause the thickness to become 'thicker than
50 nm on the glass substrate, there is a fear that'




- 39 -
uniform film following to the configuration of the
substrate is not formed on the substrate. Furthermore,
it is not preferable to adopt such conditions as to form
a film of thickness not more than 5 nm on the glass
substrate, since adhesive strength of the silicon dioxide
film containing organic colorant produced by the
precipitation process is lowered.
In the second embodiment of the present
invention, in order to form the primary film with such
thickness, it is preferable that concentration of silicon
compound contained in the coating solution is from 0.5 to
3.0 ~ by weight.
Since the silicon compound containing the
methacryloxy group represented by the general formula
(VI) contained in the primary film coated on the acrylic
substrate permeates the acrylic substrate, uniform film
is formed on the substrate even having sub-micron
concaves and convexes on its surface if the thickness of
the primary film is within a certain limit. On the other -
hand, since the hydrolyzate of the silicon compound
represented by the general formula (VII) cannot permeate
the acrylic substrate, if the blend ratio (B/A) mentioned
above is increased, uniform film following to the
configuration of the substrate cannot be formed. As a
2S result, in the second embodiment of the present
invention, the blend ratio B/A is set not more than 0.5.
In the second embodiment of the present
invention, acrylic resin molded substrate is colored by
coating silicon dioxide film containing organic colorant
on the acrylic resin substrate with the primary film is
such a manner as to contact the substrate with processing
solution prepared by adding organic colorant such as
dyestuff or pigment into hydrosilioofluoric acid solution
supersaturated with silicon dioxide.
The hydrosilicofluoric acid solution
supersaturated with silicon dioxide can be prepared by
adding additive reacting fluorine ,ion such as boric acid,
agueous ammonia, metal composed of elements having the




- 40 -
ionization tendency greater than that of hydrogen or
metal halide, to the hydrosilicofluoric acid solution in
which silicon dioxide dissolved and saturated. Likewise,
as is described in Japanese Laid-Open Patent Publication
No. 61-281047 of 1986, the above solution can also be
prepared by raising temperature of hydrosilicofluoric
acid solution saturated with silicon dioxide.
The organic colorant can directly be added to
hydrosilicofluoric acid solution containing saturated or
supersaturated silicon dioxide. Alternatively, after
preliminarily being dissolved in water, organic colorant
can also be added to the hydrosilicofluoric acid
solution. Likewise, after preliminarily being dissolved
in water-miscible organic solvent, water-insoluble
organic colorant can also be added to the
hydrosilicofluoric acid solution. It is preferable that
concentration of hydrosilicofluoric acid solution is from
1.5 to 3.5 mol/L. Examples of these organic colorant are ,
as follows: Dyestuffs such as KAYACYL YELLOW GG (a
product of NIPPON KAYAKU CO., LTD.), MALACHTTE GREEN (a
product of HODOGAYA CHEMICAL CO., LTD.), ALIZARINE ASTROL
(a product of TOKYO KASEI K.K.), METHYL VIOLET PURE SP (a
product of HODOGAYA CHEMICAL CO., LTD.), RED 21P (a
product of NIPPON KAYAKU CO., LTD:), KAYACYL RHODAMINE FB
(a product of NIPPON KAYAKU CO., LTD.), VICTORIA PURE
BLUE BOH (a product of HODOGAYA CHEMICAL CO., LTD.), BLUE
5P (a product of NIPPON KAYAKU CO:, LTD.), RED 3P (a
product of NIPPON KAYAKU CO., LTD.), VICTORIA BLUE BH (a
product of HODOGAYA CHEMICAL CO., LTD.) and GREEN 1OP (a
product of TOKYO KASEI K.K.). Disperse Pigment such as
DIACELLITON FAST RED (a product of MITSUBISHI CHEMTCAL
INDUSTRIES LTD.). Laser colorants such as ACRDINE RED,
FLUORESCEIN, RHODAMINE B, RHODAMINE 6G, RHODAMINE 19,
RHODAMINE 110, RHODAMINE 116, RHODAMINE 123,
SULFORHODAMTNE B, COUMARINE 6.
Silicon dioxide film oon~aining organic
colorant is formed on the surface of molded organic
substrate coated with the primary film by contacting the




-(. za 1' r" ~,
~~«.refi.3:9
- 41 -
processing solution prepared in the above-mentioned
manner thus functionally materializing dyeing and
coloration.
As to the method in which the substrate is
contacted with processing solution, it is simple and
preferable that the substrate is immersed in a bath in
which the processing solution is filled although the
substrate may be contacted with the processing solution
by flowing the solution on the surface of the substrate
because the immersion method securely forms uniform
silicon dioxide film containing organic colorant even if
the substrate had extremely complex configuration. The
temperature of the processing solution is enough around
the room temperature at the time of contact with the
substrate. Although there is no clear upper limit for
the temperature of processing solution, the upper limit
is preferably about 35°C. It is useless to raise
temperature of the processing solution without care
because the added organic colorant may be decomposed.
Since organic colorant is uniformly dispersed
in the processing solution, it is possible for the second
embodiment of the invention to easily form silicon
dioxide film uniformly dispersed organic colorant. Since
the reaction for the formation of film goes on in the
vicinity of the room temperature, the organic colorant in
the processing solution is uniformly introduced into the
film without being decomposed. Furthermore, since the
formed film is extremely dense and firmly adheres to the
substrate, no thermal treatment is required. Since the
formation of the film is carried out by the precipitation
from the supersaturated silicon dioxide solution, the
silicon dioxide film containing organic colorant produced
by the second embodiment of the invention is almost free
from impurities like undercomposed raw material or
solvent. The starting raw material used for implementing
the second embodiment is extremely inexpensive, and yet,
the thermal treatment at a high temperature is not
required. As a result, the film production cost can be

- 42 -
minimized. Furthermore, since reaction is carried out in
the uniformly prepared solution, silicon dioxide film
containing organic colorant having uniform thickness and
color distribution can be formed on the molded substrate
even though it has extremely complex configuration.
Third Embodiment
The third embodiment of the present invention
implements coloration of molded polycarbonate substrate
by applying a method for manufacturing the molded
polycarbonate substrate coated with silicon dioxide
proposed by Japanese Laid-Open Patent Publication No. 62-
291536 of 1987. More particularly, the third embodiment
of the present invention relates to a method for
manufacturing a molded polycarbonate substrate coated
with silicon dioxide, wherein the primary film is formed
by coating and curing organic silicon compound on the
molded polycarbonate substrate and then the molded
polycarbonate substrate coated with primary film is
contacted with the processing solution prepared by adding
organic colorant such as dyestuff or pigment to the
hydrosilicofluoric acid solution supersaturated with
silicon dioxide so that silicon dioxide film containing
organic colorant can eventually is formed on the primary
film.
The essential point of the third embodiment of
the present invention is that:
a method for manufacturing polycarbonate coated with
silicon dioxide containing organic colorant, wherein the
primary film is formed by coating and drying coating
solution including silicon compound having amino group
and at least one kind of compound selected from a group
consisting of silicon compound represented by a general
formula (VIII) and hydrolyzates thereof so that inclusion
of silicon compound having amino group is not less than
0.2 % by weight and concentration of total silicon
compound is not more than 5 % by weight.
R2lnSi(R22)4-n (VIII)




- 43 -
where R21 designates either hydrocarbon group containing
not more than 2 of carbon number like ethyl group, vinyl
group, or organic group having not more than 3 of carbon
number containing melcapto group, hydroxyl group; Rz2
designates one kind or plural kinds of bound group
selected from a group consisting of alkoxy group,
alkoxyalkoxy group, acetoxy group and chlorine; and n
designates 0 or 1.
When the surface of the molded plastic
substrate is directly coated with silicon dioxide
containing the organic colorant by precipitation process,
a film having poor adhesive ability and uneven thickness
is only obtained caused by poor reactivity and wetting
property between the hydrosilicofluoric acid solution and
the plastic substrate. On the other hand, if organic
silicon compound is preliminarily coated over the surface
of the molded plastic substrate, which is cured, since ,
silanol group on the surface provides bonding property
with the silicon component in the hydrosilicofluoric acid
solution, so that adhesive strength and unevenness of
silicon dioxide film containing organic colorant obtained
by the precipitation process can be improved.
However, when producing the primary film having
thickness not more than 2 or 3 hundreds A is formed by
means of coating and curing organic silicon compound, in
order to produce silicon dioxide film containing organic
colorant having uniform thickness and sufficient adhesive
strength, it is necessary to select organic silicon
compound in accordance with kinds of plastic.
Inventors earnest7,y studied on organic silicon
compound available for the formation of the primary film
suited for the molded polycarbonate substrate, and then
finally discovered thatthe'blend o~ silicon compound
containing amino group and at leash one kind of compound
selected from a group consisting of silicon compound
represented by the general formula (VIII) and the
hydrolyzate thereof was optimal'for use under specific




- 44
ratio.
The third embodiment of the present invention
is described below. In the third embodiment, among
silicon compounds available for the formation of the
primary film, as silicon compounds containing amino group,
Y-aminopropyltriethoxysilane, N-(8-aminoethyl)-Y-
aminopropyltrimethoxysilane, N-(s-aminoethyl)-Y-
aminopropylmethylmethoxysilance, etc are exemplified.
These silicon compounds are effective for producing
silicon dioxide film containing organic colorant and
having strong adhesive strength by the precipitation
process.
As silicon compound represented by the general
formula (VIII), methyltriethoxysilane, tetraethoxysilane,
vinyltrietoxysilane, vinyltris(B-methoxy)silane,
vinyltriacetoxysilane, Y-melcaptopropyltrimethoxysilane,
y-hydroxypropyltrimethoxysilane, etc are exemplified. As
hydrolyzates of the silicon compound represented by the
general formula (VIII) includes the followings:
a part or the whole of alkoxy group, alkoxyalkoxy group,
acyloxy group and chrolide in the silicon compound
represented by the general formula (VIII) is/are
substituted by hydroxyl groups, and part of the
substituted hydroxyl groups being condensated themselves
naturally. Any of these hydrolyzates can easily be
obtained by hydrolyzing those silicon compound cited
above in the blended solvent sudh as water and alcohol
mixture in presence of acid.
These silicon compounds cited above available
to facilitate the formation of silicon dioxide film
containing organic colorant by the precipitation method
and to obtain silicon dioxide film containing organic
colorant without unevenness.
If the primary film is formed with mexely
silicon compounds containing amino group, although
depending on cases, either uneven formation of the
colored film or milky color may occur~in the silicon
dioxide film containing organic colorant produced' by the




2~~~~~~~~~
- 45 -
precipitation method. The above-mentioned defects can be
prevented by blending silicon compound containing amino
group with the silicon compound represented by the
general formula (VIII) (or the hydrolyzate thereof).
Although the primary film is formed uniformly
with merely the silicon compound represented by the
general formula (VIII) by the precipitation method, the
obtained silicon dioxide film containing organic colorant
is poor in adhesive strength. As a result, it is
necessary for the primary film formation to use the
silicon compound represented by the general formula
(VIII) with the silicon compound containing amino group.
Either one kind or plural kinds of the silicon
compound represented by the general formula (VIII) (or
the hydrolyzate thereof) may be used. Likewise, either
one kind or plural kinds of the silicon compound
containing amino group may also be used.
In the third embodiment, th,e primary film is
formed by coating and curing coating solution containing .
the silicon compound having amino group and at least one
kind of compound selected from a group consisting of the
silicon compounds represented by the general formula
(VIII) and the hydrolyzates thereof on the molded
polycarbonate substrate, followed by the drying
process. The coating solution is prepared by dissolving
a silicon compound containing amino group and the silicon
compounds represented by the general formula (VIII) and
the hydrolyzates thereof so that the silicon compound
containing amino group is not less than 0.2 % by weight
and concentration of total silicon compound in the w
solution is not more than 5 % by weight.
Solvent used in the third embodiment must be
selected in consideration of the solubility of the
polycarbonate substrate and the wetting property of the
solvent against the substrate. In other words, such
solvent dissolving polycarbonate as toluene or xylene
must not be used. Likewise, water having poor wetting
property against the polycarbonate substrate should not



~~~~~~i~
- 46 -
be used alone. However, water of which wetting property
is improved by adding surface active agent against the
polycarbonate substrate can be used. Immersion method is
most preferable as coating method. Either method using
heat ultraviolet rays or electron beam may be used as
method for drying and curing the coated film.
It is desirable that the primary film is formed
by selecting such coating conditions such as
concentration of the silicon compound in the coating
solution and the pull-up speed as to form film on a glass
substrate (for example, a conventional plate glass or
soda-lime glass) from 5 to 100 nm of the film thickness,
preferable from 10 to 50 nm of the film thickness if the
conditions are applied thereto.
Since the silicon compound permeates the
polycarbonate substrate, thickness of the primary film
formed on the polycarbonate substrate becomes thinner
than that of the primary film formed on the glass
substrate. Accordingly, if the primary film is formed
based on the condition which allows formation of the
primary film having not more than 100nm of thickness an
the glass substrate, even if the polycarbonate substrate
had sub-micron concaves and convexes on the surface,
uniform film following the concaves and convexes can be
obtained. If the primary film were formed based on the
condition which causes the film thickness on the glass
substrate to exceed 100nm, there is a fear that uniform
film following to the concaves and convexes on the
surface of the polycarbonate substrate is not formed.
Conversely, it is not preferable to adopt such conditions
as to form a film of thickness under 5 nm on the glass
substrate, since adhesive strength of the silicon dioxide
film containing organic colorant produced by
precipitation method is lowered.
In the third embodiment of the present
invention, in order to form the primary film with such
thickness, it is preferable that the concentration of the
silicon compound contained in the coating solution is




- 4~ -
from 0.2 to 5 o by weight, and more preferably from 0.5
to 2 ~ by weight. However, in order to prevent
degradation of the adhesive strength of the silicon
dioxide film containing organic colorant produced by 'the
precipitation method, it is preferable that concentration
of silicon compound containing amino group is not less
than 0.2 ~ by weight, and more preferably not less than
0.5 ~ by caeight in the coating solution.
Since the silicon compound containing amino
group, and the other silicon compound represented by the
general formula (VIII) or the hydrolyzate thereof in the
primary film coated on the polycarbonate substrate
respectively permeate the polycarbonate substrate,
uniform film following the concaves and convexes of sub-
micron on the surface of the substrate is formed if the
thickness of the primary film is within a certain
limit. Furthermore, due to the presence of the silicon
compound containing amino group, silicon dioxide film
containing organic colorant having strong adhesive
strength can be obtained.
In the third embod3.ment of the present
invention, PC molded substrate is colored by coating
silicon dioxide film containing organic colorant on the
PC molded substrate with the primary film in such a
2S manner as to contact the substrate. with processing
solution prepared by adding organic colorant such as
dyestuff or pigment into hydrosilicofluoric acid solution
supersaturated with silicon dioxide.
The hydrosilicofluoric acid solution
supersaturated with silicon dioxide can be prepared by
adding additive reacting fluorine ion such as boric acid,
aqueous ammonia, metal composed of elements having the
ionization tendency greater than that of hydrogen or
metal halide to the hydrosilicofluoric acid solution in
which silicon dioxide is dissolved az~d saturated.
Likewise, as is described in Japanese Laid-Open Patent
Publication No. 61-281047 of 1986, the above solution can
also be prepared by raising temperature of




hydrosilicofluoric acid solution saturated with silicon
dioxide.
The organic colorant can directly added to the
hydrosilicofluoric acid solution containing saturated or
supersaturated silicon dioxide. Alternatively. organic
colorants can be added to the hydrosilicofluoric acid
solution after preliminarily being dissolved in water.
Furthermore, after preliminarily being dissolved in
water-miscible organic solvent, water-insoluble organic
colorants can also be added to the hydrosilicofluoric
acid solution.
It is preferable that concentration of
hydrosilicofluoric acid solution is from 1.5 to 3.5
molJL. Examples of the organic colorant are as follows:
Dyestuffs such as KAYACYL YELLOW GG {a product of NIPPON
KAYAKU CO., LTD.), MALACHITE GREEN (a product of HODOGAYA
CHEMICAL CO., LTD.), ALIZARINE ASTROL (a product of TOKYO
KASEI K.K.), METHYLVIOLET PURE SP {a product of HODOGAYA
CHEMICAL CO., LTD.), RED 21P (a product of NIPPON KAYAKU
CO., LTD.), KAYACYL RHODAMINE FB (a product of NIPPON
KAYAKU CO., LTD.), VICTORIA PURE BLUE BOH (a product of
HODOGAYA CHEMICAL CO., LTD.), BLUE 5P (a product of
NIPPON KAYAKU CO., LTD.), RED 3P (a product of NIPPON
KAYAKU CO., LTD.), VICTORIABLUE BH (a product of HODOGAYA
CHEMICAL CO., LTD.) and GREEN lOP (a product of NIPPON
KAYAKU CO., LTD.). Disperse pigment such as DIACELLITON
FAST RED (a product of MITSUBISHI CHEMICAL INDUSTRIES
LTD.) Laser colorant such as ACRYDINE RED, FLUORESCEIN,
RHODAMINE B, RHODAMINE 6G, ~HODAMINE 19, RHODAMINE 110,
RHODAMINE 116, RHODAMINE 123, SULFORHODAMINE B, COUMARINE
6.
Silicon dioxide film containing organic
colorant is formed on the surface of the molded
polycarbonate substrate coated with the primary film by
contacting the processing solution prepared in the above-
mentioned manner thus functionally materializing dyeing
and coloration.
As to the method in which the substrate is




- 4 9 - ~ ~.~ h J ~3'.
contacted with processing solution, it is simple and
preferable that the substrate is immersed in a bath in
cahich the processing solution is filled for although the
substrate may be contacted with the processing solution
by flowing the solution on the surface of the substrate
because the immersion method securely forms uniform
silicon dioxide film containing organic colorant even
though the substrate had extremely complex
configuration. The temperature of the processing
solution is enough around the room temperature at the
time of contact with the substrate. Although there is no
clear upper limit for the temperature of processing
solution, the upper limit is preferably about 35°C. It
is useless to thoughtlessly raise the temperature of the
processing solution because the added organic colorant
may be decomposed.
Since the organic colorant is uniformly
dispersed in the processing solution, it is possible for
the third embodiment of the invention to easily form
silicon dioxide film uniformly dispersed organic
colorant.
Since the reaction for the formation of film
goes on in the vicinity of the room temperature, organic
colorant in the processing solution is uniformly
introduced into the film without being decomposed.
Furthermore, since the formed film is extremely dense and
firmly adheres to the substrate, no thermal treatment is
required. Since the formation of the film is carried out
by precipitation from the supersaturated silicon dioxide
solution, the silicon dioxide film containing organic
colorant produced by the third embodiment of the
invention is almost free from impurities like
undecomposed raw material or solvent. The starting raw
material used for implementing the third embodiment is
extremely inexpensive, and yet, the thermal treatment at
high a temperature is not required, the film production
cost can be minimized. Furthermore, since reaction is
carried out in the uniformly prepared solution, silicon



~~~~1.~~3~~aci
- 50 -
dioxide film containing organic colorant having uniform
thickness and color distribution can be formed on the
molded substrate even though it has extremely complex
configuration.
Fourth Embodimen t
The fourth embodiment of the invention is
materialized by coating the surface of pulverulent body
with silicon dioxide film containing organic colorant
such as organic dyestuff or pigment. To implement this,
there is a conventional method called the sol-gel method
in which pulverulent body is contacted with the solution
containing hydrolyzed metal alkoxide added with organic
colorant.
Far example, this prior art is reported in a
technical paper "J. Non-Cryst. Solida, 74 (1985), 395"
describing the application of fluorescent organic
colorant to a silicon dioxide film. Another technical
paper "Ceramics, 21, No. 2, 1986, 111" proposes a doping
of organic molecules into non-crystal quartz by the sol-
gel method.
Nevertheless, it is necessary for the sol-gel
method to thermally treat the formed film in the final
production stage to fix the film to the substrate, and
yet, since the produced film cannot thermally be treated
at a high temperature which causes the internal organic
colorant to easily be decomposed, the produced film
unavoidably becomes porous. And also; in the sol-gel
method, such organic colorant which is easily decomposed
on receipt of thermal treatment under a low temperaturE
cannot be introduced to the film. Furthermore, in the
sol-gel method the heat treatment is ob~.iged to be
carried out under a low temperature, so that the problem
inherent to the sot-gel method is aggravated. Nam~ly~,
impurities such as undecomposed raw material or solvent
remain in the film: Another problem of the sol-gel
method is that since it uses expensive metal alkoxide as
the starting raw material', the'film production cost




- 51 -
G'~ F~
L ~ ~ 4.~
becomes high. Also, since in the sol-gel method the dip-
coating method is adopted, the method cannot be applied
to a substrate having complex configuration.
The fourth embodiment of the present invention
utilizes a method for forming silicon dioxide film
containing organic colorant such as dyestuff or pigment
on pulverulent body in which the pulverulent body is
contacted with processing solution prepared by adding
organic colorant such as dyestuff or pigment to
hydrosilicofluoric acid solution supersaturated with
silicon dioxide. The hydrosilicofluoric acid solution
containing supersaturated silicon dioxide can be prepared
by adding boric acid, aqueous ammonia, metal halide or
metal of which ionization tendency is greater than that
of hydrogen to the hydrosilicofluoric acid solution
saturated with silicon dioxide. Alternatively, the
hydrosilicofluoric acid solution supersaturated with
silicon dioxide can be prepared by raising temperature of
the solution after adding silicon dioxide to the
hydrosilicofluoric acid solution held at a low
temperature (this is called "temperature-differentiation
method"). Water-soluble organic colorant can directly be
added to the above solution. Water-insoluble organic
colorant can also be added to the solution after being
dissolved in water-miscible organic solvent like
alcohol. The organic colorant can be added to the
hydrosilicofluoric acid solution saturated with silicon
dioxide or it may also be added to the solution after the
solution is supersaturated with s9.licon dioxide. In the
fourth embodiment, the concentration of
hydrosilicofluoric acid is not less than 1.0 mol/L,
desirably from 1.5 to 3.0 mol/L is used. The temperature
of the processing solution at the time of contact with
the pulverulent body is from l5 to 60°C; desirably from
25 to 40°C. When the temperature-differentiation method
is applied normally, silicon dioxide is saturated at not
more than 10°C. And then, the pulverulent body fs
contacted with the processing solution of the temperature




not less than 20°C, desirably from 40°C to 60°C.
Generally, the pulverulent body is contacted with the
processing solution while being dispersed and stirred in
the solution.
Example of organic colorants are dyestuffs and
pigments such as RHODAMINE 6G, FLUORESCEIN, MALACHITE
GREEN (a product of HODOGAYA CHEMICAL CO., LTD.),
COUMARIN 6, SULFORHODAMINE B, RHODAMINE 19, RHODAMINE
110, RHODAMINE 116, RHODAMINE 123, KAYACYL YELLOW GG (a
product of NIPPON KAYAKU CO., LTD.), RED 21P (a product
of NIPPON KAYAKU CO., LTD.), ACRDINE RED, KAYACYL
RHODAMINE FB (a product of NIPPON KAYAKU CO., LTD.), RED
3P (a product of NIPPON KAYAKU CO., LTD.), VICTORIA BLUE
BH (a product of HODOGAYA CHEMICAL CO., LTD.), ALIZARINE
ASTROL (a product of TOKYO KASEI K.K.), METHYL VIOLET
PURE SP (a product of HODOGAYA CHEMTCAL CO., LTD.), GREEN
lOP (a product of NIPPON KAYAKU CO., LTD.), etc.
The pulverulent body may be composed of
inorganic crystals such as titanium oxide, ferric oxide,
barium sulfate, or mica. The pulverulent body may also
be composed of amorphous inorganic material such as glass
beads, glass balloon, or flakes. Furthermore, the
pulverulent body may be composed of organic material such
as polycarbonate resin or acrylic resin. In this case,
in order to produce colored film having sufficient
adhesive strength, it is desirable that the surface of
the organic pulverulent body is initially coated with at
least one kind of silicon compound selected from a group
consisting of organic silicon compound composed of
silane-coupling agent, hydrolyzate thereof and colloidal
silica, and then the pulverulent body is immersed and
dispersed in the processing solution before eventually
producing the silicon dioxide film containing organic
colorant.
Fifth Embodiment
The fifth embodiment of the in~rention is
materialized by coating the surfaoe of transparent




substrate with silicon dioxide film containing organic
colorant such as organic dyestuff or pigment.
To implement this, there is a conventional art
called "sol-gel" method in which the transparent
substrate is contacted with the solution containing
hydrolyzed of metal alkoxide having organic colorant.
For example, this prior art is reported in a
technical paper "J. Non-Cryst. Solids, 74 (1985), 395"
describing the application of fluorescent organic
colorant to the silicon dioxide film. Another technical
paper "Ceramics, 21, No. 2, 1986, 111" proposes the
doping of organic molecules into non-crystal quartz by
the sol-gel method.
Nevertheless, it is necessary for the sol-gel
method to thermally treat the formed film in the final
production stage to fix the film to the substrate, and
yet, since the produced film cannot thermally be treated
at a high temperature which causes the,internal organic
colorant to easily be decomposed, the produced film
unavoidably becomes porous. And also, in the sol-gel
method, such organic colorant which is easily decomposed
on receipt of thermal treatment under low temperature
cannot be introduced to the film. Furthermore, in the
sol-gel method the heat treatment is obliged to be
carried out under a low temperature, so that the problem
inherent to the sol-gel method is aggravated. Namely,
impurities such as undecomposed raw material or solvent
remain in the film. Another problem of the sol-gel
method is that since it uses expensive metal alkoxide as
the starting raw material, the film production cost
becomes high. Also; since in the sol-gel method the dip-
coating method is adopted , the method cannot be applied
to a substrate having complex configuration.
The fifth embodiment of the present invention
utilizes a method for forming silicon dioxide film
containing organic colorant such as dyestuff oz pigment
on the transparent substrate in which the substrate is
contacted with processing so~.ution prepared by adding




- 54 -
organic colorant such as dyestuff or pigment to
hydrosilicofluoric acid solution supersaturated with
silicon dioxide. The hydrosilicofluoric acid solution
containing supersaturated silicon dioxide can be prepared
by adding boric acid, aqueous ammonia, metal halide or
metal of which ionization tendency is greater than that
of hydrogen to the hydrosilicofluoric acid solution
saturated with silicon dioxide. Alternatively, the
hydrosilicofluoric acid solution supersaturated with
silicon dioxide can be prepared by raising temperature of
the solution after adding silicon dioxide to the
hydrosilicofluoric acid solution held at a low
temperature (this is called "temperature-differentiation
method"). Water-soluble organic colorants can directly
be added to the above solution. Water-insoluble organic
colorants can also be added to the solution after being
dissolved in water-miscible organic solvent like
alcohol. The organic colorant can be added to the '
hydrosilicofluoric acid solution saturated with silicon
dioxide or it may also be added to the solution after the
solution is supersaturated with silicon dioxide. In the
fifth embodiment, the concentration of hydrosilicofluoric
acid is not less than l.0 mol/L, desirably from 1.5 to
3.0 mol/L is used. The temperature of the processing
solution at the time of contact with the transparent
substrate is from 15 to 60°C, desirably from 25 to
40°C. When the temperature-differentiation method is
applied, normally, silicon dioxide is saturated at not
more than 10°C. And then, the transparent substrat-a is .
brought into contact with the prepared solution of the
temperature at not less than 20°C, desirably from 40° to
60°C. Generally, the transparent substrate is'contacted
with the processing solution while being dispersed and
stirred in the solution.
Examples of organic colorants are dyestuffs and
pigments such as DIACELLITON FP.ST RED R (a product of
MITSUBISHI CHEMICAL INDUSTRIES LTD:), BLUE SP (a product
of NIPPON KAYAKU CO., LTD.)o RHODAMINE 6G, FLUORESCEIN,




- 55 -
MALACHITE GREEN (a product of HODOGAYA CHEMICAL CO.,
LTD.), COUMARIN 6, SULFORHODAMINE B, RHODAMINE 19,
RHODAMINE 110, RHODAMINE 116, RHODAMINE 123, KAYACYL
YELLOW GG (a product of NIPPON KAYAKU CO., LTD.), RED 21P
(a product of NIPPON KAYAKU CO., LTD.), ACRDINE RED,
KAYACYL RHODAMINE FB (a product of NIPPON KAYAKU CO.,
LTD.), RED 3P (a product of NIPPON KAYAKU CO., LTD.),
VICTORIA BLUE BH (a product of HODOGAYA CHEMICAL CO.,
LTD.), ALIZARINE ASTROL (a product of TOKYO KASEI K.K.),
METHYL VIOLET PURE SP (a product of HODOGAYA CHEMICAL
CO., LTD.), GREEN lOP (a product of NIPPON KAYAKU CO.,
LTD.), etc.
The transparent substrate may be composed of
glass or other transparent organic crystal substrates, or
organic material like plastics. Since the fifth
embodiment of the invention forms silicon dioxide film
through lamination process, film having uniform thickness
can be produced regardless of the superficial shape of
the substrate, and therefore the fifth embodiment also
allows formation of film of uniform thickness not only on
the plane transparent substrates, but an transparent
substrates having concaves and convexes on the surface.
Furthermore, the fifth embodiment is effectively
applicable to such substrate composed of polycarbonate
resin or acrylic resin as well. In this case, in order
to produce colored film having sufficient adhesive
strength, it is desirable that the surface of the organic
transparent substrate is initially coated with at least a
kind of silicon compound selected from a group consistig
of organic silicon compound composed of silane-coupling
agent, hydrolyzate thereaf and colloidal silica, and then
immersed in the processing solution.before eventually
forming the silicon dioxide film containing organic
colorant.
Sixth Embodiment
The sixth embodiment of the invention is
materialized by coating the surface of transparent


- 56 -
substrate with silicon dioxide film containing organic
colorant such as organic dyestuff or pigment.
To implement this, there is a conventional art
called "sol-gel" method in which the transparent
substrate is contacted with the solution containing
hydrolyzed of metal alkoxide having organic colorant.
For example, this prior art is reported in a
technical paper "J. Non-Cryst. Solids, 74 (1985), 395"
describing the application of fluorescent organic
colorant to the silicon dioxide film. Another technical
paper "Ceramics, 2l, No. 2, 1986, 111" proposes the
doping of organic molecules into non-crystal quartz by
the sol-gel method.
Nevertheless, it is necessary for the sol-gel
method to thermally treat the formed film in the final
production stage to fix the film to the substrate, and
yet, since the produced film cannot thermally be treated
by applying high temperature which causes the internal
organic colorant to easily be decomposed, the produced
film unavoidably becomes porous. And also, in the sol-
gel method, such organic colorant which is easily
decomposed on receipt of thermal treatment under a low
temperature cannot be introduced to the film.
Furthermore, in the sol-gel method the heat treatment is
obliged to be carried out under a low temperature, so
that the problem inherent ~o the sol-gel method is
aggravated. Namely, impurities such as undecomposed raw
material or solvent remain in the film. Another problem
of the sol-gel method is that since the it uses expensive
metal alkoxide as the starting raw material, the film
production cost becomes high. Also, since in the sol-gel
method the dip-coating method is adopted , the method
cannot be applied to a substrate having complex
configuration.
The sixth embodiment of the present invention
utilizes a method for forming silicon dioxide film
containing organic colorant such as dyestuff or pigment
on the transparent substrate in which the substrate is



_ 57 _
contacted with processing solution prepared by adding
organic colorant such as dyestuff or pigment to
hydrosilicofluoric acid solution supersaturated with
silicon dioxide. The hydrosilicofluoric acid solui:ion
containing supersaturated silicon dioxide can be prepared
by adding boric acid, aqueous ammonia, metal halide or
metal of which ionization tendency is greater than that
of hydrogen to the hydrosilicofluoric acid solution
saturated with silicon dioxide. Alternatively, the
hydrosilicofluoric acid solution supersaturated with
silicon dioxide can be prepared by raising temperature of
the solution after adding silicon dioxide to the
hydrosilicofluoric acid solution held at a low
temperature (this is called "temperature-differentiation
method"). Water-soluble organic colorants can directly
be added to the above solution. Water-insoluble organic
colorants can also be added to the solution after being
dissolved in water-miscible organic solvent like
alcohol. Organic colorants can be added to the
hydrosilicofluoric acid solution saturated with silicon
dioxide or it may also be added to the solution after the
solution is supersaturated with silicon dioxide. In the
sixth embodiment, the concentration of hydrosilicofluoric
acid is not less than 1.0 mol/L, desirably from 1.5 to
3.0 mol/L is used. The temperature of the processing
solution at the time of contact with the transparent
substrate is from 15 to 60°C, desirably from 25 to
40°C. When the temperature-differentiation method is
applied, normally, silicon dioxide is saturated at not
more than 10°C. And then, the transparent substrate is
contacted with the processing solution of the temperature
not less than 20°C, desirably from 40° to 60°C.
Generally, the transparent substrate is contacted with
the processing solution while being disppersed and
stirred in the solution.
Example of organic colorants are dyestuffs and
pigments such as DIACELLITON FAST RED R (a product o~
MITSUBISHI CT~EMICAL INDUSTRIES LTD.), BLUE SP (a product




- 5$ - ~~3:~~~~
of NIPPON KAYAKU Co., LTD.), RHODAMINE 6G, FLUORESCEIN,
MALACHITE GREEN (a product of HODOGAYA CHEMICAL CO.,
LTD.), COUMATINE 6, SULFORHODAMINE B, RHODAMINE 19,
RHODAMINE 110, RHODAMINE 116, RHODAMINE 123, KAYACYL
YELLOW GG (a product of NIPPON KAYAKU CO., LTD.), RED 21P
(a product of NIPPON KAYAKU CO., LTD.), ACRYDINE RED,
KAYACYL RHODAMINE FB (a product of NIPPON KAYAKU CO.,
LTD.), RED 3P (a product of NIPPON KAYAKU CO., LTD.),
VICTORTA BLUE BH (a product of HODOGAYA CHEMICAL CO.,
LTD.), ALIZARINE ASTROL (a product of TOKYO KASEI K.K.),
METHYL VIOLET PURE SP (a product of HODOGAYA CHEMICAL
CO., LTD.), GREEN lOP (a product of NIPPON KAYAKU CO.,
LTD.), etc.
The transparent substrate may be composed of
glass or other transparent organic crystal substrates, or
organic material like plastics. Since the sixth
embodiment of the invention forms silicon dioxide film
through lamination process, film having uniform thickness
can be produced regardless of the supelrficial shape of
the substrate, and therefore, the sixth embodiment also
allows formation of film of uniform thickness not only on
the plane transparent substrates, but on transparent
substrates having concaves and convexes on the surface.
Furthermore, the sixth embodiment is effectively
applicable to such substrate composed of polycarbonate
resin or acrylic resin as well. In this case, in order
to produce colored film having sufficient adhesive
strength, it is desirable that the surface of the organic
transparent substrate is initially'caated with at least a
kind of silicon compound selected from a group consisting
of organic silicon compound composed of silane°coupling
agent, hydrolyzate thereof and colloidal silica, and then
immersed in the processing solution before eventually
forming the silicon dioxide film containing organic
colorant.
In particular, the sixth embodiment can enhance
the decorative effect by providing a colored and
colorless portions to a mirror of which configurations




- 59 -
show themselves like characters, numerals, figures, or
patterns, wherein the colored and colorless portions are
provided by forming silicon dioxide film on the substrate
on which a mask is applied before film forming, and
thereafter metal film is formed on the silicon dioxide
film.
In this case, the figurative portion may be
present in either of the colored and the colorless
portions. Furthermore, the partially colored mirror is
obtained by forming silicon dioxide film on the whole
surface of the transparent substrate and applying a mask
on the film, and thereafter removing the film not masked
by chemical etching or mechanical abrasion.
Seventh Embodiment
The seventh embodiment of the present invention
utilizes a method for forming silicon dioxide film
containing organic colorant such as dyestuff or pigment
on glass having concaves and convexes in which the glass
is contacted with processing solution prepared by adding
organic colorant such as dyestuff or pigment to
hydrosilicofluoric aoid solution supersaturated with
silicon dioxide. The hydrosilicofluoric acid solution
containing supersaturated silicon dioxide can be prepared
by adding boric acid, aqueous ammonia. metal halide or
metal of which ionization tendency is greater than that
of hydrogen to the hydrosilicofluoric acid solution
saturated with silicon dioxide: Alternatively, the
hydrosilicofluoric acid solution supersaturated with
silicon dioxide can be prepared by raising temperature of
the solution after adding silicon dioxide to the
hydrosilicofluoric acid solution held at a low
temperature (this is called "temperature-differentiation
method"). Water-soluble oxganic colorants can directly
be added to the above so7.ution. Water-insoluble organic
colorants can also be added to the solution after being
dissolved in water-mi cible organic solvent Like
alcohol. Organic colorants can be added to the



~~al_ ~ ~~~~
- 60 -
hydrosilicofluoric acid solution saturated with silicon
dioxide or it may also be added to the solution after the
solution is supersaturated with silicon dioxide. In the
seventh embodiment, the concentration of
hydrosilicofluoric acid is not less than 1.0 mo1/L,
desirably from 1.5 to 3.0 mol/L is used. The temperature
of the processing solution at the time of contact with
the glass is from 15 to 60°C, desirably from 25 to
40°C. When the temperature°differentiation method is
applied, normally, silicon dioxide is saturated not more
than 10°C. And then, the glass is contacted with the
processing solution of the temperature not less than
20°C, desirably from 40 to 60°C. Generally, the glass is
contacted with the processing solution while being
dispersed and. stirred in the solution.
Example of organic colorants axe dyestuffs and
pigments such as DIACELLITON FAST RED R (a product of
MITSUBISHI CHEMICAL INDUSTRIES LTD.), BLUE 5P (a product .
of NIPPON KAYAKU CO., LTD.), RHODAMINE 6G, FLUORESCEIN,
MALACHITE GREEN (a product of HODOGAYA CHEMICAL CO.,
LTD.), COUMARINE 6, SULFORHODAMINE B, RHODAMINE 19,
RHODAMINE 110, RHODAMINE 116, RHODAMINE 123, KAYACYL
YELLOW GG (a product of NIPPON KAYAKU CO., LTD.), RED 21P '
(a product of NIPPON KAYAKU CO., LTD.), ACRDINE RED,
KAYACYL RHODAMINE FB (a product of NIPPON KAYAKU CO.,
LTD.), RED 3P (a product of NIPPON KAYAKU CO., LTD.),
VICTORIA BLUE BH (a product of HODOGAYA CHEMICAL CO.,
LTD.), ALIZARINE ASTROL (a product of TOKYO KASEI K.K.),
METHYL VIOLET PURE SP (a product of HODOGAYA CHEMICAL
CO., LTD.), GREEN.lOP (a product of NIPPON KAYAKU CO.,
LTD.), etc.
The seventh embodiment of the invention is
effectively applicable to those glass substrates having
concaves and convexes on the surface including the
following: templane glass sheets or plane glass sheets
which are initially coated with colored melted glass
solution having low melting point by providing figurative
pattern and finally solidified, mechanically processed




- 61 -
glass such as ground glass or sand-blasted glass, or such
glass having the surface etched with anyone of
hydrofluoric acid solutions, where mast of these glass
sheets having concaves and convexes surface are used fox
decoration, elimination of see-through visibility, and
glare-proof.
Eiqhth Embodiment
Inventors followed up study on the
aforementioned problems related to the technique of
coloring on the metallic surface. As a result, inventors
successfully produced a colored film which were
chemically and mechanically stable by forming a silicon
dioxide film containing organic colorant on an inorganic
film which were previously provided on a metal substrate,
wherein characteristics of organic colorants, i.e., a
wide variety of sorts of color and brilliancy of colors
were made best use of. An thus, inventors eventually
achieved the eight embodiment of the present invention
which almost solves those problems inherent to
conventional art.
When implementing the above novel art,
inorganic compound film can be composed of the
superficial oxidized layer or sulfurated layer prepared
by chemical treatment for the metal surface. The
inorganic compound film may also be composed of anode°
oxidized layer that can be formed electrochemically. To
modify the metal surface, conventional chemical treatment
and anode oxidation treatment are available. In place of
the modified surface layer mentioned above, inorganic
compound film formed on the metal surface can be
available. In this case, as inorganic compound, majority
of inorganic compound including oxides such as Si02,
Ti02, Zr02, Fe203, Cr2C3, A1203.'CoO~ Coz03, NiO, and
Ta203; carbides such as SiC and TiC; nitride such as
Si3N4, TiN and CrN. ~iowever, in the light of the
decorative effect, that is, metal-skin visibility, it is
desirable that oxides having good light permeability are
used. On the other, hand, taking the adhesiveness to the



-- 62 -
silicon dioxide film containing organic colorant into
account, inorganic compounds containing silicon such as
Si02, SiO, Si3N~, or metallic silicide are preferred.
Needless to say, any of these inorganic compounds can be
used alone, and also mixture thereof can be used.
Furthermore, the eighth embodiment of the
invention allows the use of film composed of any of those
inorganic compounds dispersed in organic material.
Any of the conventional film formation methods
such as spraying method, CVD method, dipping method,
vacuum deposition method, sputtering method, ion-plating
method, or plating method, can be used for forming such
inorganic compounds mentioned above. These conventional
method are well known to the persons pertain to the art,
and therefore, detail explanation is omitted.
As is conventionally suggested, however, it is
desirable, that dispersion plating method is used fox the
formation of organic film containing medium composed of
inorganic compound, i.e., complex film.
As metal substrate, not only genuine metal
substance, but also a substrate composed of inorganic or
organic material of which surface coated with metallic
film can be used. There is no limitation to the
configuration available for these substrates. Examples
of the configuration are plane shape, curved shape.
shpere, or fine particle, and the ~.ike.
As to the film formation of silicon dioxide
containing, the eighth embodiment of the invention
utilizes a method for forming silicon dioxide film
containing organic colorant such as dyestuff or pigment
on the metal substrate coated with inorganic compound in
advance in which the metal substrate is contacted with
processing solution prepared by adding organic colorant
such as dyestuff or pigment to lhydrosilicofluoric acid
solution supersaturated with silicon dioxide. The
hydrosilicofluoric acid solution containing
supersaturated silicon dioxide can be prepared by adding
boric acid, aqueous ammonia, metal halide or metal of



- 63
cahich ionization tendency is greater than that of
hydrogen to the hydrosilicofluoric acid solution
saturated with silicon dioxide. Alternatively, the
hydrosilicofluoric acid solution supersaturated with
silicon dioxide can be prepared by raising temperature of
the solution after adding silicon dioxide to the
hydrosilicofluoric acid solution held at a low
temperature (this is called "temperature-differentiation
method"). Water-soluble organic colorants can directly
be added to the above solution. Water-insoluble organic
colorants can also be added to the solution after being
dissolved in water-miscible organic solvents like
alcohol. Organic colorants can be added to the
hydrosilicofluoric acid solution saturated with silicon
dioxide or it may also be added to the solution after the
solution is supersaturated with silicon dioxide. Tn the
eighth embodiment, the concentration of
hydrosilicofluoric acid is not less than 1.0 mol/L,
desirably from 1.5 to 3.O mo1/L is used. The temperature
of the processing solution at the time of contact with
the metal is from 15 to 60°C, desirably from 25 to
40°C. When the temperature-differentiation method is
applied, normally, silicon dioxide is saturated at not
more than 10°C. And then, the metal is contacted with
the processing solution of the temperature at not less
than 20°C, desirably from 40 to 60°C. Generally, the
metal is contacted with the processing solution while
being dispersed and stirred in the solution.
Examples of organic colorants are dyestuffs and
pigments such as DIACELLITON FAST RED R (a product of
MITSUBISHI CHEMICAL INDUSTRIES LTD.) BLUE 5P (a product
of NIPPON KAYAKU CO., LTD.), RHODAMINE 6G, FLUORESCEIN,
MALACHITE GREEN (a product of HODOGAYA CHEMICAL CO.,
LTD.), COUMARINE 6, SULFORHODAMINE B, RHODAMINE 19,
RHODAMINE 110, RHODAMINE 116,,RHODAMINE 123, KAYACYL
YELLOW GG (a product of NIPPON KAYAKU CO.. LTD.), RED 21P
(a product of NIQPON KAKAKU CO., LTD.), ACRDINE RED,
KAYACYL RHODAMTNE FH (a product of NIPPON KAYAKU CO.,




- 64 -
LTD.), RED 3P (a product of NIPPON KAYAKU CO., LTD.),
VICTORIA BLUE BH (a product of HODOGAYA CHEMICAL CO.,
LTD.), ALIZARINE ASTROL (a product of TOKYO KASEI K.K.),
METHYL VIOLET PURE SP (a product of HODOGAYA CHEMICAL
CO., LTD.), GREEN lOP (a product of NIPPON KAYAKU CO.,
LTD.), etc.
Ninth Embodiment
Inventors followed up study on the
aforementioned problems related to the covering glass
sheets available for clocks and wrist watches, and
finally found that coloration of these covering glass
sheets was achieved without problem by bringing the
covering glass complete with the chemical strengthening
process into contact with the processing solution
prepared by adding organic colorant to the
hydrosilicofluoric acid solution containing
supersaturated silicon dioxide. The hydrosilicofluoric
acid solution containing supersaturated silicon dioxide
can be prepared by adding boric acid, aqueous ammonia,
metal halide or metal of which ionization tendency is
greater than that of hydrogen to the hydrosilicofluoric
acid solution saturated with silicon dioxide.
Alternatively, the hydrosilicofluoric acid solution
supersaturated with silicon dioxide can be prepared by
raising temperature of the solution after adding silicon
dioxide to the hydrosilicofluoric acid solution held at a
low temperature (this is called "temperature-
differentiation method"). Water-soluble organic
colorants can directly be added to the above solution.
Water-insoluble organic colorants can also be added to
the solution after being dissolved in water-miscible
organic solvent like alcohol. The organic colorant can
be added to the hydrosilicofluoric acid solution
saturated with silicon dioxide or it may also be added to
the solution after the solution is supersaturated with
silicon dioxide. In the ninth embodiment, the
concentration of hydrosilicofluoric acid is not less than



- 65 --
1.0 mol/L, desirably from 1.5 to 3.0 mol/L is used. The
temperature of the processing solution at the time of
contact with the covering glass is from 15 to 60°C,
desirably from 25 to 40°C. When the temperature-
s differentiation method is applied, normally, silicon
dioxide is saturated at not more than 10°C. And then,
the covering glass is contacted with the processing
solution of the temperature at not less than 20°C,
desirably from 40°C to 60°C. Generally, the covering
glass is contacted with the processing solution while
being dispersed and stirred in the solution.
Example of organic colorants are dyestuffs and
pigments such as DIACELLITON FAST RED R (a product of
MITSUBISHI CHEMICAL INDUSTRIES LTD.), BLUE 5P (a product
of NIPPON KAYAKU CO., LTD.), RHODAMINE 6G, FLUORESCEIN,
MALACHITE GREEN (a product of HODOGAYA CHEMICAL CO.,
LTD.), COUMATTNE 6, SULFORHODAMTNE B, RHODAMINE 19,
RHODAMINE 110, RHODAMINE 116, RHODAMINE 123, KAYACYL
YELLOW GG (a product of NIPPOD1 KAYAKU CO., LTD.), RED 21P
(a product of NIPPON KAYAKU CO., LTD.), ACRDTNE RED,
KAYACYL RHODAMINE FB (a product of NIPPON KAYAKU CO.,
LTD.), RED 3P (a product of NIPPON KAYAKU CQ., LTD.),
VICTORIA BLUE BH (a product of HODOGAYA CHEMICAL CO.,
LTD.), ALIZARINE ASTROL (a product of TOKYO KASEI K.K.),
METHYL VIOLET PURE SP (a product of HODOGAYA CHEMICAL
CO., LTD.), GREEN lOP (a product of NIPPON KAYAKU CO.,
LTD.)r etc.
In constrast with any conventional film
produced by the sol-gel method, the silicon dioxide film
containing organic colorant produced by executing these
serial steps mentioned above is extremely dense without
defects such as foams.
The ninth embodiment of the invention allows y
the formation of the silicon dioxide film containing
organic colorant in the processing solution uniformly
prepared. Since the reaction fox the formation of the
film goes on in the vicinity of the room temperature, the
organic colorant in the solution is uniformly introduced




- 66 -
into the film without decomposition.
Furthermore, since the silicon dioxide film
formed by the ninth embodiment of the invention is
extremely dense and firmly adheres to the substrate, no
thermal treatment is required. Since the film is formed
by precipitation from the supersaturated solution of
silicon dioxide, the silicon dioxide film containing
organic colorant achieved by the ninth embodiment of the
invention is almost free from impurities such as
undecomposed raw material or solvent.
Furthermore, since the film is formed by
growing itself on the surface in the film forming process
according to the ninth embodiment, uniform thickness of
colored layer is formed even on the curved surface unlike
the conventional coating method causing uneven thickness
of colored layer.
Still further, it was found by the inventors
that extremely durable and dense silicon dioxide film
containing organic colorant was successfully formed under
a low temperature (desirably in a range from 25°C to
60°C) which does not affect the chemically promoted
strength. Inventors also found that the chemical
durability was significantly improved chemical durability
of organic colorant which was naturally lack of chemical
durability by being contained in inorganic compound, i.e,
silicon dioxide. Furthermore, as is typically
represented by dyestuff or pigment, the organic colorant '
has a wide variety of available kinds of color and
brilliancy, so that even those warm colors can easily be
developed by effectively applying organic colorant which
is not realized by the conventional method.
Application of organic fluoresoent colors or
photochromic colors significantly enhances the decorative
function of clocks and wrist watches by means of the
colored covering glass.
As is clear from the above description,. the
ninth embodiment of the invention has almost perfectly
consummated the art of coloring glass substrate Covering



. ,,.
v . c.5 ';., <...j J
- 67 -
clocks and wrist watches of which realization is
considered to be almost difficult.
BRIEF DESCRIPTION OF TEH DRAWINGS
Fig. 1 is a graph showing the result of the
etching the silicon dioxide film A containing organic
colorant embodied by the invention and a comparative film
B formed by the conventional method;
Fig. 2 is the schematic illustration of the
silicon-dioxide film forming apparatus employed for
embodying the invention;
Figs. 3 to 5 respectively designate
transmission spectra of red glass, green glass, and blue
glass; and
Figs. 6 to 8 respectively designate reflection
spectra from colored mirrors.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring more particularly to the following
examples of the invention, the invention is described
below. It should be understood that the invention is not
merely defined to the following examples unless departing
from the essential spirit and scope of the invention.
Examples of the Invention
Example 1
A plate of slide glass measuring 75 mm long, 25
mm wide, and 1 mm thick used as a test substrate which
had been cleaned and dried completely.
Various kinds of dyestuffs were mixed or
dissolved in distilled water at the room temperature to
produce an amount of 5 °s by weight or saturated additive.
Processing solution was prepared by either
adding 8 cc of 0.5 mo1/L boric acid water solution to 100
cc of hydrosilicofluoric acid solution saturated with
silica gel or dissolving 0.4 gram of metallic aluminium
into the same hydra~ilicofluoric acid solution. 1 cc of



,r,
a
68
each liquid additive was mixed with 100 cc of the
processing solution in a beaker which was in turn heated
in a water bath at 35°C after stirring. Then, the test
substrates were immersed in respective processing
solution and 16 hours later, removed out for cleaning and
dryout.
The list of additive dyestuffs and the test
result are shown in Table 2, in which the thickness of
each silicon dioxide film formed was measured by a
contacting probe type film thickness measuring
instrument.
It was acknowledged through analysis with ESCA
(Electron Spectroscopy for Chemical Analysis), SIMS
(Secondary Ion Mass Spectrometry) and IR (Infrared
Spectrophotometry), .these organic dyestuffs were
uniformly incorporated with their respective film.
In addition, each test substrate carrying the
film of silicon dioxide was kept immersed in a solution
of 99.5% ethanol for 24 hours, which result in no elution
of the dyestuffs. Also, no peeling-off of the silicon
dioxide film from the substrate was detected during tape
test and a sponge rubbing test
Table 2
Additive dyestuffs Film thickness (A) Colar tone
KAYACYL YELLOW GG 6055 Light yellow
MALACHITE GREEN 6345 Green
ALIZARINE ASTROL 8370 Light purple
Example 2
A plate of slide glass measuring 75 mm long, 25
mm wide, and 1 mm thick was used as a test substrate
which had been cleaned and dried completely.



~u
Each of laser colorants was mixed with or
dissolved in distilled water at the room temperature to
produce an amount of 5 % by weight or saturated liquid
additive. Also, processing solution was prepared by
either adding 8 cc of 0.5 mol/L boric acid water solution
to 100 cc of hydrosilicofluoric acid solution saturated
with silica gel or dissolving 0.4 g of metallic aluminium
into the same hydrosilicofluoric acid solution. 1 cc of
each liquid additive was mixed with 100 cc of the
processing solution in a beaker which was in turn heated
in a water bath at 35°C after stirring. Then, the test
substrates were immersed in respective processing
solution and 16 hours later, removed out for cleaning and
dryout.
The list of additive laser colorants and the
test result are shown in Table 3, in which the thickness
of each silicon dioxide film formed was measured by a
contacting probe type film thickness measuring
instrument.
It was acknowledged through analysis with ESCA,
SIMS, and IR that the laser colorants were uniformly
incorporated with their respective thin films. As to
RHODAMII3E 6G, fluorescence spectrum around 600 nm was
detected, so that it was confirmed that it had a function
of laser colorant. In addition, each test substrate
carrying the film of silicon dioxide was kept immersed in
a solution of 99.5 ethanol for 24 hours, which resulted
in no elution of the dyestuffs. Also, no peeling-off of
the silicon dioxide film from the substrate was detected
during a tape test and a sponge rubbing test.




i'~t~. 3 4.
~J' .: :~: o~ ':3
- 70 -
Table 3
Laser colorants Film thickness (A) Color tone
RHODAMINE 6G 1170 Red
ACRDINE RED 905 Red
FLUORESCEIN 4285 Yellow
Example 3
A plate of slide glass measuring 75 mm long, 25
mm wide, and 1 mm thick was used as a test substrate
which had been cleaned and dried completely.
Each of laser colorants was mixed with or
dissolved in distilled water at the room temperature to
produce an amount of 5 wt~ or saturated liquid
additive. Also; processing solution was prepared by
either adding 8 cc of 0.5 mol/L boric acid water solution
to 100 cc of hydrosilicofluoric acid solution saturated
with silica gel or dissolving 0.4 g of metallic aluminium
into the same hydrosilicofluoric acid aolution.' 1 cc of
each liquid additive was mixed with 100 cc of the.
processing solution in a beaker which was in turn heated
in a water bath at 35°C after stirring. Then, the test
substrates were immersed in respective processing
solution and 16 hours later, removed out for cleaning and
dryout.
The list of additive laser colorants and the
test result are shown in Table 4, in which the thickness
of each silicon dioxide fzlm formed was measured by a
contacting probe type film thickness measuring
instrument.
It was acknowledged through analysis with ESCA,
SIMS, and IR that the laser colorants were uniformly
incorporated with their respective thin,films.
Fluorescence was deter ed from each film containing




si3 s~ 'a ~ '" r
P~ ~.LS~ y~ ~~
- 71 -
colorant by radiating excitation light fox each colorant
contained in the film, so that it was confirmed that each
colorant had function of laser colorant. In addition,
each test substrate carrying the film of silicon dioxide
was kept immersed in a solution of 99.5% ethanol for 24
hours, which resulted in no elution of the dyestuffs.
Also, no peeling-off of the silicon dioxide film from the
substrate was detected during a tape test and a sponge
rubbing test.
Table 4
Laser colorants Film thickness (A) Color tone
RHODAMINE 110 5095 Light orange


RHODAMINE 116 5275 Orange


RHODAMINE B 3660 Red purple


RHODAMINE 123 3515 Yellow


RHODAMINE 19 5005 Red


RHODAMINE 6G 3595 Red


SULFORHODAMINE B 1585 Red purple


ACRDINE RED 3868 Red


FLUORESCEIN 4218 Yellow


Example 4
A plate of slide glass measuring 75mm long,
25inm wide, and lmm thick was used as a test substrate
which had been cleaned and dried completely.
A portion of disperse dye known as Diaseritone
First Red, a trade name (of Mitsubishi Chemical
Industries, Ltd.) was dispersed in distilled water at the
room temperature to produce an amount of 5 wt% liquid
additive.
Processing solution was prepared by dissolving
0.4 g of metallic aluminium into 100 cc of
hydrosilicofluoric acid solution saturated with silica
gel. The processing liquid was mixed together with 1 ca
of the disperse dye in a beaker which was in turn heated




7
in a water bath at 35°C after stirring. Then, the test
substrate was immersed in the processing liquid and 16
hours later, removed out far cleaning and dryout.
As the result, a film of silicon dioxide in red
color was formed on the substrate having a thickness of
7605 A measured with a contacting probe type film
thickness measuring instrument.
It was then acknowledged through analysis with
ESCA, SIMS, and IR that the disperse dye was uniformly
incorporated with the thin film. In addition, the test
substrate carrying the film of silicon dioxide was kept
immersed in a solution of 99.5 ~ ethanol for 24 hours,
which resulted in no elution of the disperse dye.
Also, no peeling-off of the silicon dioxide
film from the substrate was detected during a tape test
and a sponge rubbing test.
Example 5
A plate of slide glass measuring 75mm long,
25mm wide, and lmm thick was used as a test substrate
which had been cleaned and dried completely.
A portion of RHODAMINE 6G (laser,colorant) was
mixed with or dissolved in distilled water at the room
temperature to produce an amount of saturated or 5 wt~
liquid additive.
Processing liquid was made by dissolving 0.4 g
of metallic aluminium into 100 cc of hydrosilicofluoric
acid solution saturated with silica gel. 100 cc of the
processing liquid was mixed together with l cc of the
liquid additive in a beaker which was in turn heated in a
water bath at 35°C after stirring. Then; the test
substrate was immersed in the processing solution and 16
hours later, removed out for cleaning and dryout. A
resultant thin film on the substrate was designated as a
specimen A.
For the purpose of; comparison, another thin
film of organic substance containing silicon dioxide was
made by a sol-gel method: Thbre were provided 50 g of



s~ >'1:~: ~ f~ ~ J
- 73 -
ethyl silicate [Si(OC2H5)4], 75.2 g of ethanol [C2H50H],
0.6 g of 35% hydrochloric acid, 47 g of water, and 0.1 g
of RHODAMiNE 6G which were all mixed up for one hour to
produce a solution. After the solution was left aside
for one hour, a test substrate was dipped in the solution
and then pulled out by 1.5 mm/sec, so as to form a thin
film thereon. The thin film was dried out at the room
temperature in the atmosphere for about 16 hours and
then, heated up at 110°C for 7 hours. The substrate
designated as a specimen B.
Etch-rate of silicon dioxide film of the
specimens A and B were measured at a temperature of 22°C
using a solution of 1/10 diluted P-ETCH (48% HF:70o
HN03:H20 = 3:2:60).
The result is shown in Fig. l, in which the
specimen A is smaller in the etch-rate and thus, higher
in density than B.
Example 6
A plate of slide glass measuring 75mm long,
25mm wide, and lmm thick was used as a test substrate
which had been cleaned and dried completely.
Each of given dyestuffs different in property
was mixed with or dissolved in distilled water at the
room temperature to produce an amount of 5 wto or
saturated liquid additive. Also, processing liquid was
made by either adding 8 cc of 0.5 mol/W boric acid water
solution to 100 cc of hydrosilicofluoric acid solution
saturated with silica gel or dissolving 0.4 g of metallic
aluminium into the same hydrosilicofluoric acid
solution. 1 cc of each dyestuffs additive liquid was
mixed with 100 cc of the processing liquid in a beaker
which was in turn heated in a water bath at 35°C after
stirring. Then, the test substrates were immersed in
respective processing solutions and 16 hours later,
removed out for cleaning and dryout.
The list of additive dyestuffs and the test
result are shown in Table 6, in which the thickness of




- 7 4 - ~ ~~ .~ ~ %:3 ~ i~
each silicon dioxide film formed was measured by a
contacting probe type film thickness measuring
instrument.
It was acknowledged through analysis with ESCA,
SIMS, and IR that the dyestuffs were uniformly
incorporated with their respective thin films. In
addition, each test substrate carrying the film of
silicon dioxide was kept immersed in a solution of 99.5%
ethanol for 24 hours, which resulted in no elution of
organic dyestuffs. Also, no peeling-off of the silicon
dioxide film from the substrate was detected during a
tape test and a sponge rubbing test.
Table 6
Additive dyestuffs Film thickness (A) Color tone
KAYACYL RHODAMINE FB 4200 Red
METHYL VIOLET PURE SP 7700 Light blue
VTCTORIA PURE BLUE BOH 4700 Yellow green
VICTORIA BLUE BH 8100 Blue green
Example 7
A plate of slide glass measuring 75mm long,
25mm wide, and lmm thick was used as a test substrate
which had been cleaned and dried completely.
Each of given dyestuffs was mixed with or
dissolved in distilled water at the room temperature to
produce an amount of 5 wt% or saturated liquid
additive. Also, processing solution was prepared by
either adding 8 cc of 0.5 mo1/L boric acid water solution
to 100 cc of hydrosilicofluoric acid solution saturated
with silica gel or dissolving 0.4 g of metallic aluminium
into the same hydrosilicofluoric acid solution. l cc of
each liquid additive was mixed with l00 cc of the
processing solution in a beaker which was in turn heated
in a water bath at 35°C after stirring. Then, the test




a . ~ s~ ~-~. r. d
~. ~ .~~. :w ~s J a
- 75 -
substrates were immersed in respective processing
solution and 16 hours later, removed out for cleaning and
dryout.
The list of additive dyestuffs and the test
result are shown in Table 7, in which the thickness of
each silicon dioxide film formed was measured by a
contacting probe type film thickness measuring
instrument.
It was acknowledged through analysis with ESCA,
SIMS, and IR that the dyestuffs were uniformly
incorporated with their respective thin films. In
addition, each test substrate carrying the film of
silicon dioxide was kept immersed in a solution of 99.5%
ethanol for 24 hours, which resulted in no elution of
dyestuffs. Also, no peeling-off of the silicon dioxide
film from the substrate was detected during a tape test
and a sponge rubbing test.
Table 7
Additive dyestuffs Film thickness (.) Color tone
BLUE 5P 2000 Blue
RED 21P 6800 Light yellow
RED 3P 7200 Light red
GREEN lOP 2900 Yellow green
Example 8
A plate of slide glass measuring 75 mm long,
25mm wide, and lmm thick was used as a test substrate
which had been cleaned and dried completely.
Each of different laser colorant was mixed with
or dissolved in distilled water at the room temperature
to produce an amount of 5 % by weight or saturated liquid
additive. Also, processing liquid was made by either
adding 8 cc of 0.5 mol/L boric acid water solution to 100
cc of hydrosilicofluoric acid solution saturated with



- ~.~~~a
silica gel or dissolving 0.4 g of metallic aluminium into
the same hydrosilicofluoric acid solution. 100 cc of the
processing solution was mixed with 1 cc of each colorant
additive liquid in a beaker which was in turn heated in a
water bath at 35°C after stirring. Then, the test
substrates were immersed in respective processing
solutions and 16 hours later, removed out for cleaning
and dryout.
The list of additive laser colorants and the
test result are shown in Table 8, in which the thickness
of each silicon dioxide film developed was measured by a
contacting probe type film thickness measuring
instrument.
It was acknowledged through analysis with ESCA,
SIMS, and IR that the laser colorants were uniformly
incorporated with their respective thin films. When a
beam of excitation light was applied to each thin film
associated with a laser colorant, fluorescent light
emitted displaying the function of the laser colorant.
In addition, each test substrate carrying the film of
silicon dioxide was kept immersed in a solution of 99.5%
ethanol for 24 hours, which resulted in no elution of the
colorants. Also, no peeling-off of the silicon dioxide
film from the substrate was detected during a tape test
and a sponge rubbing test.
Table 8
Laser colorants Film thickness Color tone
(A)



2,5-diphenyloxazole 3840 Colorless


1,4-bis[2-(5-phenyl-
oxazolyl)]benzene 5840 Colorless


2-(1-naphthyl)-5.
S5 phenyloxazole 5080 Colorless


COUMARIN 6 4800 Dark orange


NK-125 1500 Light green







~, ,.,~ -;~ ..~. ~.._
- 7 7 - ~,r a:l: .:~ ~~:i~ ':'~ ~J i i
Example 9
A plate of slide glass measuring 75mm long,
25mm wide, and lmm thick was used as a test substrate
which had been cleaned and dried completely.
Processing solution was made by dissolving 0.4
g of metallic, aluminium into 100 cc of hydrosilicofluoric
acid solution saturated with silica gel. 0.01 g of each
of given dyestuffs was mixed with 100 cc of the
processing solution in a beaker which was in turn heated
in a water bath at 35°C after proper stirring. TG-21 was
first mixed with a concentrated acetic acid solution and
added to the processing solution. Then, the test
substrates were immersed in respective processing
solution and 16 hours later, removed out for cleaning and
dryout.
The list of additive dyestuffs and the test
result are shown in Table 9, in which the thickness of
each silicon dioxide film formed was measured by a
contacting probe type film thickness measuring
instrument.
It was acknowledged through analysis with ESCA,
SIMS, and IR that the dyestuffs were uniformly
incorporated with their respective thin films. In
addition, each test substrate carrying the film of
silicon dioxide was kept immersed in a solution of 99.5
ethanol for 24 hours, which resulted in no elution of the
dyestuffs. Also, no peeling-off of the silicon dioxide
film from the substrate was detected during a tape test
and a sponge rubbing test.
Table 9
Additive dyestuffs Film thickness (~) Color tone
TG 21 5600 Hlack
PSD-HR 4700 Red
PSD-O 10400 Orange




-° 78
Example 10
A plate of slide glass measuring 75mm long,
25mm wide, and lmm thick was used as a test substrate
which had been cleaned and dried completely.
Processing solution was made by dissolving 0.4
g of metallic aluminium into 100 cc of hydrosilicofluoric
acid solution saturated with silica gel. 0.05 g of each
of given dyestuff was mixed with 100 cc of the processing
solution in a beaker which was in turn heated in a water
bath at 35°C after proper stirring. Then, the test
substrates were immersed in respective processing
solution and 16 hours later, removed out fox cleaning and
dryout.
The list of additive dyestuffs and the test
result are shown in Table 10, in which the thickness of
each silicon dioxide film formed was measured by a
contacting probe type film thickness measuring
instrument.
It was acknowledged through analysis with ESCA,
SIMS, and IR that the dyestuffs were uniformly
incorporated with their respective thin films. In
addition, each test substrate carrXing the film of
silicon dioxide was kept immersed in a solution of 99.5%
ethanol for 24 hours, which resulted in no elution of the
dyestuff. Also, no peeling-off of the silicon dioxide
film from the substrate was detected duzing a tape test
and a sponge rubbing test.


2~3:~
- 79 -
Table 10
Additive dyestuffs Film thickness (~) Color tone
TPP 4900 Yellow green


NK-78 2600 Colorless


NK-123 3000 Yellow


NK-863 3800 Colorless


NK-1144 4200 Light yellow


NK-1331 960 Colorless


Example 11
A plate of slide glass measuring 75mm long,
25mm wide, and lmm thick was used as a test substrate
which had been cleaned and dried completely.
Each of given dyestuffs was mixed with or
dissolved into distilled water at the room temperature to
produce an amount of 5 % by weight or saturated liquid
additive. Also, processing solution was made by
dissolving 0.4 g of metallic aluminium into 100 cc of
hydrosilicofluoric acid solution saturated with silica
gel. 100 cc of the processing solution was mixed with 1
cc of each dyestuff additive liquid in a beaker which was
in turn heated in a water bath at 35°C after stirring.
Then, the test substrates were immersed in respective
processing solution and l6 hours later, removed out for
cleaning and dryout.
The list of additive dyestuff and the test
result are shown in Table 11. in which the thickness of
each silicon dioxide film formed was measured by a
contacting probe type film thickness measuring
instrument.
It was acknowledged through analysis with ESCA,
SIMS, and IR that the dyestuffs were uniformly
incorporated with their respective thin films. In
addition, each test substrate carrying the film'of
silicon dioxide ways kept immersed in a solution of 99.5%



_ so
ethanol for 24 hours, which resulted in no elution of the
dyestuff. Also, no peeling-off of the silicon dioxide
film from the substrate was detected during a tape test
and a sponge rubbing test.
Table 11
Additive dyestuffs Film thickness (~) Color tone
. RED T-BLH 1100 Light pink


RED GTLH 2800 Light pink


BLUE T-BLH 500 Purple


YELLOW TRLH 1500 Light yellow


YELLOW 7GLH 2900 Dark yellow


lOGFH 1450 Yellow green


BLACK MH 4000 Bronze


BLACK CD-BLH 1000 Yellow


BLACK 8H 350 Black


Example 12
A plate of slide glass measuring 75mm long,
25mm wide, and lmm thick was used as a test substrate
which had been cleaned and dried completely.
Each of gzven laser colorants was dissolved
into ethanol at the room temperature to produce an amount
of 0.01 mol/1 or saturated liquid additive. Also,
processing solution was made by dissolving 0.4 g of
metallic aluminium into 100 cc of hydrosilicofluoric acid
solution saturated with silica gel. 100 cc of the
processing solution was mixed with l cc of each colorant
solution in a beaker which was in turn heated in a water
bath at 35°C after stirring. Then, the test substrates
were immersed in respective processing solution and l6
hours later, removed out for cleaning and dryout.
The list of add~.tive laser colorants and the
test result are showy in Table 12, in which the thickness
of each silicon dioxide film developed was measured by a



- 81 -
contacting probe type film thickness measuring
instrument.
It was acknowledged through analysis with ESCA,
SIMS, and IR that the laser colorants were uniformly
incorporated with their respective thin films. When a
beam of excitation light was applied to each thin film
associated with a laser colorant, fluorescent light
emitted displaying the function of the laser colorant.
Iri addition, each test substrate carrying the film of
silicon dioxide caas kept immersed in a solution of 99.5%
ethanol for 24 hours, which resulted in no elution of the
laser colorant. Also,. no peeling-off of the silicon
dioxide film from the substrate was detected during a
tape test and a sponge rubbing test.
Table 12
Laser colorants Film thickness (A) Color tone
COUMARIN 504 7700 Yellow


COUMARIN 521 8800 ~ Yellow


COUMARIN 523 8500 Colorless


COUMARIN 525 8750 Orange


COUMARIN 535 ~ 8300 Colorless


COUMARIN 540A 7100 Light yellow


FLUOL 555 8300 Yellow


Accordingly, the present invention provides the
following advantages:
1. The formed thin film of silicon diAxide
containing an organic colorant. is improved in density,
allowing no defect such as air'bubbles to be developed
therein.
2. The fabrication of silicon dioxide thin
films associated with organic colorant is carried out at
about the room temperature without heat-up process at a
high temperature and thus, applicable for making a thin



- 82 -
film of thermally decomposable organic colorant.
3. The silicon dioxide thin film containing an
organic coloring agent includes a less amount of
impurities.
4. The materials to be used are less in price,
reducing the cost of production.
5. The silicon dioxide thin film containing an
organic colorant can be formed on any substrate of
complex shape.
E~~camples of the First Embodiment
The first embodiment of the present invention
will be described in detail. It should also be
understood that the first embodiment of the present
invention is not limited to the examples without
departing the scope thereof.
Example 13
A polyethylene terephthalate film known as "OP-
3" (of Teijin Limited), which is 100 mm in length and
width and 100 um in thickness (and at one side, provided
:with a resin primer layer of 0.1 um thickness) was
immersed in a solution (containing about 0.9 ~ by weight
of silicon compound) made by dissolving a mixture
(D/C=0.22) of 1.5 g of Y-methacryloxypropyltrimethoxy-
silane and 3 g of CSGL-0803P (a hydrolysis of
tetraethoxysilane available from CFILSSO CORPORATTON,
having a solid substance of 8 ~ in concentration) into
250 ml of a mixture solvent medium comprising ethanol,
isopropyl alcohol, and n-butyl alcohol at a (volume)
ratio of 5:3:2. The polyethylene terephthalate film was
then removed out at a speed of l5 cm/min and dried out at
50°C with a hot dryer oven for an hour. zn the same
process, a thin film of silicon compound was formed on a
glass substrate and its thickness was about 10 nmo
The "OP-3" film coated with an organic silicon
compound layer was used with an apparatus of making




~~r~~j
- 83 -
silicon dioxide thin film, as shown in Fig. 2, for
developing thereon color layers of silicon dioxide thin
film containing organic coloring agents listed in Table
13.
Table 13
Additive dyestuffs Film thickness (~) Color tone


KAYACYL YELLOW GG 5700 Light yellow


RED 21P 8350 Light yellow


KAYACYL RHODAMINE FB 3400 Red


RED 3P 7390 Light red


- _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _
_ _


VICTORIA BLUE BH 8950 Blue green


VICTORIA PURE BLUE BOH 5300 Yellow green


MALACHTTE GREEN 5950 Gre2n


GREEN lOP 4000 Y211ow green


- _ _ _ _ _ _ _ _ _ _ _ _ _ - _ - - _ _ _ _ _


METHYL VIOLET PURE 7750 Light blue


BLUE SP 2100 Blue


ALIZARINE ASTROL 8100 Light purple



In Fig.2, an immersing tank compr ises an outer


tank 1 and an inner tank 2, being filledth water 3
wi


between the outer and inner tanks 1 The Water 3
and 2.


remains heated to 40C by a heater 4 irred for
and st


uniform thermal dispersion. The inner 2 comprises a
tank


front section 6, an intermediate'sectionand a rear
7,


section 8, each section being,filled .5 liters of
with 6


2.5 mol/1 hydrosilicofluoric acid solutionwith .


dissolution and saturation of silicon
dioxide-of which


source of supply was industrial szlica powder.
gel


Further, the solution was added with
a water salution


having 5 ~ by weight of a dyestuffs in Table l lcc
listed






- 84 -
per 100 cc of hydrosilicofluoric acid solution. The
coloring of the substrate was carried out for each
dyestuff processing solution which was replaced with new
one in each cycle of the operation.
The coloring operation was commenced with a
circulation pump 10 actuated for circulating the water
solution from the rear section 8 of the inner tank 2
through a filter 11 back to the front section 6.
Three plates of aluminium 12 measuring 50 mm
long, 50 mm wide, and 3 mm thick were immersed into the
solution of the rear section 8 and maintained for 10
hours. Then, the solution was turned to a proper
processing solution containing a desired supersaturaing
rate of Si02. The filter 11 was adjusted to 1.5 um in
absolute filtering rate and the circulating flow of the
processing solution was set to 520 ml/min (namely about 8
$/min since the total volume of the processing solution
was about 6.5 liters). The plastic substrate coated with
silicon compound, namely, "OP-3" film 9 caas immersed
vertically into the solution of the intermediate section
7 of inner tank and maintained for 16 hours under the
foregoing condition (namely, the solution was circulated
at about 8 /min through the 1.5 um filter ll with three
of the aluminium plates remaining immersed) before
removed out fox cleaning. and dryout.
The list of employed dyestuffs and the test
result are shown in Table 13, in which the thickness of
each silicon dioxide film formed was measured by a
contacting probe type film thickness measuring
instrument.
It was acknowledged through the analysis with
Electron Spectroscopy for Chemical Analysis (ESCA)~
Secondary Ton Mass Spectrometry (STMS), and Infrared
spectrophotometry (IR) that the organic c7yeatuffs were
35' uniformly incorporated with their respective thin
films. In addition, each test substrate carrying the
film of silicon dioxide was kept'immersed in a solution
of 99.5 ethanol for 24 hours, whichresulted in no




_ $5 -
elution of the organic dyestuff.
The dyestuffs containing silicon dioxide films
developed on both the sides of the substrate which had
been coated with no resin primer layers, were easily
peeled off during a peel-off test using cellophane
tapes. However, when the primer coating was
preliminarily made on the substrate, the formed films
were kept intact without peeling-off even when pulled
upward in the same test.
When the polyethylene terephthalate film
carrying the die material containing silicon dioxide thin
films was immersed in boiling water for 10 minutes, the
dye material thin films on both sides or both colored
layers were completely removed off from the no resin
primer coated substrate, but kept intact on the
polyethylene terephthalate film coated at both the sides.
with the resin primer layers. Hence, the formed thin
films were proved having improved adhesion properties.
Example 14
In the same manner as Example 13, dyestuff
containing silicon dioxide thin films (of about 150 nm y
thickness) were formed on a polyethylene terephthalate
film of "OP-3", except that a processing solution was
prepared by dissolving a mixture of 1.5 g of y-
aminopropyltriethoxysilane and 1 g of vinyl-tris (s-
methoxyethoxy)silane into 250 ml of a mixture solvent
medium comprising ethyl alcohol, isopropyl alcohol, and
n-butyl alcohol at a (volume) ratio of 5:3:2 in this
order. In this Example, dyestuffs shpwn in Table 14 were
dissolved into ethanol at the room temperature to produce
a 5 ~ by weight liquid additive which was in turn added
to the hydrosilicofluoric acid solution at a ratio of 1
cc to 100 cc. The coloring operation was carried out in
each of the colorants listed in Table 14.
The types of the colorants and the test results
are shown in Table 14, in which the thickness of each
silicon dioxide film formed was measured by a cozitacting


~~~. ~~~~~)
86 _
probe type film thickness measuring instrument.
Table 14
Laser colorants Film thickness (~) Color tone
RHODAMINE 6G 1170 Red
ACRDINE RED 905 Red
FLUORESCEIN 4285 Yellow
It was acknowledged through the analysis with
ESCA, SIMS, and TR that the pigments were uniformly
incorporated with their respective thin films. As to
RHODAMINE 6G, a fluorescent spectrum of around 600 nm was
detected so that it was confirmed that it had a function
of the colorant. In addition, each test substrate
carrying the film of silicon dioxide was kept immersed in
a solution of 99.5 % ethanol for 24 hours, which resulted
in no elusion of the organic dyestuff.
The silicon dioxide films containing colorants
formed on the sides of the substrate which had been
coated with no resin primer layers, were easily peeled
off during the peel-off test using cellophane tapes
However, when the primer coating was preliminarily coated
on the substrate, the formed films were kept intact
providing a high degree of adhesion.
When the polyethylene terephthalate film
carrying the silicon dioxide films containing the
colorants were immersed in boiling water for 1O minutes,
the silicon dioxide films containing the colorants on the
sides which had been coated with no resin primer layers
were completely removed off from the substrate: On the
other hand, the silicon dioxide film formed on the side
which had been coated with xesin primer layers were kept
intact. As a result, the formed films were proved having



7 _
improved adhesion properties.
Example 15
In the same manner as Example 13, silicon
dioxide films (of about 150 nm thickness) containing
colorants were formed on a polyethylene terephthalate
film of "TE#100(U02-)" (a product of Diawheel), in place
of "OP-3", which is 100 um in thickness (and has at one
side a resin primer layer of 0.1 um thickness).
l0 The types of laser colorants and the test
result are shown in Table 15, in which the thickness of
each silicon dioxide film formed was measured by a
contacting probe type film thickness measuring
instrument.
Table 1S
Laser colorants Film thickness (A) Color tone
RHODAMINE 110 5095 Light orange


RHODAMINE 116 5275 Orange


RHODAMINE B 3660 Red purple


RHODAMINE 123 8515 Yellow


RHODAMINE 19 5005 Red


RHODAMINE 6G 3595 Red


SULFORHODAMINE B 1585 Red purple


ACRDINE RED 3868 Red


FLUORESCEIN 4218 Yellow


COUMARIN 6 4800 Daxk orange


It was acknowledged through the analysis with
ESCA, SIMS, and IR that the laser colorants were
uniformly incorporated with their respective films. When
excitation light fox each colorants was radiated to each
film containing colorants. fluorescence was detected, so
that it was confirmed that it had a function of the laser
colorants. In addition, each test substrate carrying the




film of silicon dioxide was kept immersed in a solution
of 99.5 % ehanol for 24 hours, which resulted in no
elusion of the organic dyestuffs. The silicon dioxide
films containing colorants formed on the sides of
substrate which had been coated with primer layers has
such strong adhesive strength that no peeling occurs
during the peel-off test using cellophane tapes. Also,
after immersion in boiling water for 10 minutes, the
silicon dioxide films containing colorants were kept
intact. As a result, the formed films were proved having
improved adhesion properties. On the other hand, the
silicon dioxide films containing colorants formed on the
side of the substrate which had not been coated with
primer layers was poor in bonding and adhesion.
Example 16
A biaxially oriented film of polypropylene
measuring 100 mm long, 100 mm wide and 25 um thick, and
corona treatment on both sides. was immersed into a
solution of Unistol P (a product of MITUSI PETROCHEMICAL
INDUSTRIES LTD.) twice diluted with toluene, pull up at
cm/min, and dried out at 90°C in a hot air oven for 30
minutes in order to form resin primer layers (of 2.0 um
t:~ickness) on both the sides.
25 The biaxially oriented polypropylene films
coated with the resin primer layers was immersed into a
processing solution prepared by dissolving a mixture of
1.5 g of Y-aminopropyltriethoxysilane and 1.5 g of vinyl-
tris(S-methoxyethoxy)silane into 250 ma, of a mixture
30 solvent medium comprising ethyl alcohol, isopropyl
alcohol, and n-butyl alcohol at a (volume) ratio of 5:3:2
in this order, pull up at 15 cm/min and then dryout at
90°C in a hot air oven for 30 minutes in order to form
the first coating films thereon.
In the same manner as of Example l3, additive
solution of 5 ~ by weight prepared by dispersing disperse
dyestuff of DIACELLITON FAST RED (a product of MITSUBISHI
CHEMICAL INDUSTRIES LTD:) into distilled water, is added


_ 89 _
at the rate of 1 cc per 100 cc of hydrosilicofluoric acid
solution supersaturated with silicon dioxide, and then
silicon dioxide film is formed on the biaxially oriented
polypropylene film.
The silicon dioxide films formed was in red
color and their thickness was 2200 ~ measured by a
contacting probe type film thickness measuring
instrument.
It was acknowledged through the analysis with
ESCA, SIMS, and IR that the disperse dyestuff was
uniformly incorporated with the formed thin films. In
addition, each test substrate carrying the films of
silicon dioxide was kept immersed in a solution of 99.5
ethanol for 24 hours, which resulted in no elution of the
disperse dyestuff. Also, no peeling-off of the silicon
dioxide film from the biaxially oriented polypropylene
film was detected during an adhesive tape test and a
sponge rubbing test.
As described above, the method of manufacturing
an organic molded substrate coated with silicon dioxide
film containing organic colorant of the first embodiment
of the present invention, comprises the steps of: forming
a first coating film composed of organic silicon
compound, desirably, forming an organic resin primer
layer having good adhesion ability to the surface of the
organic substrate in advance and then, forming a first
organic silicon compound film; and forming silicon
dioxide film containing an organic colorant; wherein the
silicon dioxide film having good adhesive ability for the
thin organic resin primer layer is formed as the primary
layer, and then the silicon dioxide film, containing
organic colorant, having good adhesive ability for the
primary layer is formed thereon as secondary layer. As a
result, the first embodiment of the present invention has
the following advantages:
1. The silicon dioxide film can be provided
ensuring improved durability and having high adhesive
properties and bond strength, as compared with that




0 _ ~~:~~~.a~
formed directly on the surface of a plastic molded
substrate by a vapor deposition method or sputtering
method.
2. Since the organic silicon compound film
which is less flexible in "bending" and "folding" is
formed very thin, the silicon dioxide film containing an
organic colorant can be provided without lowering the
flexibility with an organic film or a fiber even if it
applied thereto.
3. The silicon dioxide films containing organic
colorant can simultaneously be provided on both the
sides, the circumferential surface, or the entire
periphery of the organic moldbd substrate and also the
obtained silicon dioxide film containing organic colorant
has an ability for interrupting the passing of aqueous
vapor, oxygen, or the like, so that not only oxidation
and hydrolysis of the organic colorant is avoided but
also the colorant dissolving into the water from the
coloring layer causing lowering the coloring is
prevented.
4. The obtained silicon dioxide film containing
organic colorant has an ability to prevent organic
solvent from passing therethrough; so that it can improve
in resistance to solvents and chemicals of the coloring
layer.
5. The silicon dioxide film containing organic
colorant is formed at about the room temperature without
heating at a high temperature, sa that the method can be
employed for application to thermally unstable organic
colorants.
6. The silicon dioxide film, containing organic
colorant, having slight impurities can be obtained.
7. The raw materials are low in price, so that
the cost of manufacturing can be reduced.
8. The silicon dioxide film containing organic
colorant can be formed on any substrate of complex
configuration.



- 91 -
Example of the Second Embodiment
The second embodiment of the present invention
will now be described in detail. It would also be
understood that the second embodiment of the present
invention is not limited to the example without departing
the scope thereof.
Example 21
An acrylic resin plate (an extruded plate of
57000 in number-average molecular weight) measuring 100
mm long, 100 mm wide, and 1.5 mm thick was immersed in a
solution (containing about 0.9 ~ by weight of silicon
compound) prepared by dissolving a mixture (D/C=0.22) of
1.5 g of Y-methacryloxypropyltrimethoxysilane and 3 g of
CSGL-0803P (a hydrolysis of tetraethylorthosilicate
available from CHISSO CORPORATION, having a solid
substance of 8 ~ in concentration) into 250 m~ of a
mixture solvent medium comprising ethanol, isopropyl
alcohol, and n-butyl alcohol in a (volume) ratio of 5:3:2
in this order. The acrylic resin plate was hen pulled
up at a speed of 15 cm/min and dried out at the room
temperature for an hour. In the same process, a primary
thin film was formed on a glass substrate and its
thickness was about 10 nm.
The acrylic resin plate coated with primary
films was processed with the apparatus of forming silicon
dioxide thin film, shown in Fig. 2, for forming thereon
coloring layers of silicon~dioxide film containing
organic colorants shown in Table 21.




_ 92 _
Table 21
Additive dyestuffs Film thickness (~) Color tone
KAYACYL YELLOW GG 5350 Light yellow


GREEN 6200 Green


ALIZARINE ASTROL 8000 Light purple


RHODAMINE 6G 1200 Red


ACRDINE RED 900 Red


FLUORESCEIN 4300 Yellow


RHODAMTNE 19 5500 Red


SULFORHODAMINE B 1220 Red purple


As shown in Fig. 2, an immersing tank comprises
an outer tank 1 and an inner tank 2, being filled with
water 3 between the outer and inner tanks 1 and 2. The
water 3 is kept heated to 40°C by a heater 4 and stirred
for uniform thermal dispersion. The inner tank 2
comprises a front section 6, an intermediate section 7,
and a rear section 8, each section being filled with 6.5
liters of 2.5 mol/~, hydrosilicofluoric acid solution
prepared by dissolving and saturating silicon dioxide fed
by industrial silica-gel powder. In addition, in the
solution a solution having 5 % by weight of a dyestuffs
listed in Table 21 is added at the rate of l cc per 100
cc of hydrosilicofluoric acid solution. In practice, the
coloring was carried out in each dyestuffs associated
with its processing solution which was replaced with new
one in each cycle of the operation.
The coloring operation way commenced with a
circulation pump l0 actuated for circulating the water
solution from the rear section 8 of the inner tank 2
through filter 11 back to the front section 6.
A plate of aluminium l2 measuring 50 mm long,
50 mm wider and 3 mm thick was immersed into the solution
of the rear section 8 and maintained for 10 hours. Then,
the solution was turned to a proper processing solution




- 93 -
containing a desired supersaturating rate of Si02. The
filter 11 was adjusted to 1.5 um in absolute filtering
rate and the circulating flow of the processing solution
was set to 520 m~./min (namely, about 8 %/min since the
total volume of the processing solution was about 6.5
liters). The acrylic resin plate 21 coated with the
silicon compound primary layers was immersed vertically
into the solution of the intermediate tank 7 and
maintained for 16 hours under the foregoing condition
(namely, the solution was circulated at about 8 o/min
through the 1.5 um filter 11 with three of the aluminium
plates remaining immersed) before removed out for
cleaning and dryout.
The list of employed dyestuffs and the test
result are shown in Table 21, in which the thickness of
each silicon dioxide film formed was measured by a
contacting probe type film thickness measuring
instrument.
It was acknowledged through the analysis with
Electron Spectroscopy for Chemical Analysis (ESCA),
Secondary Ion Mass Spectrometry (SIMS), and Infrared
Spectrophotometry (IR) that the organic dyestuffs were
uniformly incorporated with their respective thin
films. In addition, each test substrate carrying the
silicon dioxide film was kept immersed in a solution of
99.5 ~ ethanol for 24 hours, which resulted in no elution
of the organic dyestuffs.
The silicon dioxide films containing organic
colorant formed were kept intact without peeling-off
during a peel-off test using adhesive cellophane tapes,
demonstrating a high degree of adhesion. Also, after the
acrylic resin plate coated with silicon dioxide films
containing organic colorant were immersed in boiling
water for an hour, no change in the adhesion of the films
was detected.
As described above, the method of forming an
acrylic resin molded substrate coated with silicon
dioxide films containing organic colorant of the second




- 94 - '~'~~.w~~
embodiment of the present invention, in which on the
surface of the acrylic resin molded substrate, a very
thin film, containing silicon, having good adhesive
ability is formed as a primary layer by coating and
curing mixture containing s?.licon compound having
methacryloxy group represented by the general formula
(VI) and hydrolysis of silicon compound represented by
the general formula (VII) at a specific rate, and then a
silicon dioxide film containing organic colorant, which
has good adhesive ability to the primary layer, is formed
thereon. Accordingly, the second embodiment of the
present invention provides the following advantages:
1. The silicon dioxide films containing organic
colorant can simultaneously be provided on both the
sides, the circumferential surface, or the entire
periphery of the acrylic resin molded substrate and also
the obtained silicon dioxide films containing organic
colorant has an ability for interrupting the passing of
aqueous vapor, oxygen, or the like, so that not only
oxydation and hydrolysis of the organic colorant is
avoided, but also the colorant dissolving into the water
from the coloring layer causing lowering the coloring is
prevented.
2. The obtained silicon dioxide film containing
organic colorant can have an ability to prevent organic
solvents and chemicals from passing therethrough and
thus, so that it can improve in resistance to solvents
and chemicals of the coloring layer.
3. Since organic colorant is protected with
silicon dioxide in structure, the coloring layer can be
provided ensuring high endurance and resistance to wear
and climate.
' 4. The silicon dioxide film containing organic
colorant is formed at about the room temperature without
heat-up at a high temperature, so that the method can be
employed for application to thermally unstable organic
colorants.
5. In the process for foaming the primary

~~ "s g f
~~~.a~~d~~-~t~
_ 95 _
layer, dilute solution of silicon compound can be
employed as coating solution for use, and the silicon
compound diffuses into the acrylic resin, so that thin
film following the configuration can be formed on the
acrylic resin substrate even having fine concaves and
convexes without deffect.
Examples of the Third Embodiment
The third embodiment of the present invention
will be described in detail. It would also be understood
that the third embodiment of the present invention is not
limited to the these examples without departing the scope
thereof .
Example 31
A polycarbonate plate measuring 100 mm long,
100 mm wide, and 1 mm thick was immersed in a solution
(containing about 0.9 ~ by weight of silicon compound)
prepared by dissolving a mixture of 0. 5 g of N-(s-
aminoethyl)-Y°aminopropyltrimethoxysilane and 1.2 g of
vinyl-tris(s-methoxyethoxy)silane into 250 m~, of a
mixture solvent medium comprising ethanol, isopropyl
alcohol, and n-butyl alcohol in a (volume) ratio of 5:3:2
in this order. The polycarbonate plate was then pulled
up at a speed of 15 cm/min and dried out at 100°C in a
hot air oven for an hour. In the same process. a primary
film layer was formed on a glass substrate and its
thickness was about 10 nm.
The polycarbonate (PC) plate coated with
organic silicon compound film layers was processed with
the apparatus of forming silicon dioxide film, shown in
Fig. 2, for forming thereon color layers of silicon
dioxide film containing organic colorants shown in Table
31.
As shown in Fig. 2, an immersing tank comprises
an outer tank 1 and an inner tank 2, being filled with
water 3 between the outer and inner tanks l and 2, The



~r~~~~~c
,,~ ~ a,J ';3
- 96 -
water 3 is kept heated to 40°C by a heater 4 and stirred
for uniform thermal dispersion. The inner tank 2
comprises a front section 6, an intermediate section 7,
and a rear section 8, each section being filled with 6.5
liters of 2.5 mol/~, hydrosilicofluoric acid solution
prepared by dissolving and saturating silicon dioxide fed
by industrial silica°gel powder. In addition, in the
solution a solution having 0.5 % by weight of a dyestuffs
listed in Table 31 is added at the rate of 1 cc per 100
cc of hydrosilicofluoric acid solution. In practice, the
coloring was carried out in each dyestuffs associated
with its processing solution which was replaced with new
one in each cycle of the operation.
The coloring operation was commenced with a
circulation pump 10 actuated for circulating the water
solution from the rear section 8 of the inner tank 2
through a filter 11 back to the front section 6.
A plate of aluminium 12 measuring 50 mm long,
50 mm wide, and 3 mm thick was immersed into the solution
of the rear section 8 and maintained for 1.0 hours. Then,
the solution was turned to a proper processing solution
containing a desired supersaturating rate of si02. The
filter 11 was adjusted to 1.5 um in absolute filtering
rate and the circulating flow of the processing solution
was set to 520 ma,/min (namely, 8 %/min since the total
volume of the processing solution was about 6.5
liters). The polycarbonate plate 31 coated with the
silicon compound first film layers was immersed
vertically into the solution of the'intermediate tank 7
and maintained for 16 hours under the foregoing condition
(namely, the solution was circulated at about 8 %/min
through the 1.5 um filter 11 with three of the aluminium
plates remaining immersed) before removed out for
cleaning and dryout.
The list of employed dyestuffs and the test
result are shown in Table 3l, in which the thickness of
each silicon dioxide film developed was measured by a
contacting probe type film thickness measuring




it .T.
!e ~ ~. ~ ~.~ r ~i
-- 9 7 _
instrument.
Table 31
Additive dyestuffs Film thickness (~) Color tone
KAYACYL YELLOW GG 5200 Light yellow


MALACHITE GREEN 6000 Green


ALIZARINE ASTROL 7800 Light purple


RHODAMINE 6G 1200 Red


ACRDINE RED 900 Red


FLUORESCEIN 4000 Yellow


RHODAMINE 19 5000 Red


SULFORHODAMINE B 1220 Red purple


It was acknowledged through the analysis with
Electron Spectroscopy for Chemical Analysis (ESCA),
Secondary Ion Mass Spectrometry (SIMS), and Infrared
Spectrophotometry (IR) that the organic dyestuffs were
uniformly incorporated with their respective thin
films. In addition, each test substrate carrying the
film of silicon dioxide was kept immersed in a solution
of 99.5 % ethanol for 24 hours, which resulted in no
elution of the organic dyestuffs:
The silicon dioxide films containing organic
colorant were kept intact without peeling-off during a
peel-off test using adhesive cellophane tapes,
demonstrating a high degree of adhesion. Also, after the
polycarbonate plate coated with'the dioxide thin films
containing organic colorant was immezsed in boiling water
for an hour, the films remained unchanged ensuring
effectiveness in the adhesion.
As described above, the method of foaming a
polycarbonate structure coated with silicon dioxide films
containing organic colorant of the third embodiment of
the present invention, in which on the surface of
polycarbonate molded substrate, a very thin film,



- 98 -
containing silicon, having good adhesive ability is
formed as a primary layer by coating and curing mixture
containing silicon compound having amino gxoup, and
silicon compound represented by the general formula
(VIII) or hydrolysis thereof at a specific rate, and then
a silicon dioxide film containing organic colorant, which
has good adhesive ability to the primary layer, is formed
thereon. Accordingly, the third embodiment of the
present invention provides the following advantages:
1. The silicon dioxide thin films containing
organic colorant can simultaneously be provided on the
front and back sides, the circumferential surface, or the
entire periphery of the polycarbonate molded substrate
and also the obtained silicon dioxide films containing
organic colorants has an ability for interrupting the
passing of aqueous vapour, oxygen, or the like, so that
not only oxyda'tion and hydrolysis of the organic coloring
agent is avoided, but also from the coloring layer
causing lowering the coloring is prevented.
2p 2. The silicon dioxide film containing organic
colorant can have an ability to prevent an organic
solvent and chemicals from passing therethrough and thus,
so that it can improve in resistance to solvents and
chemicals of the coloring layer.
3. Since the organic colorant is protected with
silicon dioxide in structure, the coloring layer can be
provided ensuring high endurance and resistance to wear
and climate.
4. The silicon dioxide film containing organic
colorant is formed at about the room temperature without
heat-up at a high temperature, the method can be employed
for application to thermally unstable organic colorants.
5. In the process for forming the primary
layer, dilute solution of silicon compaund can be
employed as coating solution for use, and the silicon
compound diffuses into the polycarbonate, so that thin
film following the configuration can be formed on the
polycarbonate substrate even having fine concaves and




ib Y.7 .~ ~!
- 99 -
convexes without deffect.
Examples of the Fourth Embodiment
The fourth embodiment of the present invention
will now be described in detail referring to the
examples.
Example 41
Using the foregoing apparatus of Fig. 2, films
of silicon dioxide containing organic colorant listed in
Table 41 were produced on the surfaces of Ti02
particles. Accordingly, colored particles of Ti02 were
obtained.
In practice; the water 3 contained in the outer .
tank 1 was kept at 35°C by the heater 4.
The inner tank 2 of 500 cc capacity which was
installed inside of the outer tank 1, was filled with a
processing solution prepared by adding 15 cc of 0.5
mol/~, boric acid water solution to 250 cc of 2.5
mol/a hydrosilicofluorzc acid solution saturated with
silica gel which was kept at 34°C: Each of the dyestuffs ,
listed in Table 41 was dissolved at the room temperature
into water to produce a 5 ~ by weight or saturated
additive solution which was in turn added to the
processing solution at the rate of l cc per l00 cc of
hydrosilicofluoric acid solution. The coloring operation
with each dyestuffs of Table 41 was carried out.
For the coloring operation, 10 g of Ti02
particles which is about l micron in average diameter,
was added to the processing solution. After stirring for
20 hours, silicon dioxide films containing dyestuffs were
formed on the surfaces of the Ti02 particles. ~'or
evaluation of the silicon dioxide films containing
35. dyestuffs for thickness and quality; a glass plate of 1.1
mm (thickness) x 20 mm x 50'mm was simultaneously
immersed in the processing solution to form a color layer
thereon.



- loo -
The list of employed dyestuffs and the test
result are shown in Table 41, in which the thickness of
each silicon dioxide film formed was measured by a
contacting probe type film thickness measuring
instrument.
Table 41
Additive dyestuffs Film thickness (A)* Color tone
KAYACYL YELLOW GG 2100 Light yellow


RED 21P 2700 Light yellow


KAYACYL RHODAMINE 1400 Light red
FB


RED 3P 2500 Light red


VICTORIA BLUE BH 3400 Blue green


VICTORIA PURE BLUE 1800 Light yellow
BOH


green


MALACHITE GREEN 2100 Light green


GREEN lOP 1600 Light yellow


green


METHYL VIOLET PURE 7750 Light blue


_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _
_ _


ALIZARINE ASTROL 8100 Light purple


* Film thicknesses for the films formed on the glass
are


substrates.



It was acknowledged
through the analysis
with


Electron Spectroscopyfor Chemical Analysis (ESCA),


Secondary Ion Mass ctrometry (SIMS), and Infrared
Spe


Spectrophotometry that the organic colorants were
(IR)


uniformly incorporatedwith their respective thin


films. In addition, he Ti02 particles coated with the
t


silicon dioxide filmswere kept immersed in a solution of


99.5 ~ ethanol for hours, which resulted in no elusion
24 ,, i






- lol -
of the organic dyestuff.
Example 42
Using the foregoing apparatus of Fig. 2, films
of silicon dioxide containing laser colorants listed in
Table 42 were formed on the surfaces of glass flakes.
Accordingly, colored glass flakes were obtained. In this
case, the processing solution was prepared by saturating
hydrosilicofluoric acid solution of -3°C with silica gel
for about 2 hours and then by adding each of laser
colorants listed in Table 42 to the solution at the rate
1 cc per 100 cc of the solution. The processing solution
was transferred to the inner tank shown in Fig. 2 and the
water in the outer tank was heated up to 50°C. In the
same manner as Example 41, glass plates for evaluation
standard as well as 10 g of glass flakes were immersed
into the solution transferred.
After stirring for 20 hours, the coloring was
completed with a result shown in Table 42. The colored
glass flakes were kept immersed in a solution of 99.5
ethanol for 24 hours, which resulted in no elution of the
laser colorants.
Table 42
Laser colorants Film thickness (A)* Color tone
RHODAMINE 110 2000 Light orange


RHODAMINE 116 2300 Light orange


RHODAMINE B 1400 Light red


purple


RHODAMINE 123 3100 Yellow


RHODAMINE 19 1600 Light red


RHODAMINE 6G 1740 Light red


FLUORESCEIN 1700 Light yellow


COUMARTNE 6 1900 Orange


* Film thickness are for the filmsformed on the glass


substrate.






- loz -
Example of the Fifth Embodiment
The fifth embodiment of the present invention
will now be described in detail referring to the
examples.
Example 51
A glass plate measuring 1.1 mm thick, 25 mm
caide, and 50 mm long which had been cleaned by an
ultrasonic-wave cleaner and dried out, was provided with
a masking of 200-micron-wide stripes arranged thereon at
intervals of 100 microns (for parts without mask) by a
photo-resist method. As accompanied with a glass plate
of the same kind without masking, the glass plate with
the masking was immersed into the solution prepared by
adding an organic dyestuff commercially known as
DIACELLITON FAST RED R to hydrosilicofluoric acid
solution saturated with silicon dioxide for producing
red-color layers. The coloring was carried out using the
apparatus of Fig. 2.
In this case, the water filled in the outer
tank 1 of 2 s capacity was kept at 35°C by the heater 4.
The 500 cc capacity inner tank 4 installed in
the outer tank 1 was filled with a processing solution
prepared by adding 15 cc of 0.5 mo1/~; boric acid water
solution to 250 cc of 2:5 mol/~ hydrosilicofluoric acid
solution containing silica gel in saturation which was
kept at 34°C.
In order to color the processing solution, 5
by weight additive prepared by dispersing DIACELLITON
FAST RED R into water at the room temperature, is added
to the processing solution at a rite of 1 cc per 100 cc
of hydrosilicofluoric acid solution, and thereafter
coloring operation is carried out.
Then, the obtained colored glass plate with no
masking was examined in film thickness,,distribution of
dyestuff throughout film, film resistance to solvent; and
optical spectrum characteristics. The total film




.~ 4 l /
.N ~ i r,J ~: ~.9 'L~
- 103 -
thickness (namely, both sides) of 2.5 microns was
measured using a contacting probe type film thickness
measuring instrument. It was also acknowledged through
the analysis with Electron Spectroscopy for Chemical
Analysis (ESCA), Secondary Ion Mass Spectrometry (SIMS),
and Infrared Spectrophotometry (IR) that the dyestuff was
uniformly incorporated with the film.
The colored glass plate coated with silicon
dioxide films were also immersed in a solution of 99.9
alcohol for 24 hours, which results in no elusion of the
dyestuff. Its optical sgectrum for the glass without
mask is shown in Fig. 3.
On the other hand, the glass plate with 200
micron-wide striped masking was cleaned for removal of
masking agents using organic solvent. After dried out,
the glass plate was prepared for coloring in green and
provided with 200-micron-wide masking stripes arranged
thereon by a photo resist method so as to lap over the
100-micron-wide red color stripes and simultaneously,
leave 100-micron-wide stripes of no masking region.
Then, the masked glass plate was immersed, as
accompanied with the no-masking glass plate, into the
solution containing an organic dyestuff of MALACHITE
GREEN for coloring in green in the same manner as those
of coloring in red. The colored glass plates were
examined in the same manner as of red color coloring.
The (total) thickness of the films formed on both sides
was 3.4 microns while no defect was detected in the
distribution of dyestuff throughout the film and the
resistance to alcohol like red coloring. The spectrum of
the green color glass plate is shown in Fig. 4.
The masked glass plate after cleaned down for
removal of masking agents, was processed for coloring in
blue of the uncolored region of 100-micron-wide (stripes)
with the rest of the surface being masked, using a blue
dyestuff of BLt~E 5P.
In a similar manner for coloring in red and
green, the no masked glass plate was also processed for



- 104 -
comparison.
The optical spectrum of the blue color glass
plate is shown in Fig. 5, in which the thickness of the
films formed on both sides is 3.0 microns total. Similar
to coloring in red and green, no defect was detected in
the resistance to alcohol.
After the masking agents coated over the red
and green color region were removed from the surface
which was then cleaned and dried out, the 100-micron-wide
stripes of red, green, and blue were formed on the glass
plate representing an arrangement of striped RGB matrix
as viewed through an optical microscope.
Examples of the Sixth Embodiment
The sixth embodiment of the present invention
will now be described in detail referring to the
examples.
Example 61
Using the foregoing apparatus of Fig.2, silicon
dioxide films containing organic dyestuff listed in Table
61 were developed on the surface of a glass plate
measuring 1.1 mm thick, 25 mm wide, and 50 mm long. Tn
practice, the water 3 contained in the outer tank 1 of 2
liter capacity was kept at 35°C by the heater 4.
The inner tank 2 of 500cc capacity which was
installed within the outer tank 1, was filled with a
processing solution prepared by adding l5 cc of 0.5 mo1/1
boric acid water solution to 250 cc of 2.5 mol/1
hydrosilicofluoric acid solution saturated with silica
gel which was kept at 34°C. Each of the dyestuff listed
in Table 61 was dissolved at the room temperature into
water to produce 5 % by,weight or saturated additive
solution which was in turn added to the processing
solution at the rate of 1 cc per 100 cc of
hydrosilicofluoric acid solution. The coloring operation
with each dyestuff of Table 6l was carried out.




- l05 - ~~~.~~~J
Table 61
Additive dyestuffs Film thickness (~) Color tone
KAYACYL YELLOW GG 4800 Light yellow


RED 21P 6800 Light yellow


KAYACYL RHODAMINE FB 4200 Red


RED 3P 7200 Light red


- _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _
_ _ _ _ _ _ _


VICTORIA BLUE BH 8100 Blue green


VICTORIA PURE BLUE BOH 4700 Yellow green


MALACHITE GREEN 4600 Green


GREEN lOP 2900 Yellow green


It was acknowledged through the analysis with
Electron Spectroscopy for Chemical Analysis (ESCA),
Secondary Ion Mass Spectrometry (SIMS), and Infrared Ray
Spectrometry (IR) that the organic colorants listed in
Table 61 were uniformly incorporated with their
respective thin films. In addition, the colored glass
plate carrying silicon dioxide films was kept immersed in
solution of 99.5 o ethanol for 24 hours, which resulted
in no elution of the organic dyestuff.
Among the glass coated with sili:com dioxide
containing organic colorants, the glass coated with
MALACHITE GREEN is formed AZ film on one side by the
vacuum deposition method to produce colored mirror. The
3p reflection spectra are shown in Fig. 6.
Example 62
Using the foregoing apparatus of Fig:2, films
of silicon dioxide containing laser dolorant listed in
Table 62 were formed on the surface of a glass plate
measuring 1.1 mm thick, 25 nun wide, and 5O mm long. In
this case; the processing solution was prepared by
saturating hydrosilicofluoric acid solution of ~3°C with




c-~~-~fa.
.~ ed s,J 'i~'
- 106 -
silica gel for about 2 hours and then, by adding each of
the laser colorants listed in Table 62 at the rate 1 cc
per 100 cc of the solution. The processing solution was
transferred to the inner tank shown in Fig.2 and the
water in the outer tank was heated up to 50°C. Then, the
glass plate was immersed into the processing solution
transferred.
After coloring for 16 hours, it resulted as
shown in Table 62. The colored glass plate was then
immersed in a solution of 99.9 % ethanol for 24 hours,
which resulted in no elution of the organic dyestuffs.
Table 62
Laser colorants Film thickness (~.) Color tone
METHYL VIOLET PURE SP 7?00 Light blue
BLUE 5P 2000 Blue
ALIZARINE ASTROL 9300 Light purple
DIACELLITON FAST RED R 7500 Red
Among the glass coated with silicon dioxide
containing organic colorants, the glasses coated with
BLUE 5P and DIACELLITON FAST RED R are formed AZ film on
one side by vacuum deposition method to produce colored
mirrors. The reflection spectra are shown in Figs. '7 and
8.
It is understandable from the examples that the y
sixth embodiment of the present invention provides a
highly durable color mirror.
Examples of the Seventh Embodiment
The seventh embodiment of the present invention
will be described in detail. It would also be understood



-;a ~ ~? n s
~~.~;T~~a~
- 107 -
that the present invention is not limited to the examples
without departing the scope thereof.
Example 71
A plate of slide glass measuring 75 mm long, 25
mm wide, and 1 mm thick was used as a test substrate
which had been cleaned and dried completely.
Various kinds of laser colorants were dissolved
in distilled water at the room temperature to produce an
amount of 5 ~ by weight or saturated liquid additive.
Also, processing solution was prepared by
either adding 8 cc of 0.5 mol/L boric acid water solution
to 100 cc of hydrosilicofluoric acid solution saturated
with silica gel or dissolving 0.4 g of metallic aluminium
into the same hydrosilicofluoric acid solution. 100 cc
of the processing solution was mixed with 1 cc of each
laser colorant additive liquid in a beaker which was in
turn heated in a water bath at 35°C after stirring.
Then, the test substrates were immersed in respective
processing solutions and 16 hours later, removed out for
cleaning and dryout:
The list of additive laser colorant and the
test result are shown in Table 7l, in which the thickness
of each silicon dioxide film formed on the slide glass
was measured by a contacting prove type film thickness
measuring instrument.




- 108 -
Table 71
Laser colorants Film thickness (A) Color tone
RHODAMINE 110 4400 Light orange


RHODAMINE 116 4700 Orange


RHODAMINE B 2900 Red purple


RHODAMINE 123 7800 Yellow


RHODAMINE 19 4600 Red


RHODAMTNE 6G 3000 Red


SULFORHODAMINE B 2200 Red purple


AGRDINE RED 3400 Red


FLUORESCEIN 4100 Yellow


It was acknowledged through analysis with
Electron Spectroscopy for Chemical Analysis (ESCA),
Secondary Ion Mass Spectrometry (SIMS). and Infrared
Spectrophotometry (IR) that the laser colorants were
uniformly incorporated with their respective thin
films. In addition, each test substrate carrying the
film of silicon dioxide was kept immersed in a solution
of 99.5 ~ ethanol for 24 hours, which resulted in no
elution of the colorants.
Also, no peeling-off of the silicon dioxide
film from the substrate was detected during a tape test
and a sponge rubbing test:
Example 72
A plate of slide glass measuring 75 mm long, 25
mm wide, and 1 mm thick was used as a test substrate
which had been cleaned and dried completely.
Various kinds of dyestuffs were dissolved in
distilled water at the room emperature to produce an
amount of 5 ~ by weight or saturated liquid additive.
Also, processing solution was prepared by
either adding 8 ac of 0.5 mol/L boric acid water solution
to 100 cc of hydrosilicofluoric acid solution saturated




~~ ,~_ 4~ L3 ~.~ 1~~
- 109 -
with silica gel or dissolving 0.4 g of metallic aluminium
into the same hydrosilicofluoric acid solution. 100 cc
of the processing solution was mixed with 1 cc of each
dyestuffs additive liquid in a beaker which was in turn
heated in a water bath at 35°C after stirring. Then. the
test substrates were immersed in respective processing
solutions and 16 hours later, removed out for cleaning
and dryout.
The list of additive dyestuffs and the test
result are shown in Table 72, in which the thickness of
each silicon dioxide film formed on the slide glass was
measured by a contacting probe type film thickness
measuring instrument.
Table 72
Additive dyestuffs Film thickness (~) Color tone
KAYACYL YELLOW GG 6400 Light yellow
MALACHITE GREEN 5800 Green
ALI~ARINE ASTROL 7300 Light purple
It was acknowledged through analysis with ESCA,
SIMS, and IR that the dyestuffs were uniformly
incorporated with their respective thin films.
In addition, each test substrate carrying the
film of silicon dioxide was kept immersed in a solution
of 99.5 $ ethanol for 24 hours, which resulted in no
elution of the pigment. Also, no peeling-off of the
silicon dioxide film from the substrate was detected
during a tape test and a sponge rubbing test.
Example 73
A plate of slide glass measuring 75 mm long, 25




.y i. ,~ p
!. ~ ~ .~ e.7 ~ta ~V' i 1
- llo -
mm wide, and 1 mm thick caas used as a test substrate
which had been cleaned and dried completely.
A disperse dyestuffs known as DIACELLITON FAST
RED R (a product of MITSUBISHI CHEMICAL INDUSTRIES LTD.)
was dispersed into distilled water at the room
temperature for producing an amount of 5 o by weight
liquid additive.
Processing solution was prepared by dissolving
0.4 g of dissolved metallic aluminium into 100 cc of
hydrosilicofluoric acid solution saturated with silica
gel. 1 cc of the disperse dyestuff solution was mixed
with the processing solutions in a beaker which was in
turn heated in a water bath at 35°C after stirring.
Then, the test substrate was immersed in the processing
solution and 16 hours later, removed out for cleaning and
dryout.
The formed silicon dioxide film appeared in red
and its thickness was 7300 A measured by a contacting
probe type film thickness measuring instrument.
It was acknowledged through analysis with ESCA,
SIMS, and IR that the disperse dyestuff was uniformly
incorporated with the thin film. In addition, the test
substrate carrying the film of silicon dioxide was kept
immersed in a solution of 99.5 ~ ethanol for 24 hours,
cahich resulted in no elution of the disperse dyestuff.
Also, no peeling-off of the silicon dioxide
film from the substrate was detected during a tape test
and a sponge rubbing test.
Examples of the Eighth Embodiment
The eighth embodiment of the present invention
will be described in detail. It would also be understood .
that the present invention is not limited to the examples
without departing the scope thereof.
Example 81
A stainless steel plate coated with a Si02 film




~a ~ri .:~
f,,. r .:,~ :~~~ '~ '.~i r.
- 111 -
of 1000 ~ thickness by the sol-gel method was employed as
a test substrate which is 75 mm in length, 25 mm in
width, and 1 mm thickness.
Various kind of laser colorant were dissolved
in distilled water at the room temperature to produce an
amount of 5 % by weight or saturated liquid additive.
Also, processing solution was prepared by
either adding 8 ec of 0.5 mol/L boric acid water solution
to 100 cc of hydrosilicofluoric acid solution saturated
with silica gel or dissolving 0.4 g of metallic aluminium
into the same hydrosilicofluoric acid solution. 100 cc
of the processing solution was mixed with 1 cc of each
laser colorant additive liquid in a beaker which was in
turn heated in a water bath at 35°C after stirring.
Then, the test substrates were immersed in respective
processing solutions and 16 hours later, removed out far
cleaning and dryout.
The list of additive laser colorants and the
test result are shown in Table 81, in which the thickness
of each silicon dioxide film formed on the slide glass
was measured by a contacting probe type film thickness
measuring instrument.
Table 81
Laser colorants Film thickness (A) Color tone
RHODAMINE 110 4400 Light orange


RHODAMINE 116 4700 Orange


RHODAMINE B 2900 Red purple


RHODAhiINE 123 7800 Yellow


RHODAMINE 19 4600 Red


RHODAMINE 6G 3000 Red


SULFORHODAMINE B 2200 Red purple


ACRDINE RED 3400 Red


FLUORESCEIN 4100 Yellow




~~:' ~:~~~~a~~
- 112 -
It was acknowledged through analysis with
Electron Spectroscopy for Chemical Analysis (ESCA),
Secondary Ion Mass Spectrometry (SIMS), and Infrared
Spectrophotometry (IR) that the laser colorants were
uniformly incorporated with their respective thin
films. In addition, each test substrate carrying the
silicon dioxide film was kept immersed in a solution of
99.5 o ethanol for 24 hours, which resulted in no elution
of the organic colorants.
Also, no peeling-off of the silicon dioxide
film from the substrate was detected during a tape test
and a sponge rubbing test.
Example 82
A plate of slide glass coated with an aluminium
layer of 1000 ~ thickness and a Si02 layer of 300 A
thickness by a sputtering method was used as a test
substrate measuring 75 mm long, 25 mm wide, and 1 mm
thick.
Various kind of dyestuffs were dissolved in
distilled water at the room temperature to produce an
amount of 5 ~ by weihgt or saturated liquid additive.
Also, processing solution was prepared by
either adding 8 ec of 0.5 mol/L boric acid water solution
to 100 cc of hydrosilicofluoric acid solution saturated
with silica gel or dissolving 0.4 g of metallic aluminium
into the same. 100 cc of the processing solution was
mixed with 1 CC Of each dyestuff additive liquid in a
beaker which was in turn heated in a water bath at
35°C. Then, the test substrates were immersed in
respective processing solutions and Z6 hours later,
removed out for cleaning and dryout.
The list of additive dyestuffs and the test
result are shown in Table 82, in which the thickness of
each silicon dioxide film developed was measured by a
contacting probe type film thickness measuring
instrument.

- 113 -
Table 82
Additive dyestuffs Film thickness (A) Color tone
KAYACYL YELLOW GG 6400 Light yellow
MALACHITE GREEN 5800 Green
ALIZARINE ASTROL 7300 Light purple
It was acknowledged through analysis with ESCA,
SIMS, and IR that the dyestuffs were uniformly
incorporated with their respective thin films.
In addition, each test substrate carrying the
silicon dioxide film was kept immersed in a solution of
99.5 % ethanol for 24 hours, which resulted in no elution
of the dyestuffs. Also, no peeling-off of the silicon
dioxide film from the substrate was detected during a
tape test and a sponge rubbing test.
Example 83
A stainless plate measuring 75 mm long, 25 mm
wide, and 1 mm thick and coated with a Ti02 layer of
1000 A thickness by a sol-gel method was used as a test
substrate.
A disperse dyestuffs known as DIACELLITON FAST
RED R (a product of MITSUBISHI CHEMICAL INDUSTRxES LTD.)
was dispersed into distilled water at the room
temperature for producing an amount of 5 % by weight
liquid additive.
Processing solution was prepared by dissolving
0.4 g of metallic aluminium into 100 cc of
hydrosilicofluoric acid solution saturated with silica
gel. 1 cc of the disperse dyestuff solution caas mixed
with the processing solution'in a beaker which was in
turn heated in a water bath at 35°C after stirring.
Then, the test substrate was immersed in the processing


,.
~,~~a~~:d'~~7
- 114 -
solution and 16 hours later, removed out for cleaning and
dryout.
The formed silicon dioxide film appeared in red
color and its thickness was 7300 A measured by a
contacting probe type film thickness measuring
instrument.
It was acknowledged through analysis with ESCA,
SIMS, and IR that the disperse dyestuff was uniformly
incorporated caith the thin film. In addition, the test
substrate carrying the silicon dioxide film was kept
immersed in a solution of 99.5 o ethanol for 24 hours,
which resulted in no elution of the disperse dyestuffs.
Also, no peeling-off of the silicon dioxide
film from the substrate was detected during a tape test
and a sponge rubbing test.
Examples of the Ninth Embodiment
The ninth embodiment of the present invention
will now be described in detail referring to the
examples.
Example 91
A cover glass measuring 30 mm in diameter and 1
mm in thickness was used as a test substrate which had
been cleaned and dried completely.
Various kind of laser colorants were dissolved
in distilled water at the room temperature to produce an
amount of 5 o by weight,or saturated liquid additive.
Also, processing solution was prepared by
either adding 8 cc of 0.5 mol/L boric acid water solution
to 100 cc of hydrosilicofluoric acid solution saturated
with silica gel or dissolving 0.4 g of metallic aluminium
into the same hydrosilicofluoric acid solution. 100 cc
of the processing solution was mixed with l cc of each
laser colorant additive liquid in a beaker which was in
turn heated in a water bath at 35°C after stirring.
Then, the test substrates were. immersed in respective



cy ,.a ~~ ;f-[~ gy
T'z %.:~' z 7; ;) ::? lJ
115 -
processing solutions and 16 hours later, removed out for
cleaning and dryout.
The list of additive laser pigments and the
test result are shown in Table 91, in which the thickness
of each silicon dioxide film formed on the slide glass
was measured by a contacting probe type film thickness
measuring instrument.
Table 91
Laser colorants Film thickness (A) Color tone
RHODAMINE 110 4700 Light orange


RHODAMINE 116 5200 Orange


RHODAMINE B 3900 Red purple


RHODAMINE 123 8600 Yellow


RHODAMINE 19 4700 Red


RHODAMINE 6G 3400 Red


SULFORHODAMINE B 2000 Red purple


ACRDINE RED 3900 Red


FLUORESCEIN 4000 Yellow


It was acknowledged through analysis with
Electron Spectroscopy for Chemical Analysis (ESCA),
Secondary Ion Mass Spectrometry (SIMS), and Infrared
Spectrophotometry (IR) that the laser colorants were
uniformly incorporated with their respective thin
films. In addition, each test substrate carrying the
film of silicon dioxide was kept immersed in a solution
of 99.5 ~ ethanol for 24 hours, which resulted in no
elution of the organic colorant.
Also, no peeling-off of the silicon dioxide
film from the substrate was detected during a tape test
and a sponge rubbing test.
Example 92
A cover glass measuring 30 mm in diameter and l



rLfJ ~ c:)
- 116 -
mm in thickness was used as a test substrate which had
been cleaned and dried completely.
Various kinds of dyestuffs were dissolved in
distilled water at the room temperature to produce an
amount of 5 % by weight or saturated liquid additive.
Also, processing solution caas prepared by
either adding 8 cc of 0.5 mol/L boric acid water solution
to 100 cc of hydrosilicofluoric acid solution saturated
with silica gel or dissolving 0.4 g of metallic aluminium
into the same hydrosilicofluaric acid solution. 100 ec
of the processing solution was mixed with 1 ec of each
dyestuff additive liquid in a beaker which was in turn
heated in a water bath at 35°C after stirring. Then, the
test substrates were immersed in respective processing
solutions and 16 hours later, removed out for cleaning
and dryout.
The list of additive dyestuffs and the test
result are shown in Table 92. in which the thickness of
each silicon dioxide film formed on the slide glass was
measured by a contacting probe type film thickness
measuring instrument.
Table 92
Additivedyestuffs Film thickness (A) Color tone


KAYACYL YELLOW GG 5100 Light yellow


MALACHITE GREEN 6100 Green
ALIZARINE ASTROL 7900 Light purple
It was acknowledged through analysis with ESCA,
SIMS, and IR that the dyestuffs were uniformly
incorporated with their respective thin films.
In addition, each test substrate carrying the
silicon dioxide film was kept immersed in a solution of




/ 4
i~ ~~.~ ~ ~J ~ ~J
- 117 -
99.5 % ethanol for 24 hours, which resulted in no elution
of the dyestuff. Also, no peeling-off of the silicon
dioxide film from the substrate was detected during a
tape test and a sponge rubbing test.
Example 93
A cover glass measuring 30 mm in diameter and 1
mm in thickness was used as a test substrate which had
been cleaned and dried completely.
A disperse dyestuff known as DIACELLITON FAST
RED R (a product of MITSUBISHI CHEMICAL INDUSTRIES LTD.)
was dispersed into distilled water at the room
temperature for producing an amount of 5 % by weight
liquid additive.
Processing solution was prepared by dissolving
0.4 g of metallic aluminium into 100 cc of
hydrosilicofluoric acid solution saturated with silica
gel. 1 cc of the disperse dyestuff liquid additive was
mixed with the processing solution in a beaker which was
in turn heated in a water bath at 35°C after stirring.
Then, the test substrate was immersed in the processing
solution and 16 hours later; removed out for cleaning and
dryout.
The formed silicon dioxide film appeared in red
color and its thickness was 7500 ~ measured by a
contacting probe type film thickness measuring
instrument.
It was acknowledged through analysis with ESCA,
SIMS, and IR that the disperse dyestuff was uniformly
incorporated with the thin film. In addition, the test
substrate carrying the silicon dioxide film was kept
immersed in a solution of 99.5 % ethanol for 24 hours,
which resulted in no elution of the disperse dyestuff.
Also, no peeling-off of the silicon dioxide
film from the substrate was detected. during a tape test
and a sponge rubbing test.

Representative Drawing