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Patent 1046826 Summary

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(12) Patent: (11) CA 1046826
(21) Application Number: 1046826
(54) English Title: PHOTO-SENSITIVE COMPOSITION FOR DRY FORMATION OF IMAGE
(54) French Title: COMPOSE PHOTOSENSIBLE POUR FORMATION D'IMAGE PAR VOIE SECHE
Status: Term Expired - Post Grant Beyond Limit
Bibliographic Data
(51) International Patent Classification (IPC):
  • G03C 1/72 (2006.01)
  • G03C 7/02 (2006.01)
  • G03F 3/10 (2006.01)
(72) Inventors :
  • KIMOTO, KOICHI
  • UMEDA, YASUSI
  • SAITO, SHIN
  • TANABE, KUNSEI
  • TAKIMOTO, YASUYUKI
(73) Owners :
  • NIPPON PAINT CO.
(71) Applicants :
  • NIPPON PAINT CO.
(74) Agent:
(74) Associate agent:
(45) Issued: 1979-01-23
(22) Filed Date:
Availability of licence: N/A
Dedicated to the Public: N/A
(25) Language of filing: English

Patent Cooperation Treaty (PCT): No

(30) Application Priority Data: None

Abstracts

English Abstract


PHOTO-SENSITIVE COMPOSITION FOR DRY FORMATION OF IMAGE
Abstract of the Disclosure:-
A photo-sensitive composition for dry formation
of image comprising a dyestuff having a photo-fading property,
a ketonic sensitizing agent and a high molecular polymer as
a binding agent, which can provide a visible image by the
irradiation of light and maintain the image without any fix-
ing treatment.
- 1 -


Claims

Note: Claims are shown in the official language in which they were submitted.


The embodiments of the invention in which an exclusive
property or privilege is claimed are defined as follows:
1. A photo-sensitive composition used for the dry
formation of an image consisting essentially of a dye-stuff
having photo-fading properties selected from the group con-
sisting of azo dyestuffs, azomethine dyestuffs, triphenyl-
methane dyestuffs, xanthene dyestuffs, oxazine dyestuffs,
naphthol dyestuffs and anthraquinone dyestuffs, an aryl
ketone sensitizing agent selected from the group consisting
of benzophenones, acetophenones, benzoins, acyloins and
.alpha.-diketones and a high molecular polymer binding agent sel-
ected from the group consisting of polyamide resins, urethane
resins, N-substituted high polymers having acrylamide and/or
methacrylamide units, vinyl acetate polymers and their
partially saponified products, polymers of vinyl monomers
having a secondary hydroxyl group, epoxy resins, copolymers
of styrene or its derivatives and phenol resins wherein the
proportions of the dyestuff, the ketonic sensitizing agent
and the high molecular polymer are 0.05 to 20 : 0.2 to 200 :
100 parts by weight.
2. The photo-sensitive composition according to claim
1, wherein the proportions of the dyestuff, the ketonic
sensitizing agent and the high molecular polymer are 0.2 to 5:
1 to 100 : 100 parts by weight.
3. The photo-sensitive composition according to claim
1, wherein the dyestuff is a triphenylmethane dyestuff.
4. The photo-sensitive composition according to claim
1, wherein the dyestuff is a xanthene dyestuff.
5. The photo-sensitive composition according to claim
1, wherein the dyestuff is an oxazine dyestuff.
6. The photo-sensitive composition according to claim
1, wherein the deystuff is an azo dyestuff.
37

7. The photo-sensitive composition according to claim
1, wherein the aryl ketone sensitizing agent is a benzo-
phenone.
8. The photo-sensitive composition according to claim
7, wherein the benzophenone is benzophenone, 4-methyl-
benzophenone, 4-chlorobenzophenone, 4-ethylbenzophenone
or 4,4'-dimethoxybenzophenone.
9. The photo-sensitive composition according to claim
1, wherein the aryl ketone sensitizing agent is an aceto-
phenone.
10. The photo-sensitive composition according to claim
9, wherein the acetophenone is acetophenone, 4-methyl-
acetophenone, propiophenone, benzalacetophenone or
.omega.-bromoacetophenone.
11. The photo-sensitive composition according to claim
1, wherein the aryl ketone sensitizing agent is a benzoin
12. The photo-sensitive composition according to claim
11, wherein the benzoin is benzoin, benzoin methyl ether,
benzoin ethyl ether, benzoin isopropyl ether, benzoin
n-butyl ether, .alpha.-methylbenzoin, .alpha.-benzylbenzoin or anisoin
ethyl ether.
13. The photo-sensitive composition according to claim
1, wherein the high molecular polymer binding agent is an
N-substituted high polymer having acrylamide and/or
methacrylamide units.
14. The photo-sensitive composition according to claim
1, wherein the high molecular polymer binding agent is a
polyamide resin.
15. The photo-sensitive composition according to claim
1, wherein the high molecular polymer binding agent is a
vinyl acetate polymer or its partially saponified product
38

16. A material for the dry formation of an image pre-
pared by incorporating the photo-sensitive composition
according to claim 1 into a plastic material and molding
the resulting product.
17. A material for dry formation of image prepared
by applying the photo-sensitive composition according to
claim 1 on a supporter to form a layer of the photo-
sensitive composition.
18. A material for color-proof prepared by applying a
solution of the photo-sensitive composition according to
claim 1 in an appropriate solvent on a supporter to form a
layer of the photo-sensitive composition.
19. A method for production of an image which comprises
applying a light to a material for dry formation of an
image through an original picture corresponding to the
image, the said material being one comprising a photo-
sensitive composition comprising a dyestuff having photo-
fading properties selected from the group consisting of
azo dyestuffs, azomethine dyestuffs, triphenylmethane
dyestuffs, xanthene dyestuffs, oxazine dyestuffs, naphthol
dyestuffs and anthraquinone dyestuffs, an aryl ketone
compound selected from the group consisting of benzophenones,
acetophenones,benzoins, acyloins and .alpha.-diketones as a
sensitizing agent and a high molecular polymer selected
from the group consisting of polyamide resins, urethane
resins, N-substituted high polymers having acrylamide
and/or methacrylamide units, vinyl acetate polymers and
their partially saponified products, polymers of vinyl
monomers having a secondary hydroxyl group, epoxy resins,
copolymers of styrene or its derivatives and phenol resins
as a binding agent.
39

20. The method according to claim 19 wherein said
light is applied to a material formed by incorporatring
said photo-sensitive composition into a plastic material
and molding the resulting product.
21. The method according to claim 19 wherein said light
is applied to a material formed by applying said photo-
sensitive composition or its solution in an appropriate
solvent on a supporter to form a layer of the photo-sensitive
composition.
22. The method according to claim 19, 20 or 21, wherein
the photo-sensitive composition contains the dyestuff in
an amount of 0.05 to 20 parts by weight; the aryl ketone
sensitizing agent in an amount of 0.2 to 200 parts by
weight and the high molecular polymer in an amount of 100
parts by weight.

Description

Note: Descriptions are shown in the official language in which they were submitted.


1l)46BZ6
The present invention relates to a photo-sensitive
composition for dry formation of image. More particularly,
it relates to a photo-sensitive composition for dry formation
of image which can afford a visible image by the irradiation
of light and maintain the image without any fixing treatment.
By the recent remarkable progress in the field of
materials for formation of image, there have been developed
a variety of materials, which have become more and more
excellent and convenient in cooperation with improvement of
apparatuses. Among them, a material of dry reproduction type
is excelling the rest in facility on handling. Expecially,
a striking development has been made in an electrophotography
method. However, for all its merits such as the nigh speed in
reproduction and easy handling due to dry operation, the
'~ electrophotography method is disadvantageous in several points
that the resolving power is insufficient and the edge
phenomenon occurs, that the use of a toner requires conserving
of the apparatus, that a high electric pressure is necessitated
so that the apparatus is made large, etc.
~ 20 For improving these disadvantages, the present
- inventors have made studies on various materials for formation
of image, and, as the result, there has now been completed a
novel photo-sensitive composition for formation of image
which can overcome the said drawbacks by utilization of the
photo-fading reaction of dyestuffs.
The photo-fading reaction of dyestuffs itself is
a well-known phenomenon, and the utilization of this reaction
in materials for formation of image has been proposed in
several literatures. For example, the photo-fading reaction
of cyanine
~L
~'
- 2 -

10468Z6
dyes has been described in Japanese Patent Publication Nos.
17236/1963 and 17237/1963, and the photo-fading reaction
of acid-base type reagents has been reported in Japanese
Patent Publication No. 16084/1962. Further, in U.S. Patent
No. 2,281,895, there is proposed a material utilizing the
- photo-fading reaction of azo dyes. However, these reactions
are all insufficient in the sensitivity, and a s~tisfying
contrast cannot be obtained, so that the proposals are
not yet made practicable.
According to one aspect of the invention there is
provided a photo-sensitive composition used for the dry
formation of an image consisting essentially of a dye-
stuff having photo-fading properties selected from the
group consisting of azo dyestuffs , azomethine dyestuffs,
triphenyl-methane dyestuffs, xanthene dyestuffs, oxazine
dyestuffs, naphthol dyestuffs and anthraquinone dyestuffs,
an aryl ketone sensitizing agent selected from the group
,l consisting of benzophenones, acetophenones, benzoins,
acyloins and a-diketones and a high molecular polymer binding
20 agent selected from the group consisting of polyamide -
resins, urethane resins, N-substituted high polymers having
acrylamide and/or methacrylamide units, vinyl acetate
polymers and their partially saponified products, polymers
of vinyl monomers having a secondary hydroxyl group, epoxy
resins, copolymers of styrene or its derivatives and
phenol resins wherein the proportions of the dyestuff, the
ketonic sensitizing agent and the high molecular polymer
are 0.05 to 20 : 0.2 to 200 : 100 parts by weight.
According to another aspect of the invention there
;~ 30 is provided a method for production of an image which
comprises applying a light to a material for dry formation
~ - 3 -
. ~ ~
B

10468Z6
of an image through an original picture corresponding to
the image, the said material being one comprising a
photo-sensitive composition comprising a dyestuff having
photo-fading properties selected from the group consisting
- = of azo dyestuffs, azomethine dyestuffs, triphenylmethane
dyestuffs, xanthene dyestuffs, oxazine dyestuffs, naphthol
dyestuffs and anthraquinone dyestuffs, an aryl ketone
, compound selected from the group consisting of benzophenones,
acetophenones, benzoins, acyloins and ~-diketones as a
sensitizing agent and a high molecular polymer selected
- from the group consisting of polyamide resins, urethane
resins, N-substituted high polymers having acrylamide and/or
methacrylamide units, vinyl acetate polymers and their
t partially saponified products, polymers of vinyl monomers
having a secondary hydroxyl group, epoxy resins,copolymers
of styrene or its derivatives and phenol resins as a binding
agent.
i The composition of the present invention thus com-
prises a dyestuff, a sensitizing agent and a binding agent
as the essential components. As the dyestuff, there may be
used any one conventionally employed in the formation of
`~ image. The sensitizing agent is required to be a ketonic
sensitizer, particularly an aryl ketone sensitizer. The
binding agent is to be a high polymeric material which is
compatible with the dyestuff and the sensitizing agent, can
promote the action of the sensitizing agent and is capable of
combining the composition on a supporter.
~n the composition of the invention, a highly sensitive
photo-fading reaction of the dyestuff can be caused. Sur-
^ 30 prisingly, the presence of oxygen or air containing oxygen
prevents the occurence of the reaction, while the progress of
the reaction is promoted by the irradiation of strong light and
not by the irradiation of weak light such as scatter~g light in a rxx~
~ B
- 3a -

`` ~046826
Therefore, the fixing operation after the formation of image
is not required.
Accordingly, a main advantage of the present
invention, at least in the preferred embodiments, is that it
can provide a composition for dry formation of image which
can form a visible image by a highly sensitive photo-fading
reaction. Another advantage of this invention, at least in
the preferred embodiments, is that it can provide a composition
for dry formation of image which can form a visible image by
a highly sensitive photo-fading reaction. Another advantage
of the invention, at least in the preferred embodiments, is
that it can provide a composition for dry formation of image
which does not necessarily require the fixing operation after
the formation of a visible image. A further advantage of the
; invention, at least in the preferred embodiments, is that it
can provide a composition for dry formation of image which
can form a visible image being able to be optionally eliminated.
These and other advantages of the invention will be apparent
to those conversant with the art to which the present inv~ntion
pertains from the foregoing and subsequent descriptions.
As the dyestuff, there may be employed any conven-
tional one insofar as a desired photo-fading property is
exhibited in the presence of the photo-sensitizing agent and
the high polymeric material. Examples of the dyestuff are
azo dyestuffs, azomethine dyestuffs, triphenylmethane dye-
stuffs, xanthene dyestuffs, oxazine dyestuffs, naphthol dye-
stuffs, anthraquinone dyestuffs, cyanine dyestuffs, etc.
More specifically, the following organic dyestuffs may be
employed: magenta color, C.I. acid red 249 (color index
18134), C.I. direct red 20 (color index 15075), C.I. acid
red 32 (color index 17065), C.I. acid red 92 lcolor index
.. ~.
- 4 -
.

`` 1046826
45410), C.I. basic violet 7 (color index 48020~, C.I. basic
~ red 13 (color index 48015); cyan color, C.I. acid blue 83
(color index 42660), C.I. acid blue 9 (color index 42090),
: C.I. basic blue 1 (color index 42025), C.I. basic blue 5
: (color index 42140), C.I. direct blue 106 (color index 51300),
- C.I. disperse blue 26 (color index 63305); yellow color, C.I.
acid yellow 25 (color index 18835), C.I. acid yellow 29
.
.
- 4a _

104682~;
(color index 18900), C.I. acid yellow 42 (color index 22910),
C.I. disperse yellow 3 (color index 11855), C.I. reactive
yellow 2 (color index 18972); black color, C.I. acid black
52 (color index 15711), C.I. acid black 24 (color index
26370), C.I. direct black 17 (color index 27700)~ etc.
~ s the sensitizing agent, there is used a ketonic
sensitizer, particularly an aryl ketone sensitizer. Specific
examples of the aryl ketone sensitizer are as follows: benzo-
phenones (e.g. benzophenone, 4-methylbenzophenone, 4-chloro- i
benzophenone, 4-ethylbenzophenone, 4,4'-dimethoxybenzophenone),`
acetophenones (e.g. acetophenone, 4-methylacetophenone, propio-
phenone, benzalacetophenone, C~-bromoacetophenone), benzoins
(e.g. benzoin, benzoin methyl ether, benzoin ethyl ether,
benzoin isopropyl ether, benzoin n-butyl ether, a-methyl-
benzoin, a-benzylbenzoin, anisoin ethyl ether), acyloins (e.g.
acetoin, phenylacetoin, butyroin), ~-diketones (e.g. biacetyl
benzyl, 4-methylbenzyl, 1-phenylbutanedione-1,2)
As the binding agent, there may be used any high
polymeric material which is compatible with the dyestuff and
the sensitizing agent and can promote the action of the
sensitizing agent and combine the composition on a supporter.
Particularly preferred high polymeric materials are a high
polymer containing an N-C bond wherein the carbon atom bears
one or more hydrogen atoms, a high polymer containing a second-
ary OH group and a high polymer containing a benzene ring
bearing at least one of methyl, methylene or methine. Specific
examples are as follows:
(1) Polyamide resins such as nylons (e.g. nylon 6,
nylon 8, nylon 11, nylon 12, nylon 66, nylon 610, nylon 612),
nylon copolymers (e.g. nylon 6/66, nylon 6/12, nylon 6/66/610,

1046826
- nylon 6/66/12) and N-substituted nylons. Examples of the
substituent in ~-substituted nylons are lower alkyl (e.g~
methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl),
hydroxy(lower)alkyl (e.g. hydroxymethyl, ~-hydroxyethyl,
2-hydroxypropyl), cyano(lo~er)alkyl (e~g. 2-cyanoethyl),
halo(lower)alkyl (e.g. 2-chloroethyl), lower alkoxy(lower)-
alkyl (e.g. methoxymethyl, ethoxymethyl, n-butoxymethyl,
2-methoxyethyl, 2-n-butoxyethyl, 4-methoxybutyl), phenoxy-
(lower)alkyl (e.gO phenoxymethyl), etc.
(2) Urea resins such as butylated urea resin.
(3) Urethane resins.
(4) MelamineresinsO
(5) N-substituted high polymers having acrylamide
and/or methacrylamide units. Examples of the substituent
may be those as described in (1).
(6) Vinyl acetate polymers (homopolymers and co-
polymers) and their partially saponified products. Exa~ples
are polyvinyl acetate, 50 % saponified polyvinyl acetate,
vinyl acetate-vinyl chloride-maleic acid copolymer, vinyl
acetate-ethylene copolymer, vinyl acetate-acrylic acid
copolymer, etc. In case of the copolymers wherein the
vinyl acetate ~nits are partially saponified, the content
of the vinyl alcohol units is preferred to be 5 to 95 mol %
based on the total amount of the monomeric units.
(7) Polymers of vinyl monomers having a secondary
hydroxyl group. Examples of such vinyl monomers are 2- ¦
~ydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxy-
propyl p-vinylbenzoate, p-2-hydroxypropoxystyrene, etc.
(~) Epoxy resins.
(9) Cellulose resins such as nitrocellulose, cellu-
-- 6 --

1046826
lose phthalate, hydroxymethylcellulose, hydroxypropylcellulose
and hydroxypropylmethylcellulose phthalate.
(10) Butyral resins such as polyvinylbutyral and
vinylacetal butyral copolymer.
(11) Acetal resins such as polyvinylacetal dimethyl-
aminoacetate.
(12) Acryl resins such as a copolymer containing
a methacrylic moiety as the main constituent.
(13) Alkyd resins.
(14) Unsaturated polyester resins.
(15) Copolymers of styrene or its derivative (e.g.
p-vinyltoluene, p-chloromethylstyrene) with any other monomer,
preferably an acrylic monomer. Examples are styrene-n-butyl ~
acrylate-2-hydroxyethyl methacrylate copolymer, styrene-ethyl -
acrylate-acrylamide copolymer and alkyd resin-styrene-diacetone
acrylamide graft copolymer, and their p-vinyltoluene and
p-chloromethylstyrene alternatives.
~ 16) Phenol resins.
The above essential components may be admixed in
an appropriate proportion depending on the use. Usually,
to 100 parts by weight of the binding agent, 0.05 to 20
parts by weight (preferably 0.2 to 5 parts by weight) of the
dyestuff and 0.2 to 200 parts by weight (preferably 1 to 100
parts by weight) of the sensitizing agent are employed. When
the amount of the dyestuff is smaller than the said lower
limit, the coloring becomes weak resulting in the decrease
of the contrast. When the amount is larger than the said
upper limit, a long time is required in the photo-fading
reaction to reduce the practical value. When the amount of
the sensitizing agent does not reach the said lower limit,
the sensitivity becomes insufficient. On the contrary, the

1~46826
amount exceeding the said upper limit is undesirable from
the practical viewpoint, because the effect of the binding
agent is not exerted. As for the relationship between the
amounts of the dyestuff and the sensitizing agent, the
sensitizing agent is always used in a larger a unt, preferably
5 to 200 times as large as that of the dyestuff.
In addition to the said essential components, there
may be incorporated into the composition of the invention
any additive such as a plasticizer, a dispersing agent, an
emulsifying agent or the like or various purposes such as
increasing the compatability between the dyestuff and the
sensitizing agent or the adhesion between the composition and
the supporter. Further, for increasing the sensitivity so
as to improve the contrast, there may be also employed any
other additive such as an aldehyde (e.g. benzaldehyde, o- -
anisaldehyde, phenylacetaldehyde), an amide (e.g. N-n-
propylbenzamide, benzanilide, N,N-diisopropylacetamide) or
a'thiocarbonyl compound (e.g. phenylthiocarbamide, 4,4'-
dimethoxythiobenzophenone, thiocyanamine, N,N-dimethyl-N'-
allylthiourea, N-hydroxyethyl-N'-allylthiourea). These
additives may be used in an appropriate amount depending on
the purpose.
For preparation of a material for image formation,
the thus obtained composition of the invention may be
incorporated into a plastic sheet (e.g. polyester, polyamide)
or applied on a suitable supporter such as a sheet made of
plastics, metals (e.g. iron, aluminum), paper, woods, glass,
ceramics or the like, if necessary, in the form of a
solution, by a per se conven~ional procedure such as dipping,
brushing, spraying or coating. After application, tne
composition is dried in a usual manner such as air drying,
-- 8 --
__ ,, _ . . . .

10468Z6
drying under reduced pressure or hot air drying to form a
film having a thickness of S to 100 ~, preferably 10 to 50 ~.
When the thickness of the film is smaller than the said lower
limit, the amount of the dyestuff is insufficient to decrease
the contrast. When the thickness is larger tnan the said
upper limit, light does not reach the inside of the composition,
so that the sensitivity is reduced.
The thus prepared photo-sensitive material is sub-
jected to irradiation of light by the aid of a suitable light
source such as a low pressure mercury lamp, a high pressure
mercury lamp, a super high pressure mercury lamp, a xenon lamp,
a chemical lamp or a carbon arc lamp. When an appropriate
original picture is placed on the material at the irradiation,
the image of the original picture can be well reproduced
minutely with excellent contrast. The formation of an image
having an excellent contrast can be achieved in an irradiation
time of only 1 to 10 seconds by selecting appropriately the
kind and proportion of the components of the composition,
the kind of the supporter, the thickness of the film of the
composition, the kind of llght source, the irradiation distance
and the like.
The thus prepared photo-sensitive material of the
invention can afford a visible image by a simple operation of
irradiation of light without any development procedure. The
visible image can be stably kept for a long time under
irradiation of weak light such as scattering light in a room
without any fixing operation.
For well understanding this characteristic phenomenon,
the present inventors have made extensive studies and found
that the fading of the image progresses gradually even under
irradiation of weak light such as scattering light in a room
_ g _

1046826
in the atmosphere of an inert gas (e.g. nitrogen gas, carbon
dioxide gas) or in vacuum, or in such an air-free state as
being tightly covered by a transparent material (e.g. glass
sheet, plastic sheet). Namely, by the irradiation of strong
light, the fading progresses in the air, while by the
irradiation of weak light such as scattering light in a room,
the fading does not occur in the air but gradually progresses
in an air-free state. Supposedly, this interesting phenomenon
is attributable to the balance b~tween the rate of oxygen
consumption by light and the rate of diffusion of oxygen from
the air to the system. Thus, according to the invention, a
visible image can be stored for a long time in the air without
fixing and, if necessary, it can be eliminated with ease by
the irradiation of light to the whole surface or by dipping
into an aqueous solution of a weak acid or base, so that the
material of the invention is particularly useful in the
preparation of special secret documents. Further, the forma-
tion of visible image can be executed simply and rapidly
without any development or fixing procedure requiring the
use of chemicals. Furthermore, the resolving power of the
image is increased, and optional shading is obtained by
varying the amount of light, which results in attaining an
excellent reproducibility.
The material for image formation of the invention
can exhibit, merely by the specific combination of the
sensitizing agent and the binding agent, an excellent
sensitivity of 10 to 100 times as high as that of a conven-
tional material for image formation utilizing the fading
reaction of a dyestuff.
The material for image formation of the invention
can be employed, due to its superior quality as mentioned
-- 10 --

1046826
above, in a variety of uses such as usual copying paper,
reproduction of photographs of multi-step tone, microscope
photographs, precision pictures, scientific literatures,
artistic works, photographs for technical information, figures,
special secret documents and the like.
One of the effective utilizations of the composition
of the invention is the preparation of a color-proof material
therewith. Therefore, such utilization will be hereinafter
illustrated in details.
Hitherto, the rough reading in plate making has been
effected through proof sheets. However, the operation requires
a long time, and the result is varied by the individual
difference, so that there has been highly desired the
appearance of materials for color-proofs which can satisfy
various requirements such as being handled with ease and
good workability and without any harmful influence to human
bodies.
For this purpose, there have been already proposed
various materials for color-proofs and methods for preparation
of color-proofs therefrom. For example, in Japanese Patent
Publication Nos. 6403/1969 and 16045/1971, there are described
the so-called overlay method by which a color image is formed
on a transparent supporter and the supporters to be used in
such method. Further, Japanese Patent Publication Nos. 15326/
1971 and 35682/1971 disclose the so-called transfer method
by which a color image once formed is transcribed on another
supporter. In these conventional arts, however, there are
caused various drawbacks in the preparation of color-proofs,
since a photopolymer is employed in the material for color-
proofs: that iæ, the development procedure is required forremoving the photopolymer in the unhardened part, a large
-- 11 --

1046~26
and precise apparatus is necessitated for assuring sufficient
transcription of the photopolymer in the hardened part (color
image part), the color image concentration or the spot percent
is changed depending on the pressure and the temperature at
the transcription, the toner of the coloring matter for
development has a harmful influence to human bodies, the
workability is low, etc.
While the complete reproduction of the color image
concentration and the spot percent necessa~y for materials
for color-proofs is difficult insofar as a photopolymer
requiring the development step or the transcription step
is employed, the use of the composition of the invention having
a photo-fading property attributable to the photo-fading
reaction of a dyestuff can overcome all of the above mentioned
drawbacks makes it possible to provide a material for color-
proofs from which a color-proof can be readily prepared under
a dry condition by the irradiation of light or the simple
transcription operation without any development and fixation
steps.
For preparation of a color-proof materLal, the
composition of the invention having a photo-fading property
is, in the form of a solution in a suitable solvent, applied
on a supporter to form a layer of the composition thereon.
As the solvent, there may be used any one which
can dissolve the essential three components in the composition
uniformly. Examples of such a solvent are water, haloalkanes
(e.g. chloroform), a alkanols (e.g. methanol, ethanol,
propanol), ketones (e.g. acetone, methyl ethyl ketone, methyl
isobutyl ketone), aromatic hydrocarbons (e.g. benzene, xylene,
toluene), etc. These solvents may be used alone or in
combination. The amount of the solvent is decided depending
- 12 -

`` 10468Z6
on the physical properties of the high polymeric material as
the binding agent. Usually, it is used in such an amount
that the concentràtion of the composition (i.e. the combina-
tion of the three essential components~ having a photo-fading
property becomes 5 to 60 % by weight, preferably 10 to 40 %
by weight. When the concentration is 5 % by weight or smaller,
the formation of the layer of a sufficient film thickness is
often difficult due to the small viscosity of the solution.
When the concentration exceeds 60 ~ by weight, the dissolution
of the three components becomes very difficult.
Since the preparation of color-proofs having a
decomposed color image from the color-proof material of the
invention is effected by a conventional overlay or transfer
method, the said supporter should be made of a material
suitable for these methods.
In case of adopting the overlay method, a trans-
parent, thin sheet is employed as the supporter. Particularly
the one having a high transparency is preferable for the
prevention of the turbidity due to the cloudiness of the
supporter as usually seen in the overlay method. Examples
of such a sheet are transparent sheets made of plastics
such as polyester, polypropylene, polyethylene, polyvinyl
chloride, triacetate resin, polystyrene, polyolefin,
polycarbonate, polyamide and cellulose. The thickness of
the sheet may be 10 to 300 ~, preferably 50 to 100 ~, in view
of the stability of the measurement.
In case of the transfer method, there is no
particular limitation unlike the case of the overlay method,
and a sheet having a surface sufficiently susceptible to
peeling off may be employed. Examples of such a sheet
include the above mentioned transparent plastic sheets and
- 13 -
_~ .

1046826
non-transparent sheets such as a metal plate (e.g. aluminum,
iron, copper) and a rubber plate (e.g. silicon rubber, latex
rubber). For increasing the peeling-off property, the surface
o~ the supporter may be coated with an appropriate peeling
agent or subjected to a physical or chemical treatment.
The applicatian of the composition of the invention
having a photo-fading property on the supporter may be
executed by a per se conventional procedure such as dipping,
brushing, spraying or coating. The applied material is dried
by an appropriate procedure (e.g. air-drying, drying under
reduced pressure, hot air drying) to form a layer of the
composition having a photo-fading property (photo-sensitive
layer). The thickness of the layer is desired to be in the
range of 10 to 100 ~, preferably 20 to 60 ~. With a thickness
smaller ~han 10 ~, the concentration of the dyestuff becomes
small to decrease the contrast of the color image. With a
thickness larger than 100 ~, on the contrary, the photo-
sensitivity becomes lowered, and the irradiated part is apt
to become turbid.
From the thus obtained material for color-proofs
of the invention, a color-proof is prepared by the conventional
overlay or transfer method, as explained in the following
descriptions.
In case of the overlay method, the photo-sensitive
layer of the material for color-proof of the invention is
contacted closely with an original plate for color decomposition
and subjected to the irradiation of light by the aid of an
appropriate light source such as a low pressure mercury la~,
a high pressure mercury lamp, a super high pressure mercury
lamp, a xenone lamp, a chemical lamp or a carbon arc lamp.
These light sources can effectively generate light of short
- 14 -
, . . .
: ~

1046826
wave length being well absorbed by the photo-sensitizing agent.
Therefore, by employing the photo-sensitizing agent which
absorbs light of short wave length, the fading of the
material for color-proof is not caused under the scattering
light in a room, and the color imaqe can be formed in an
extremely short time. For example, when benzophenone which
absorbs light of wave length of around 365 m~ is used as the
photo-sensitizing agent, the most preferred light source is a
high pressure mercury lamp generating light of wave length of
365 m~. Under such a condition, the fading of the material
for color-proof takes place rapidly to form a color image.
Since the scattering light in a room hardly contains light
of wave length of 400 m~ or shorter, the material for color-
proof does not fade at all under the scattering light in a
room. By the irradiation of light, the color image of the
original plate is excellently transcripted. The obtained
positive color image can be as such stored with good stability
for a long duration of time under weak irradiation of
scattering light in a room. By piling transparent color
image sheets having a positive color image of each decomposed
color in order with estimation, there is completed a color-
proof by the overlay method. The piling may be executed by
heating the sheets to make the binding agent of high polymer
viscous, or by applying a suitable colorless, transparent
adhesing agent such as polyolefin, acryl resin, vinyl
acetate resin, epoxy resin or nitrile rubber between the
sheets.
In the transfer method, the photo-sensitive layer
of the material for color-proof of the invention is closely
contacted with an original plate for color decomposition and
subjected to the irradiation of light by the aid of a suitable
- 15 -

1046826
light source as mentioned in the overlay method to form a
positive color image. The thus obtained color images are
transcribed in order on a white supporter so as to complete
a color-proof. As the white supporter, there may be used
art paper, synthetic paper, plastic sheet containing a white
pigment, white thick paper or the like,having a good
stability in the measurement. The white supporter exhibits
excellent adhesion with the positive color image, since it
is not subjected to the surface treatment unlike the
supporter for the material for color-proof of the invention,
so that the transcription of the positive color image is
executed by simply heating or under pressure. As the case
may be, the white supporter is applied an appropriate adhesing
agent on its surface or subjected to a surface treatment
so as to improve the adhesion. The conditions at heating
or giving pressure in the transcription are varied depending
on the properties of the two supporters (i.e. the supporter
for the material for color-proof and the white supporter).
Pressure-giving is usually executed by using a pressure roller
for adhesion or a gum roller. More simply, it may be
accomplished by tightly pressing the piled supporter down
by hands whereby the transcription is executed due to the
difference of the adhesion between the two supporters. After
the first color image is transcribed on the white supporter,
the second color image is transcribed in the same manner on
the transcribed first color image, the transcription operation
is thus repeated. In usual, the adhesion and the transcription
between color images are executed with ease by heating, though
the condition is varied depending on the kind of the binding
agent of high polymer. If necessary, an appropriate adhesing
agent may be applied on the first color image to improve
- 16 -

10468Z6
the adhesion with another color image. It is favorable to
coat the top of the color images with a transparent film in
order to protect the transcribed color images.
As mentioned above, the material for color-proof
of the invention may be treated by the overlay method or
transfer method. By employing a transparent supporter in
the material for color-proof, both methods can be adopted.
The material for color-proof of the invention can readily
afford a color-proof under a dry condition by the irradiation
of light and the piling with estimation or the simple
transcription operation without any development procedure.
In the conventional material for color-proof, a photopolymer
is employed to cause the photopolymerization, so that the
difference between the photo-hardened part and unhardened
part i8 utilized, while the half-hardened part as the
intermediate state can not be utilized. In the present
invention, on the contrary, since the photo-fading reaction
is adopted, the fading of the dyestuff is proportional to
the amount of light, and therefore the intermediate state
can be well utilized. Consequently, there can be obtained
a color image having continuous multi-step tone which have
never been attained by the conventional material using a
photopolymer. Such a color image can be utilized in the
proofreading of an original color decomposition plate for
plate making of gravure. Furt,ner, it is the most suitable
as a color-proof, since the fading of the color image is
hardly caused under the scattering light in a room without
the fixing.
By employing an apparatus in which the material
for color-proof to be irradiated can be kept under vacuum
condition without air, the material for color-proof is
- 17 -

1046826
highly sensitized, and the formation of a color image can
be executed by the irradiation in an instant to save the
operation time. The most advantageous feature of the
material for color-proof of the invention is that it can be
used in both of the overlay method and the transfer method
when a transparent supporter is employed. Particularly, when
used in the overlay method, there can be obtained a color
image having tone of color quite identical to that of the
original plate, because a dye is used as the dyestuff in
the photo-sensitive composition having photo-fading property
By the use of the material for color-proof of the
invention, the operation of the inner proofreading in the
plate making can be executed in a shortened time without
formation of harmful substance and individual difference,
and thus the stability required as a color-proof can be well
maintained. Further, the material for color-proof of the
invention is useful not only in the proofreading of original
color decomposition plate for offset and relief printing but
also in the proofreading for gravure which has hitherto been
difficult, because it can afford a color image having multi-
step continuous tone of color.
Practical and presently preferred embodiments of
the invention are illustratively shown in the following
Examples wherein parts and % are by weight.
Example 1
A 10 % aqueous methanol solution (10 parts) of 50
saponified polyvinyl acetate resin ("Corponyl PK-40" - Trade
Mark - manufactured by Nihon Gosen Kagaku Industry Co., Ltd.
number average polymerization degree, 1700) and benzophenone
(0.5 part) are admixed and dissolved each other, and a 1 %
methanol solution (1.5 parts) of Solar Cyanine 6B (a
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1046826
triphenyl-methane dye manufactured by Sumitomo Chemical Co.,
Ltd.; color index, 42660) is added thereto to make a uniform
mixed solution. The thus obtained mixed solution is applied
on an aluminum plate by the aid of a bar coater and dried
at 45 ~ 5C in a hot air dryer for 2 minutes to obtain a
photo-sensitive material (thickness of film, 20 ~), which
is subjected to the irradiation of light through Kodak Step
Tablet No. 2 by the aid of a carbon arc lamp (30 A) from a
distance of 40 cm for 3 seconds. The thus irradiated photo-
sensitive material possesses as such the ability to show acontinuous tone. The sensitivity amounts to 9 steps. When
the continuous tone is stored without fixing for a week, any
appreciable change is not observed.
The thus stored image is then subjected to the
irradiation of light on the whole surface under the same
condition as above whereby the original image disappears
clearly, and the whole surface is completely faded.
When the image of the photo-sensitive material
before the storage is subjected to the irradiation of light
through the test chart No. 1 of the electrophotography
society under the same condition as above, the reproduction
is satisfactorily executed up to a resolving power of 16
lines~mm.
Example 2
The preparation of a photo-sensitive material is
executed as in Example 1 uslng the 10 % aqueous methanol
solution (10 parts) of 50 % saponified polyvinyl acetate
resin, benzophenone (0.4 part), the 1 % methanol solution
(1.5 parts) of Solar Cyanine 6 B and thiocyanamine (0.2
part). The thus prepared photo-sensitive material is
subjected to the irradiation of light as in Example 1.
-- 19 --

1046826
The sensitivity and the resolving power are shown in Table 1.
Example 3
The preparation of a photo-sensitive material is
executed as in Example 1 using the 10 % aqueous methanol
solution (10-parts) of 50 % saponified polyvinyl acetate
resin, benzophenone (0.2 part), a 1 % methanol solution
(2 parts) of Sunchromine Blue FBG (a triphenylmethane dye
manufactured by Sumitomo Chemical Co., Ltd.; color index,
43855), o-anisaldehyde (0.2 part) and benzaniline (0.2 part).
The thus prepared photo-sensi~ive material is subjected to
the irradiation of light as in Example 1. The sensitivity
and the resolving power are shown in Table 1.
Example 4
The preparation of a photo-sensitive mate-rial is
executed as in Example 1 using the 10% aqueous methanol
solution (10 parts) of 50 % saponified polyvinyl acetate
resin, acetophenone (0.4 part), a 1 % methanol solution
(2.2 parts) of Aizen Rose bengal B ~a xanthene dyestuff
manufactured by Aizen Corp.; color index, 45440) and phenyl-
acetaldehyde (0.2 part). The thus prepared photo-sensitive
material is subjected to the irradiation of light as in
Example 1. The sensitivity and the resolving power are
shown in Table 1.
Example 5
The preparation of a photo-sensitive material is
executed as in Example 1 using the 10 % aqueous methanol
solution (10 parts) of 50 % saponified polyvinyl acetate
resin, benzyl (0.2 part), butyroin (0.2 part), the 1 %
methanol solution of Aizen Rose bengal ~ (2.2 parts) as
in Example 4 and N-n-propylbenzamide (0.2 part). The thus
prepared photo-sensitive material is subjected to the
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1046826
irradiation of light as in Example 1. The sensitivity and
the resolving power are shown in Table 1.
Example 6
The preparation of a photo-sensitive material is
executed as in Example 1 using a 10 % isopropanol-acetone
(1:1) solution (10 parts) of nitrocellulose (nitration
degree, L; viscosity, 1/2), benzophenone (0.4 part) and the
1 % methanol solution of Solar Cyanine 6B (1.5 parts) as in
Example 1. The thus prepared photo-sensitive material is
subjected to the irradiation of light as in Example 1. The
sensitivity and the resolving power are shown in Table 1.
Example 7
The preparation of a photo-sensitive material is
executed as in Example 1 using a 10 % aqueous methanol
solution (10 parts) of 40 % saponified ethylene-vinyl
acetate copolymer (vinyl acetate, 80 mol %), 4-chlorobenzo-
phenone (0.4 part) and the 1 % methanol solution of Solar
Cyanine 6 B (1.5 parts) as in Example 1. The thus prepared
photo-sensitive material is subjected to the irradiation of
light as in Example 1. The sensitivity and the resolving
power are shown in Table 1.
Example 8
The preparation of a photo-sensitive material is
executed as in Example 1 using a 10 % ethanol-acetone ~1:1) :
solution (10 parts) of a copolymer mainly consisting of
2-hydroxypropyl methacrylate and n-butyl acrylate (molecular
weight, 48000), benzophenone (0.2 part), benzoin ethyl ether
(0.2 part) and the 1 % methanol solution of Solar Cyanine ~B
(1.5 parts) as in Example 1. The thus prepared photo-
sensitive material is subjected to the irradiation of light
as in Example 1. The sensitivity and the resolving power

~0468Z6
are shown in Table 1.
Example 9
The preparation of a photo-sensitive material is
executed as in Example 1 using a 10 % methanol-chloroform
(7:3) solution (10 parts) of copolymerized nylon resin
("CM 8000" - Trade Mark - manufactured by Toyo Rayon Co.,
Ltd.; specific gravity, 1.12, melting point, 128C),
acetophenone (0.5 part) and the 1 % methanol solution of
Solar Cyanine 6 B (1.3 parts) as in Example 1. The thus
prepared photo-sensitive material is subjected to the
irradiation of light as in Example 1. The sensitivity
and the resolving power are shown in Table 1.
Exa~le 10
The preparation of a photo-sensitive material is
executed as in Example 1 using a 10 % methanol-chloroform-
water (7:2:1) solution (10 parts) of N-methoxymethylnylon 6
("Type 8 nylon" manufactured by Unichika Co., Ltd.; N-methoxy-
methylation degree, 28 - 30 ~), benzophenone (0.3 part) and
the 1 ~ methanol solution of Solar Cyanine 6 B (1.5 parts)
as in Example 1. The thus prepared photo-sensitive material
is subjected to the irradiation of light as in Example 1.
The sensitivity and the resolving power are shown in Table 1.
Example 11
The preparation of a photo-sensitive material is
executed as in Example 1 using a 10 ~ ethanol-chloroform
(8:2) `solution (10 parts) of N-n-butylnylon 66 (number average
molecular weight, 3200; N-n-butylation degree, 22 - 25 %),
benzophenone (0.3 part) and a 1 % methanol solution (1.5
parts~ of Acid Violet 5B (a triphenylmethane dyestuff
manufactured by Sumitomo Chemical Co., Ltd.; color index,
42640). The thus prepared photo-sensitive material is
- 22 -

1046826
subjected to the irradiation of light as in Example 1. The
sensitivity and the resolving power are shown in Table 1.
Example 12
The preparation of a photo-sensitive material is
executed as in Example 1 using a 10 % 'ethanol-acetone (3:7)
solution tlO parts) of copolymer mainly consisting of
p-chloromethylstyrene and n-butyl acrylate (number average
molecular weight, 35000), benzophenone (0.4 part) and the
1 % methanol solution of Solar Cyanine 6B (1.5 parts) as
in Example 1. The thus prepared photo-sensitive material
is subjected to the irradiation of light as in Example 1.
The sensitivity and the resolving power are shown in Table 1.
Example 13
The uniform mixed solution obtained as in Example 2
is applied on a sheet of paper coated with polystyrene to
~make a photosensitive material as in Example 1. The thus
obtained material is subjected to the irradiation of light
through Kodak Step Tablet No. 2 by the aid of a high pressure
mercury lamp (3 KW) from a distance of 40 cm for 3 seconds.
The sensitivity amounts to 9 steps. When the test for the
resolving power is executed as in Example 1 under the same
irradiation condition as above, the reproduction is satis-
factorily perfPrmed up to 16 lines/mm.
Example 14
The uniform mi~xed solution obtained as in Example 1
is applied an a sheet of paper coated with polystyrene
to make a photo-sensitive material as in Example 1. The
thus obtained material is subjected to the irradiation of
light through Kodak Step Tablet No. 2 by the aid of a xenone
lamp (2 KW~ from a distance of 30 cm for 5 seconds. The sensi-
tivity amounts to 10 steps. When the test for the resolving
- 23 -

10468Z6
power is executed as in Example 1 under the same irradiation
condition as above, the reproduction is satisfactorily
performed up to 16 lines/mm.
Example 15
The uniform mixed solution obtained as in Example 10
is applied on a sheet of paper coated with polystyrene to
make a photo-sensitive material as in Example 1. The thus
obtained material is subjected to the irradiation of light
through Kodak Step Tablet No. 2 by the aid of a hign pressure
mercury lamp (3 KW) from a distance of 40 cm for 3 seconds.
The sensitivity amounts to 10 steps. When the test for
the resolving power is executed as in Example 1 under the
same irradiation condition as above, the reproduction is
- satisfactorily performed up to 16 lines/mm.
Reference Example 1
The preparation of a photo-sensitive material is
executed as in Example 1 using a 20 % methanol-acetone (1:4)
solution ~10 parts) of poly-n-butyl acrylate (molecular
weight, 63000), benzophenone (0.2 part), the 1 ~ methanol
solution of Solar Cyanine 6B (1.5 parts) as in Example 1 and
o-anisaldehyde (0.2 part). The thus prepared photo-sensitive
material is subjected to the irradiation of light as in
Example 1. The sensitivity and the resolving power are
shown in Table 1.
Reference Example 2
The preparation of a photo-sensitive material is
executed as in Example 1 using the 10 ~ aqueous methanol
solution (10 parts) of 50 % saponified polyvinyl acetate
resin as in Example 1, 5-nitroacetonaphthene (0.2 part)
and the 1 % methanol solution of Solar Cyanine 6B (1.5 parts)
as in Example 1. The thus prepared photo-sensitive material
- 24 -

1046826
is subjected to the irradiation of light as in Example 1.
The sensitivity and the resolving power are shown in
Table 1.
Reference Example 3
A sheet of commercially available diazo copying
paper is subjected to the irradiation of light as in
Example 1. The sensitivity and the resolving power are
shown in Table 1.
Table 1
10 ~ Results _ _
Photo~ \ Sensitivity Resolving power
sensitive material \ (Number of stePs)_ _ (lines/mm)
20 ~ Exa ~ e ~ ~ ~ S ~ :
16
121 1 10 1 16
Reference 1 2 8
Example
_ 14 --~ 16.3
Example 16
A 40 % solution of partially saponified polyvinyl
acetate (saponification degree, 30 - 50 %; number average
polymerization degree, 1700; viscosity, 3Q000 cps at 25C
- 25 -

1046826
on a 40 % methanol solution) in aqueous methanol is diluted
to make a 10 % aqueous methanol solution. The thus prepared
dilution (10 parts) and benzophenone (0.5 part) are admixed
and dissolved each other, and a 1 % methanol solution (4.0
parts) of C.I. acid blue 83 (color index, 42660) is added
thereto to make a uniform solution. The obtained solution is
applied on a triacetyl cellulose film (thickness, 80 ~) by
the aid of a bar coater (No. 36), and the film is dried in
a hot air drier at 45 + S C for 2 minutes to make a material
for blue-proof, which is subjected to the irradiation of
light by a high pressure mercury lamp (3 KW) through Xodak
Step Tablet No. 2 from a distance of 70 cm for 60 seconds
whereby a clear blue image having 10 continuous steps of
tone is obtained. ~ -
The above procedure is repeated but using C.I. acid
yellow 29 (color index, 18900) in place of C.I. acid blue 83
whereby a yellow image having 8 continuous steps of tone is
obtained.
Similarly, when C.I. acid red 32 (color index, 17065)
is employed, a red image having 10 steps is obtained.
Further similarly, the use of C.I. acid black 2
(color index, 15711) affords a black image having 6 steps.
Reference Example 4
Each of the materials for color-proof prepared in
Example 16 is closely contacted with an original color
decomposition plate for offset and subjected to the
irradiation of light by a carbon arc lamp (2 KW) from a
distance of 70 cm for 80 seconds. The reproduction of the
original color decomposition plate is executed satisfactorily
on every color. When the thus obtained color image sheets
of each color are piled up each other with conjectural
- 26 -

1046826
estimation, and the piled product is compared with the
original plate under a transmission light source, they
prove to be quite identical eacn other.
Reference Example 5
On the surface of the photosensitive layer of each
material for color-proof prepared in Example 16, a transparent
thin film of vinylidene chloride resin (thickness, 13 ~) is
piled, and the piled product is subjected to the irradiation
of light in the absence of air for 30 seconds as in Example 16
whereby a color image corresponding to the one obtained in
Example 16 is prepared. After the irradiation, the transparent
thin film is removed off, and the material is allowed to stand
in a room under the scattering light for 15 days. The color
image is stable and not changed.
Reference Example 6
One of the color image sheets obtained in Reference
Example 4 is closely contacted with a sheet of art paper
previously applied an adhesive agent (an acryl resin). After
pressed by the aid of a gum roller, the sheet is peeled off
whereby the whole color image is transcribed on the art paper.
On the thus transcribed color image, the adhesive agent is
applied, and another color image sheet is closely contacted
therewith. After pressed by the aid of a gum roller, tne
sheet is peeled off whereby the second color image is removed
from the supporter to give a two-colored image. Similarly,
the third and the fourth color images are transcribed to give
a product consisting of the color images obtained from the
original plates for color decomposition of yellow, cyan,
magenta and black. The thus obtained product reproduces
satisfactorily the original plate and corresponds to the
cdor image obtained by the proof sheet.
- 27 -

1046826
Reference Example 7
-
As in Reference Example 6, the color images obtained
in Example 16 are closely contacted with a white plastic
sheet (polyethylene containing 10 % of titanium oxide; thick-
ness, 300 ~) previously applied the adhesive agent and
subjected to pressing by the aid of a gum roller and peeling
off whereby the whole color images are well transcribed on
the white plastic sheet.
Example 17
The preparation of materials for color-proof is
executed in the same manner as in Example 16 but using, as
the supporter, a polypropylene film (stretched at two axes;
thickness, 60 ~) in place of the triacetyl cellulose film,
and from the thus prepared materials, color image sheets are
obtained as in Reference Example 4. Each of the sheets is
closely contacted with a sheet of white thick paper, heated
in a hot air drier at 100 + 5C, pressed by the aid of a -
gum roller and, after cooling, peeled off whereby the whole
color image is transcribed on the white plastic sheet.
Example 18
The preparation of materials for color-proof is
executed in the same manner as in Example 16 but using, as
the binding agent of high polymer, a 10 % solution of N-
methoxymethylnylon 6 (degree of N-methoxymethylation, 28 to
30 %; viscosity, 500 to 800 cps at 20C on a 20 % methanol
solution) in a mixture of methanol, chloroform and water
(7:2:1) in place of the 10 % aqueous methanol solution of
partially saponified polyvinyl acetate. Each of the thus
prepared materials is subjected to the irradiation of light
for 40 seconds under the same condition as l~n Example 16.
The formed color image corresponds to the one obtained in
- 28 -
,

lQ46826
Example 16.
Exam~le 19
The preparation of materials for color-proof is
executed in the same manner as in Example 16 but using the
10 % solution of N-methoxymethylnylon 6 in a mixture of
methanol, chloroform and water (7:2:1) as in Example 18
(10 parts), benzophenone (0.4 part) and a 1 ~ methanol
solution (4.0 parts) of a dye as shown in Table 2. The thus
prepared materials are subjected to the irradiation of
light under the same conditions as in Example 16. The
results are shown in Table 2.
- 29 -

- iO468Z6
Table 2
. _ _ ._ _ _ _ _
Dyestuffs Result - :
Name Color index (No.) (Number of steps)
Magenta Acid red 249 18134 8
Acid red 32 17065 10
Acid red 92 45410 9
Basic red 13 48015 10
Basic violet 7 48020 10
Direct red 20 15075 11
_ .
Cyan Acid blue 83 42660 10
color
Acid blue 9 42090 11
Basic blue 1 42025 9
Basic blue 5 42140 10
Direct blue 106 51300 10
Disperse blue 26 63305 10
Yellow Acid yellow 25 18835 8
color .
Acid yellow 29 18900 8
Acid yellow 42 22910 9
Disperse yellow 3 11855 10
Reactive yellow 2 18972 8
. _ ........ __ . . _ .
Black Acid black 52 15711 6
color
Direct black 27700 7
Acid black 24 26370
Example 20
A 10 % solution ~10 parts) of polyvinylbutyral resin
(tripolymer of vinylbutyral, vinyl acetate and vinyl alcohol;
degree of butyralation, 65 + 2 mol %; number average polymeri-
zation degree, 1000 to 2000) in a mixture of methanol and
-30-
'

10468Z6
acetone (7:3), benzophenone (0.5 part) and a 1 % methanol
solution (4.0 parts) of C.I. acid red 249 (color index, 18134)
are admixed as in Example 16 to prepare a uniform solution.
The thus obtained solution is applied on a polyester film
(polyethylene terephthalate; thickness, 800 ~) to prepare
a material for red color-proo~ as in Example 16.
Example 21
A material for yellow color-proof is prepared as in
Example 16 using a 10 % methanol solution (10 parts) of
hydroxypropylmethylcellulose phthalate (content of carboxy-
benzoyl group, 20 to 35 %; content of hydroxypropyl group,
6 to 12 %; content of methoxy group, 20 to 25 %; viscosity,
250 + 50 cps at 20C on a 15 % methylene chloride-methanol
solution), benzophenone (0.5 part) and a 1 % methanol solution
(4.0 parts) of C.I. disperse yellow 3 (coloF index, 11855).
Example 22
A material for blue color-proof is prepared in the
same manner as in Example 16 but using C.I. acid blue 9
(color index, 42090) in place of C.I. acid blue 83.
Reference Example 8
Each of the material for black color-proof obtained
in Example 16 and the materials for color-proof prepared in
Examples 20, 21 and 22 is closely contacted with an original
color decomposition plate for offset and subjected to the
irradiation of light by the aid of a carbon arc lamp (2 KW)
from a distance of 70 cm for 80 seconds whereby the reproduction
of the original color decomposition plate is executed satis-
factorily. When the thus obtained color image sheets are
subjected to the pile printing as in Example 20, there can be
formed a color image almost identical to the one obtained by
a proof sheet.
- 31 -

10468Z6
Example 23
The preparation of materials for color-proof is
executed in the same manner as in Example 16 but using, as
the binding agent of high polymer, a 10 % solution of vinyl
chloride-vinyl acetate-maleic acid copolymer (proportion of
the monomers, vinyl chloride:vinyl acetate:maleic acid =
86:13:1 (% by weight); number average polymerization degree,
400) in a mixture of acetone and methanol (7:3) in place of the
10 % aqueous methanol solution of partially saponified poly-
vinyl acetate. Each of the thus prepared materials is subjected
to the irradiation of light through Kodak Step Tablet No. 2
by the aid of a high pressure mercury lamp (3 KW) from a ~-
distance of 70 cm for 50 seconds whereby a good color image can
be obtained.
Example 24
A material for yellow color-proof is prepared in the
same manner as in Example 16 but using C.I. acid yellow 29
and, as the binding agent of high polymer, a 10 % solution
of acryl resin (copolymer mainly containing methacryl moiety;
viscosity, 600 to 800 cps at 25C on a 40 % toluene solution)
in a mixture of toluene and methanol in place of the 10 %
aqueous methanol solution of par~ially saponified polyvinyl
acetate.
Example 25
A material for blue color-proof is prepared as in
Example 24 but using C.I. acid blue 9 (color index, 42090)
and a 10 % methanol solution of diethylaminoethyl methacrylate-
methyl methacrylate copolymer as the binding agent of high
polymer.
Reference Example 9
Each of the material for black color-proof obtained
- 32 -

1046826
- in Example 16 and the materials for color-proof prepared in
Examples 20, 24 and 25 is closely contacted with an original
color decomposition plate for offset and subjected to the
irradiation of light by the aid of a high pressure mercury
lamp (3 KW) from a distance of 70 cm for 90 seconds whereby
the reproduction of the original color decomposition plate
is executed satisfactorily. When the thus prepared color image
sheets are subjected to the pile printing as in Reference
Example 6, there can be obtained a color image almost identical
to the one obtained by a proof sheet.
Example 26
A material for yellow color-proof is prepared as in
Example 16 but using C.I. disperse yellow 3 and, as the
binding agent of high polymer, a 10 % solution of butylated
urea resin (acid value, 3.0; Gardner viscosity, N-0.2) in a
mixture of methanol and butanol (4:6) in place of the 10 %
aqueous methanol solution of partially saponified polyvinyl
acetate.
Example 27
A material for blue color-proof is prepared as in
Example 26 but using C.I. acid blue 9 and, as the binding
agent of high polymer, a 10 % methanol solution of polyvinyl
acetate (number average polymerization degree, 1000; viscosity,
16000 cps at 25C on a 50 % methanol solution).
Example 28
A material for red color-proof is prepared as in
Example 26 but using C.I. acid red 249 (color index, 18134)
and, as the binding agent of high polymer, a 10 % methanol
solution of vinylacetal butyral copolymer (acetal group, 37 -
41 % by weight; butyral group, 37 - 41 % by weight, hydroxyl
group, 17 to 23 % by weight~.
- 33 -

1~46826
Reference Example 10
Each of the material for black color-proof obtained
in Example 16 and the materials for color-proof prepared in
Examples 26, 27 and 28 is closely contacted with an original
color decomposition plate for offset and subjected to the
irradiation of light by the aid of a high pressure mercury
lamp (3 KW) from a distance of 70 cm for 90 seconds whereby
the reproduction of the original color decomposition plate
is executed satisfactorily. When the thus prepared color
image sheets are subjected to the pile-printing as in Reference
Example 6, there can be obtained a color image almost identical
to the one obtained by a proof sheet.
Example 29
The preparation of materials for yellow color-proof
is executed as in Example 16 using a 10 % diluted solution
(10 parts) of a binding agent of high polymer as shown in .
Table 2, benzophenone (0.5 part) and a 1 % methanol solution
(4.0 parts) of C.I. disperse yellow 3. The thus prepared
materials are subjected to the irradiation of light as in
Example 16. The results are shown in Table 3.
- 34 -

lQ468Z6
Table 3
I _ _
Binding agent of Solvent for Result
high polymer dilution (Number of steps)
_ . . ._
Partially saponified Aqueous methanol 9
polyvinyl acetate
N-methoxymethyl- Methanol-chloroform- 10
nylon 6 water (7:2:1)
Polyvinyl butyral Methanol-acetone 8
resin (7:3)
10 Hydroxypropylmethyl- Methanol 10
cellulose phthalate
Vinyl chloride- Acetone-methanol 9
vinyl acetate- (7:3)
maleic acid copolyme
Acryl resin Toluene-methanol 10
(7:3)
Diethylaminoethyl Methanol 9
methacrylate-
methyl methacrylate
20 copolymer
Butylated urea Methanol-butanol 9
resin (4:6)
Polyvinyl acetate Methanol 9
Polyvinyl acetal Methanol 8
butyral copolymer
. _ _ , . _ _
Example 30
The preparation of materials for red color-proof
is executed as in Example 16 using the 10 ~ aqueous methanol
solution (10 parts) of partially saponified polyvinyl acetate
as in Example 16, a photo-sensitizing agent as shown in Table
4 (0.5 part) and a 10 % methanol solution of C.I. acid red
32 (4.0 parts). The thus prepared materials are subjected
to the irradiation of light as in Example 16. The results
are shown in Table 4.
- 35 -

46826
Table 4
_ _ .
Photo-sensitizing agent Result ~ -
(Number of steps)
_ _ _ _ _ __
Benzophenone 10
4-Methylbenzophenone 8
4,4'-Dimethoxybenzophenone 9
Acetophenone 10
Propiophenone 10
Benzal acetophenone ¦ -
- 36 -

Representative Drawing

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Administrative Status

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Event History

Description Date
Inactive: IPC from MCD 2006-03-11
Inactive: IPC from MCD 2006-03-11
Inactive: Expired (old Act Patent) latest possible expiry date 1996-01-23
Grant by Issuance 1979-01-23

Abandonment History

There is no abandonment history.

Owners on Record

Note: Records showing the ownership history in alphabetical order.

Current Owners on Record
NIPPON PAINT CO.
Past Owners on Record
KOICHI KIMOTO
KUNSEI TANABE
SHIN SAITO
YASUSI UMEDA
YASUYUKI TAKIMOTO
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.
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Document
Description 
Date
(yyyy-mm-dd) 
Number of pages   Size of Image (KB) 
Claims 1994-04-14 4 127
Cover Page 1994-04-14 1 17
Drawings 1994-04-14 1 5
Abstract 1994-04-14 1 15
Descriptions 1994-04-14 37 1,237