Note: Descriptions are shown in the official language in which they were submitted.
1329669
.
COATING COMPOSITION
; ,
BACKGROUND OF THE INVENTION
The present invention relates to a coating
; composition, and more particularly to a coating
composition remarkably e~cellent in storage stability in
5 comparison with conventional coating compositions, which
: can be suitably used as a coating material for a
substrate such as metal.
- Recent years, in electrical or electronic
industry, there have been desired transparent coating
10 materials having heat resistance, corrosion resistance,
scratch resistance, weather resistance, and the like.
Examples of the transparent coating materials are, for
instance, transparent coating materials which have been
used to-protect reflectors of lighting equipments or
15 thermal apparatuses, and the like.
S In order to satisfy the above-mentioned
requirements, there have hitherto been studied organic
paints such as silicone resin and fluorine-containing
resin, inorganic paints such as alkaline metal silicate,
20 and the like. However, there has not yet been provided a
coating composition sufficiently having the above
properties. That is, with respect to the former, there
are some defects in heat resistance, weather resistance,
corrosion resistance and scratch resistance, and with
25 respect to the latter, there are some defects in that an
- alkaline material remained in the coating material reacts
with carbon dioxide gas presented in air and a carbonate
is deposited on the surface of the coating, which is so
called "efflorescence", with the passage of time, and
, 30 that the coating composition is poor in workability for
s coating.
- It has been studied to use silica-organosilane
coating compositions having abrasion resistance as a
coating materials whicn are mainly coated on the surface
35 of a plastic material. However, these coating materials
:,:
,. , ~a~
'
1329~9
; are poor in storage stability and workability for
coating. Accordingly, various investigations have been
made to solve these problems. However, there has not yet
been produced a coating material having the sufficient
properties of matter. For instance, silica-organosilane
. . .
compositions for coating having abrasion resistance are
disclosed in Japanese Examined Patent Publication No.
39691/1977, Japanese Examined Patent Publication No.
18626/1981, and the like. However, these compositions
are poor in workability for coating and storage stability
since they contain a large amount of water derived from
aqueous colloidal silica.
A composition for coating which solves the
above-mentioned problems is proposed in Japanese
Unexamined Patent Publication No. 68377/1984. The
workability for application of the composition has been
- surely somewhat improved by distilling water from the
composition. However, the composition has not yet been
satisfied with storage stability. The process for
preparing the composition is complicated since there is a
necessity to distill water from the composition, and
there are some defects in the composition that turbidity
is easily generated, that the viscosity is easily
increased and that the transparency of the coating film
is deteriorated.
In consideration of the above-mentioned
problems of prior art, in the course of studying to give
a composition not only having suffient properties of
matter such as heat resistance, surface hardness,
chemical resistance, abrasion resistance, scratch
resistance, stain resistance and weather resistance, but
~ also having excellent storage stability and workability
; for coating, it has been found that the storage stability
of the composition is remarkably improved by using as a
solvent, a solvent containing a specified amount of
; ethylene glycol monobuty~ ether in comparison with that
7' of the conventional coating compositions, and the present
invention has been accomplished.
:'
_ 3 _ 1329~69
..
SUMMARY OF THE INVENTION
According to the present invention, there is
provided a coating composition comprising silica,
organohydroxysilane, a partial condensate of the
; 5 organohydroxysilane and liquid medium containing ethylene
glycol monobutyl ether in an amount of at least 20 ~ by
weight.
These and other objects of the invention will
be apparent to one skilled in the art upon consideration
of the following description and appended claims.
DETAILED DESCRIPTION
The coating composition of the present
' invention comprises silica, organohydroxysilane, partial
condensate of the organohydroxysilane and liquid medium
~ containing ethylene glycol monobutyl ether in an amount
`, of at least 20 % by weight.
.~ In the present invention, a colloidal silica is
employed as the above-mentioned silica. The colloidal
. 20 silica is usually used as a dispersion. The dispersion
of the colloidal silica is classified into an aqueous
dispersion of colloidal silica which is prepared by
dispersing silicic anhydride having a high molecular
weight in water and a non-aqueous dispersion which is
prepared by dispersing the silicic anhydride in an
alcoholic solvent. The aqueous dispersion of the
- colloidal silica is mainly used in the present
invention. A part of the aqueous dispersion of the
- colloidal silica can be substituted by the non-aqueous
dispersion of the colloidal silica.
The average particle size of the silica
dispersed in the above-mentioned dispersion of the
colloidal silica is preferably not more than 150 m~m and
more preferably not more than 30 m~m. When the average
~ 35 particle size of the silica is more than 150 m~m, there
`~ is a tendency that the coating film does not become
-~ transparent.
~ The con~ent of the silica in ~he above-
.,
~ ',
.,
':
~ 13296~9
-- 4
;.
mentioned dispersion of the colloidal silica is suitably
adjusted to be within a range that dispersion is stable.
It is desirable that the dispersion of the
colloidal silica is acidic since the storage stability of
the obtained coating composition is lowered when the
composition is basic.
The organohydroxysilane and the partial
condensate of the organohydroxysilane used in the coating
composition of the present invention are prepared by
~ 10 hydrolyzing organoalkoxysilane.
; Typical examples of the above-mentioned
~' organoalkoxysilane are, for instance, an
$ organoalkoxysilane represented by the general formula
(II):
'.~,' 15
~' Rl Si(OR2)3 (II)
.'
wherein Rl is a group selected from the group consisting
of alkyl group having 1 ~o 3 carbon atoms, vinyl group,
3,4-epoxycyclohexyl ethyl group, gamma-glycidoxypropyl
group, gamma-methacryloxypropyl group, gamma-
mercaptopropyl group and gamma-chloropropyl group, and R2
is a group selected from the group consisting of alkyl
group having 1 to 4 carbon atoms, alkoxyethyl group
having 1 to 4 carbon atoms and aryl group.
Typical examples of the organohydroxysilane
prepared by hydrolyzing the above-mentioned
organoalkoxysilane are, for instance, an
organohydroxysilane represented by the general formula
: 30 (I):
Rl Si(OH)3 (I)
wherein Rl is the same as mentioned above.
Examples of the partial condensate of the
organohydroxysilane are, for instance, oliqomers prepared
by subjecting the organohydroxysilane represented by the
above-mentioned general formula ~I) to a partial
~:,
.
- 5 ~ 1329~69
condensation.
In the coating composition of the present
invention, the liquid medium is composed of (a) water
contalned in the aqueous dispersion of the colloidal
silica and water derived from the condensation of the
organohydroxysilane, (b) alcohol derived from hydrolysis
of the organoalkoxylsilane and (c) a solvent.
In conventional coating compositions, lower
' aliphatic alcohols such as isopropanol are used as a main
component of the solvent (c), and glycols such as
ethylene glycol and propylene glycol; glycol derivatives
such as ethylene glycol monoethyl ether; and aliphatic
ketones such as acetone and methyl ethyl ketone are used
as a co-solvent of the solvent (c). However, when these
solvents are used in the coating composition, the coating
, composition does not satisfy all of the properties such
as sufficient storage stability, workability for coating,
: film forming property and transparency of the coating
~; film.
In the course of studying about the liquid
.,
-~ medium contained in the coating composition, it is found
that when ethylene glycol monobutyl ether is included in
,~ the liquid medium of the coating composition in an amount
of at least 20 ~ by weight, storage stability,
workability for coating and film forming property of the
coating composition is remarkably improved and the
~, coating film is excellent in transparency, and all of the
defects of conventional coating compositions are
$ removed. When ethylene glycol monoethyl ether or
ethylene glycol monomethyl ether is used instead of
. ethylene glycol monobutyl ether in the coating
`~ composition, the effects derived from ethylene glycol
- monobutyl ether are not revealed. The remarkable effects
are revealed only in case that ethylene glycol monobutyl
- 35 ether is used as a solvent. Usually, there is a tendency
that the storage stability of the silica-organosilane
coating composition is lowered when the water content of
the liquid medium is not less than 20 % by weight. For
.
1329~69
-- 6
instance, the composition disclosed in Japanese Examined
Patent Publication No. 39691/1977 does not have a
sufficient storage stability since the liquid medium of
the composition contains water in an amount of not less
than 20 ~ by weight. The storage stability of the
- composition disclosed in Japanese Unexamined Patent
Publication No. 68377/1984 is somewhat improved since the
water contained in the composition is reduced to not more
than 10 ~ by weight of the liquid medium by means of
azeotropic distillation. However, the storage stability
of the composition has not yet been sufficiently
improved.
' On the other hand, when ethylene glycol
monobutyl ether is contained in the liquid medium in an
amount of not less than 20 % by weight, it has been
-~ confirmed that the obtained coating composition has
' sufficient strorage stability even though the water
content of the liquid medium is not less than 20 % by
weight. Further, it has been confirmed that the obtained
coating composition has not only excellent workability
for coating, but also has no defects in film forming
property and transparency of the coating film.
-~- Furthermore, when ethylene glycol monobutyl
- ether is contained in the liquid medium in an amount of
~; 25 at least 20 % by weight of the liquid medium, it has been
confirmed that the coating composition shows excellent
film forming proper;y and has a sufficient storage
stability even though the solvents such as acetic esters
- and aliphatic ketones, which are the solvents imparting
wrong film forming property to a silica-organisilane
coating composition when the solvents are solely
contained in the coating composition, are contained in
the coating composition as a main solvent.
~ Examples of the solvents other than ethylene
- 35 glycol mor,obutyl ether are, for instance, lower aliphatic
alcohols such as methanol, ethanol, propanol,
isopropanol, n-butanol and t-butanol; glycols such as
, ethylene glycol, propylene glycol and butylene glycol;
: .
1329~g~
-- 7
glycol derivatives such as ethylene glycol monomethyl
ether, ethylene glycol monoethyl ether and ethylene
glycol monoethyl ether acetate; aliphatic ketones such as
acetone, methyl ethyl ketone, methyl isobutyl ketone,
~, 5 cyclohexanone, isophorone and diacetone alcohol; and
acetic esters such as ethyl acetate.
n the coating composition of the present
. invention, the solid component is composed of silica,
organohydroxysilane and a partial condensate of
organohydroxysilane. The solid content of the coating
composition is adjusted to be within a range of 5 to 40 %
by weight, preferably 10 to 30 % by weight based on the
, obtained coating composition with the aid of the solvent
(c). When the solid content is less than 5 % by weight,
it becomes difficult to control the thickness of the
coating film, and when the solid conten~ is more than 40
% by weight, the workability for coating is lowered and
5~ the thickness of the coating film becomes too thick and
cracking easily generates in the coating film.
The mixing ratio of the weight of the solid
component of the above-mentioned silica to the weight of
the solid components of the organohydroxysilane and the
partial condensate of organohydroxysilane is adjusted to
~ be within a range of 30/70 to 90/10, preferably within a
s 25 range of 40/60 to 70/30. When the mixing ratio is less
than 30/70, there is a tendency that the hardness and
tnermal resistance of the coating film is lowered, and
when the mixing ratio is more than 90/10, there is a
tendency that the coating film comes to be brittle.
It is desirable that the pH of the coating
- composition of the present invention is adjusted to be
within a range of 2 to 7, preferably within a range of 3
to 6, more preferably within a range of 4 to 5 with the
aid of, for instance, aqueous ammonia or organic amines
- 35 such as triethanolamine and dimethyl aminoethanol. When
the pH or the coating composition is either less than 2
or more than 7, there is a tendency that storage
stability of the coating composition is lowered.
1329~69
Examples of the process for preparing the
coating composition of the present invention are, for
instance, (i) a procesc comprising adding the
organoalkoxysilane to the dispersion of colloidal silica,
hydrolizing the mixture to give organohydroxysilane and a
partial condensate of the oranohydroxysilane and diluting
the reaction mixture with the solvent (c), (ii) a process
comprising diluting the dispersion of colloidal silica
with the solvent (c), adding the organoalkoxysilane to
the dispersion, and hydrolyzing the mixture, and the
like. In the present invention, any processes mentioned
above can be employed.
When the organoalkoxysilane is added to the
dispersion of the colloidal silica to hydrolyze the
organoalkoxysilane, the hydrolysis is carried out at a
liquid temperature of 10 to 80C under atmospheric
pressure for about 1 to 24 hours with stirring. A part
of the non-aqueous colloidal silica can be added after
`3. the completion of the reaction.
When the organoalkoxysilane is subjected to the
, hydrolysis, as a catalyst for hydrolysis, a small amount
of inorganic acid or organic acid can be added to the
dispersion.
Further, additives such as alcohol soluble
resins as a component to impart flexibility to a coating
~ film; coloring agents such as pigments znd dyes;
$ levelling agents, thickening agents and defoaming agents
r can be added to the coating composition of the present
:' invention as occasion demands. Examples of the alcohol
~ 30 soluble resins are, for instance, resins soluble in lower
,-5~ aliphatic alcohols or in glycol derivatives such as
' butyral resins, acrylic resins and urethane resins.
-~- The process for coating and curing the coating
composition of the present invention on a substrate is
35 explained hereinbelow.
.- Various conventional coating methods such as
`~ spraying, dipping, flow coating, roller coating, screen
printing and electrostatic coating can be employed in the
:
- 9 - 132~9
present invention.
After the coating composition is coated onto a
substrate, the coated film is heated at 80 to 200C for
10 to 120 minutes to give a cured coating film being
excellent in adhesion property to the substrate. The
, thickness of the coating film cannot be absolutely
determined since the thickness of the coating film
depends on the kinds of the substrate and the uses of the
substrate. The thickness of the coating film is usually
adjusted to be within a range of 1 to 100 ~m, preferably
within a range of 5 to 50 ~m.
Examples of the substrate onto which the
$~ coating composition of the present invention can be
applied are, for instance, metallic materials such as
iron, stainless steel, aluminium, copper and brass;
, ::
~, inorganic materials such as glass and ceramics; organic
-~ materials such as plastics, and the like. As mentioned
i above, various materials can be employed in the present
~; invention. In the present invention, there is no
; 20 necessity to apply a primer coating and the like on the
. surface of a substrate; and the coating film is superior
in adhesion property to the substrate, to conventional
coatings. The coating composition of the present
invention can be applied onto the surface of a metallic
or ceramic vacuum-evaporated film or a metal plated film.
. The presen~ invention is more specifically
described and explained by means of the following
examples. Tt is to be understood that the present
invention is not limited to the examples, and various
changes and modifications may be made in the invention
without departing from the spirit and scope thereof. In
each example and comparative example, all of "part" and
"%" are by weight unless otherwise noted.
Exam~les 1 to 5 and ComParative Examples 1 to 10
An amount of 184 parts of a dispersion of
aqueous colloidal silica having a silica content of 30 ~,
a particle size of 5 to 20 m~m and a pH of 3.0, and 100
: 13~9669
-- 10
:
parts of methyltrimethoxysilane were mixed together.
After the mixture was stirred at 30C for 5 hcurs to
complete the hydrolysis, to which the solvents shown in
Table l was added. Then, the pH of the mixture was
adjusted to be 4.5 by adding aqueous ammonia into the
mixture to give a coating composition.
The properties of matter, i.e., (l) film
property and (2) storage stability of the obtained
coating compositions were investigated in accordance with
, lO the following methods. The results are shown in Table 3.
, (1) Film property
An aluminium plate was coated with an obtained
coating composition by method of spraying and the coated
film was heated at 160C for 20 minutes to give a cured
film having a thickness of about 10 ~m. The plate was
used as a test piece and the properties of matter of the
~, coating film were measured in accordance with the
, following methods.
, [A] Transparency
,i 20 The coating film formed on the test piece was
observed with the naked eyes, and the transparency
was evaluated according to the following criteria.
~, O : There was no turbidity, and the substrate was
~, clearly observed through the coating film.
~'- 25 ~ : There was a slight turbidity.
X : There was turbidity.
[B] Appearance of film
The coating film formed on the test piece was
observed with the naked eyes.
[C] Pencil hardness test
~; Pencil hardness was evaluated in accordance
s with JlS K 5400.
[D] Adhesion test
After the test pieces were subjected to the
cross-cut adhesion test in accordance with JIS D
0202. The numbers of remaining squares on the
substrate were counted.
~E] Solvent resistance test
.
.
.
~-
132~S~9
After the test pieces were dipped into toluene
- and isopropanol, respectively, for 24 hours at a
room temperature (about 20C), the surface appear-
ance of the coating film was observed with the naked
eyes, and evaluated according to the following cri-
, terla.
: There was no change.
: There was generated a slight clouding in the
coating film.
X : There was found erosion in the coating film.
, [F] Boiling water resistance test
~, After the test pieces were dipped into boiling
water for 10 hours, the surface appearance of the
: coating film was observed with the naked eyes, and
was evaluated according to the following criteria.
O : There was no change.
/\ : There was generated a slight clouding or
; cracking in the coating film.
, ~,
. X : There was generated peeling of the film or
cracking in the coating film.
[G] Salt spray test
, After the test pieces were subjected to salt
spray test for 1000 hours in accordance with JIS K
5400, changes of the appearance of the coating film
were observed with the naked eyes, and were evalu-
ated according to the following criteria.
O : There was no change.
- ~ : There was found a little rust.
X : There was found peeling of the coating film.
- 30 [H] Accelerated weathering test
After the test pieces were subjected to the ac-
celerated weathering test by means of a sunshine car-
bon arc lamp style weathering tester for 2000 hours,
changes of the appearance of the coating film were
observed with the naked eyes, and were evaluated ac-
cording to the following criteria.
O : There was no change.
here was generated a slight clouding and
. -- .
''`
.
- 12 - 1~296~9
cracking in the coating film.
X : There was generated turbidity, blistering,
peeling and cracking in the coating film.
[I] Heat resistance test
After the test pieces were allowed to stand in
the atmosphere having a temperature of 200C,
300C, 400C and 500C, respectively, for 24 hours,
changes of the appearance of the coating film were
observed with the naked eyes. The temperature when
changes were not observed, was defined as a
temperature of heat resistance.
~2) Storage stability test:
s A container was charged with the coating
'~ composition and was sealed. The sealed container
' 15 was allowed to stand in the atmosphere having a
s temperature of 50C, and changes of the coating
f' ' composition was observed with the naked eyes as
well as an aluminium plate was coated with the
. .
~ coating conposition by method of spraying and was
"'f 20 heated at 160C for 20 minutes everyday. Changes
of the coating film were observed with the naked
eyes.
. ~ .
,.~
,.
'
` ,
'
- 13 - 1329~9
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. - 14 - 1329~9
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1329669
1 5
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~32~9
-- 16
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- 17 - 1329~69
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13~9S69
- 18
Examples 6 and 7
` The procedure of Example 1 was repeated except
that the amounts of the dispersion of the aqueous
colloidal silica and the solvent (isopropanol/ethylene
glycol monobutyl ether) were changed to give coating
compositions. The amounts are shown in Table 2.
The obtained coating compositions were observed
in the same manner as in Example 1. The results are
shown in Table 3.
Examples 8 to 11
The procedure of Example 6 was repeated except
that the amount of ethylene glycol monobutyl ether was
changed as shown in Table 2 and that the isopropanol was
not used to give coating compositions.
; The obtained coating compositions were observed
in the same manner as in Example 1. The results are
shown in Table 3.
. .
:i~
~ 20 Exam~les 12 and 13
s The procedure of Example 2 was repeated except
that the pH of the composition was changed to 2.5
(Example 12) or 6.5 (Example 13) to give coating
- compositions.
The obtained coating compositions were observed
~, in the same manner as in Example 1. The results are
;, shown in Table 3.
:,
Example 14
The procedure of Example 2 was repeated except
that triethanolamine was used instead of the aqueous
ammonia to give a coating composition.
The obtained coating composition was observed
~'- in the same manner as in Example 1. The results are
shown in Table 3.
- 19 - 1329~69
C C~ ~ C
" C~ C o o ~ o o CO o o o o o o
_ c E ~J -- o o ~ r~ o o o
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- 20 _ 1 32 966 9
Example 15
An amount of 30 parts of a dispersion of an
aqueous colloidal silica having a silica content of 20 %,
a particle size of 5 to 20 m~m and a pH of 3.0, 36.7
parts of methyl triethoxysilane and 0.1 part of acetic
anhydride were mixed together. After the mixture was
stirred at 30C for 24 hours to complete the hydrolysis,
to which 32 parts of ethanol was added. Then the excess
water in the mixture was removed by azeotropic
distillation with the ethanol at 30C under a reduced
pressure of lO0 Torr. An amount of 50 parts of ethylene
, glycol monobutyl ether was added to the mixture to give a
coating composition having a solid content of about 20~.
The properties of matter of the obtained
, 15 coating composition was observed in the same manner as in
Example 1. The results are shown in Table 3.
' ~'.
i Comparative Example 11
,' The procedure of Example 15 was repeated except
-~ 20 that an amount of 50 parts of isobutanol was used instead
,. of 50 parts of ethylene glycol monobutyl ether to give a
coating composition.
- The obtained coating composition was observed
in the same manner as in Example 1. The results are
shown in Table 3.
:~ ,
.,
. .
:
,~ ~
- 21 - 1329669
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.,
The coating compositon prepared in Example l
was allowed to stand for about one year in an atmosphere
, having a room temperature to observe the storage
stability. As the results, there was not found abnormal
~` 5 changes in the coating composition and the properties of
- the coating film. The storage stability of the coating
composition prepared in Comparative Example 1 was also
observed in an atmosphere having a room temperature. As
the results, after 3 months, the composition gelled.
In Table 3, the mark " -" means that the
coating film was not formed. Accordingly, the properties
of matter were not evaluated.
As mentioned-above, the coating composition of
the present invention is sufficiently improved in storage
stability which has been desired in conventional coating
compositions. That is, the coating composition of the
present invention shows remarkably excellent storage
stability for a long period of time, i.e., not less than
one year although conventional coating compositions show
storage stability for about not more than 3 months at a
room temperature. Further, the process for preparing the
coating composition of the present invention is very
simple and convenient since there is no necessity to
remove water from the coating composition by means of a
complicated process of azeotropic distillation in order
to control the water content in the coating
composition. The various solvents, which could not been
used in the conventional coating compositions, can be
, used since the film forming property of the coating
composition of the present invention is not deteriorated
even though the solvents are contained. Further,
according to the present invention, the coating
composition having excellent storage stability is
provided even though the composition has a large solid
content.
The present invention shows not only improved
- storage stability but also remarkably enlarged the range
of the formulations. Accordingly, the coating
1329~9
- 28
composition of the present invention can be applied to
.- various uses.
Reasonable modification and variation are
- within the scope of this invention which is directed to
S novel coating compos1tions.
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