U.S. patent number RE38,850 [Application Number 10/336,919] was granted by the patent office on 2005-10-25 for functional coated product and process for producing the same and the use thereof.
This patent grant is currently assigned to Matsushita Electric Works, Ltd.. Invention is credited to Junko Ikenaga, Hirotsugu Kishimoto, Toshiharu Sako, Koichi Takahama, Takeyuki Yamaki.
United States Patent |
RE38,850 |
Ikenaga , et al. |
October 25, 2005 |
Functional coated product and process for producing the same and
the use thereof
Abstract
The present invention provides a functional coated product
having excellent adhesion properties of a coating to a substrate,
hardly causing the deterioration of the substrate and the coating
due to a photocatalyst, hardly having dirt because the smoothness
of the surface coating is high, and having high photocatalytic
action; a method for producing the same and the use thereof. The
coated product of the present invention has the first coating layer
comprising a cured coating made of an acryl-modified silicone resin
coating material, which is formed on the surface of the substrate,
and the second coating layer comprising a cured coating made of a
functional coating material containing the photocatalyst, which is
formed con the surface of the first coating layer. When producing
such a coated product, the acryl-modified silicone resin coating
material is applied to the surface of the substrate as the first
coating layer and it is semi-cured. After that, a
photocatalyst-containing functional coating material is applied to
the surface of this first coating layer in a semi-cured condition
and then both of the coating layers are cured. Thereby, a coated
product having a higher effect can be obtained.
Inventors: |
Ikenaga; Junko (Osaka,
JP), Yamaki; Takeyuki (Nara, JP), Takahama;
Koichi (Amagasaki, JP), Sako; Toshiharu (Suita,
JP), Kishimoto; Hirotsugu (Toyonaka, JP) |
Assignee: |
Matsushita Electric Works, Ltd.
(Kadom, JP)
|
Family
ID: |
26386209 |
Appl.
No.: |
10/336,919 |
Filed: |
December 24, 2002 |
PCT
Filed: |
December 11, 1997 |
PCT No.: |
PCT/JP97/04559 |
371(c)(1),(2),(4) Date: |
August 05, 1998 |
PCT
Pub. No.: |
WO98/25711 |
PCT
Pub. Date: |
June 18, 1998 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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Reissue of: |
117738 |
Dec 11, 1997 |
06165619 |
Dec 26, 2000 |
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Foreign Application Priority Data
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Dec 13, 1996 [JP] |
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8-334024 |
Feb 28, 1997 [JP] |
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9-046087 |
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Current U.S.
Class: |
428/448; 427/387;
427/388.1; 427/397.7; 427/407.1; 427/409; 428/447; 428/450;
428/451 |
Current CPC
Class: |
B05D
7/546 (20130101); Y10T 428/31663 (20150401); Y10T
428/31667 (20150401) |
Current International
Class: |
B05D
7/24 (20060101); B32B 15/08 (20060101); B05D
007/24 (); B32B 015/08 () |
Field of
Search: |
;427/387,388.1,397.7,407.1,409,419.8 ;428/447,448,450,451 |
Foreign Patent Documents
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0 633 064 |
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Jun 1994 |
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EP |
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0 923 988 |
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Jun 2004 |
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EP |
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8-67835 |
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Mar 1996 |
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JP |
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8-259891 |
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Oct 1996 |
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JP |
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Other References
European Search Report, EP 97 94 7894 dated Jan. 26, 2001..
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Primary Examiner: Nakarani; D. S.
Attorney, Agent or Firm: Birch, Stewart, Kolasch &
Birch, LLP
Claims
What is claimed is:
1. A functional coated product having a first coating layer formed
of a cured coating of an acryl-modified silicone resin coating
material comprising the following components (A), (B), (C) and (D)
on a surface of a substrate, and a second coating layer formed of a
cured coating of a functional coating material comprising the
following components (E) and (F), over the first coating layer;
Component (A): a silica-dispersed organosilane oligomer solution
obtained by partially hydrolyzing a hydrolyzable organosilane
represented by the general formula
wherein R.sup.1 indicates a monovalent hydrocarbon group having 1
to 8 carbon atoms, which may be the same or different, m indicates
an integer of 0 to 3, and X indicates a hydrolyzable group in
colloidal silica dispersed in an organic solvent, water or a mixed
solvent of them, under the condition that 0.001 to 0.5 mol of water
is used based on 1 mol equivalent of the above-mentioned
hydrolyzable group (X);
Component (B): a polyorganosiloxane represented by the average
compositional formula
wherein R.sup.2 indicates a monovalent hydrocarbon group having 1
to 8 carbon atoms, which may be the same or different, a and b
separately satisfy the following condition:
which contains a silanol group in the molecule structure and has an
average molecular weight (in terms of polystyrene) of 700 to
20,000;
Component (C): a curing catalyst;
Component (D): an acrylic resin of copolymer of first
(meth)acrylate represented by the general formula (III)
in which R.sup.3 is a hydrogen atom or a methyl group, and R.sup.4
is a hydrocarbon group having 1 to 9 carbon atoms, the second
(meth)acrylate of the general formula (III) in which R.sup.3 is a
hydrogen atom or a methyl group, and R.sup.4 is at least one group
selected from the group consisting of an epoxy group, a glycidyl
group, and a hydrocarbon group containing at least either of the
above, and the third (meth)acrylate of the general formula (III) in
which R.sup.3 is a hydrogen atom or a methyl group, and R.sup.4 is
a hydrocarbon group containing an alkoxy silyl group or a
halogenated silyl group, and said acrylic resin having an average
molecular weight (in terms of polystyrene) of 1,000 to 50,000;
Component (E): an organosiloxane comprising a hydrolyzed
polycondensate of; 5 to 30,000 parts by weight of a silica compound
represented by the general formula:
and/or colloidal silica, 100 parts by weight of a silica compound
represented by the general formula:
and 0 to 60 parts by weight of a silica compound represented by the
general formula:
wherein R.sup.5 and R.sup.6 indicate a monovalent hydrocarbon group
and said weight-average molecular weight being adjusted to 800 or
more in terms of polystyrene; and
Component (F): a photocatalyst.
2. The functional coated product according to claim 1, wherein, in
the above-mentioned acryl-modified silicone resin coating material,
1 to 94 parts by weight of Component (B) and 5 to 35 parts by
weight of Component (D) are formulated in 1 to 94 parts by weight
of Component (A), based on the solid content of the whole
condensate (provided that the total amount of Components (A), (B)
and (D) comes to 100 parts by weight).
3. The functional coated product according to claim 1, which
further contains a pigment.
4. The functional coated product according to claim 1, wherein a
substrate is selected from the group consisting of a metallic
substrate, an organic substrate and an organic coating substrate in
which either one of the above substrates has a coating formed from
an organic compound on the surface thereof.
5. A member related to building construction at least a part of
which is equipped with the functional coated product according to
claim 1.
6. A gate for a building at least a part of which is equipped with
the functional coated product according to claim 1.
7. The gate for building of claim 6, in which the part is a gate
pier.
8. A wall for a building at least a part of which is equipped with
the functional coated product according to claim 1.
9. The functional coated product according to claim 1, wherein the
substrate is a member for using the gate.
10. A window at least a part of which is equipped with the
functional coated product according to claim 1.
11. The window according to claim 10, which is a lighting
window.
12. The window according to claim 10, the part is a window
frame.
13. An automobile at least a part of which is equipped with the
functional coated product according to claim 1.
14. Mechanical equipment having at least a part of which is
equipped with the functional coated product according to claim
1.
15. A member for highway-related construction at least a part of
which is equipped the functional coated product according to claim
1.
16. The member for highway-related construction according to claim
15, which is a traffic-control sign, a side wall of the road, an
electric-light pole or a protection fence.
17. A post for public notice at least a part of which is equipped
with the functional coated product according to claim 1.
18. An illuminator at least a part of which is equipped with the
functional coated product according to claim 1.
19. The functional coated product according to claim 1, wherein the
substrate is a resin material to be used for an illuminator.
20. The functional coated product according to claim 1, wherein the
substrate is a metal material to be used for an illuminator.
21. A functional coated product having a first coating layer formed
of a cured coating of an acryl-modified silicone resin coating
material comprising the following components (A), (B), (C) and (D)
on a surface of a substrate, and a second coating layer formed of a
cured coating of a functional coating material comprising the
following components (A), (B), (C), .[.(E).]. and (F), over the
first coating layer;
Component (A): a silica-dispersed organosilane oligomer solution
obtained by partially hydrolyzing a hydrolyzable organosilane
represented by the general formula
wherein R.sup.1 indicates a monovalent hydrocarbon group having 1
to 8 carbon atoms, which may be the same or different, m indicates
an integer of 0 to 3, and X indicates a hydrolyzable group in
colloidal silica dispersed in an organic solvent, water or at mixed
solvent of them, under the condition that 0.001 to 0.5 mol of water
is used based on 1 mol equivalent of the above-mentioned
hydrolyzable group (X);
Component (B): a polyorganosiloxane represented by the average
compositional formula
wherein R.sup.2 indicates a monovalent hydrocarbon group having 1
to 8 carbon atoms, which may be the same or different, a and b
separately satisfy the following condition:
which contains a silanol group in the molecule structure and has an
average molecular weight (in terms of polystyrene) of 700 to
20,000;
Component (C): a curing catalyst;
Component (D): an acrylic resin of copolymer of first
(meth)acrylate represented by the general formula (III)
in which R.sup.3 is a hydrogen atom or a methyl group, and R.sup.4
is a hydrocarbon group having 1 to 9 carbon atoms, the second
(meth)acrylate of the general formula (III) in which R.sup.3 is a
hydrogen atom or a methyl group, and R.sup.4 is at least one group
selected from the group consisting of an epoxy group, a glycidyl
group, and a hydrocarbon group containing at least either of the
above, and the third (meth)acrylate of the general formula (III) in
which R.sup.3 is a hydrogen atom or a methyl group, and R.sup.4 is
a hydrocarbon group containing an alkoxy silyl group or a
halogenated silyl group, and said acrylic resin having an average
molecular weight (in terms of polystyrene) of 1,000 to 50,000;
.[.Component (E): an organosiloxane comprising a hydrolyzed
polycondensate of; 5 to 30,000 parts by weight of a silica compound
represented by the general formula:
and/or colloidal silica, 100 parts by weight of a silica compound
represented by the general formula:
and 0 to 60 parts by weight of a silica compound represented by the
general formula:
wherein R.sup.5 and R.sup.6 indicate a monovalent hydrocarbon group
and said weight-average molecular weight being adjusted to 800 or
more in terms of polystyrene;.]. and
Component (F): a photocatalyst.
22. A process for producing a functional coating material
comprising the following steps: forming a first coating layer by
applying an acryl-modified silicone resin coating material
containing the following components (A), (B), (C) and (D) to
surface of a substrate, forming a semi-cured layer by semi-curing
the first coating layer, forming a second coating layer by applying
a functional coating material containing the following components
(E) and (F) to surface of said semi-cured layer, and curing said
semi-cured layer and said second coating layer;
Component (A): a silica-dispersed organosilane oligomer solution
obtained by partially hydrolyzing a hydrolyzable organosilane
represented by the general formula
wherein R.sup.1 indicates a monovalent hydrocarbon group having 1
to 8 carbon atoms, which may be the same or different, m indicates
an integer of 0 to 3, and X indicates a hydrolyzable group in
colloidal silica dispersed in an organic solvent, water or a mixed
solvent of them, under the condition that 0.001 to 0.5 mol of water
is used based on 1 mol equivalent of the above-mentioned
hydrolyzable group (X);
Component (B): a polyorganosiloxane represented by the average
compositional formula
wherein R.sup.2 indicates a monovalent hydrocarbon group having 1
to 8 carbon atoms, which may be the same or different, a and b
separately satisfy the following condition:
which contains a silanol group in the molecule structure and has an
average molecular weight (in terms of polystyrene) of 700 to
20,000;
Component (C): a curing catalyst;
Component (D): an acrylic resin of copolymer of first
(meth)acrylate represented by the general formula (III)
CH.sub.2.dbd.CR.sup.3 (COOR.sup.4) (III)
in which R.sup.3 is a hydrogen atom or a methyl group, and R.sup.4
is a hydrocarbon group having 1 to 9 carbon atoms, the second
(meth)acrylate of the general formula (III) in which R.sup.3 is a
hydrogen atom or a methyl group, and R.sup.4 is at least one group
selected from the group consisting of an epoxy group, a glycidyl
group, and a hydrocarbon group containing at least either of the
above, and the third (meth)acrylate of the general formula (III) in
which R.sup.3 is a hydrogen atom or a methyl group, and R.sup.4 is
a hydrocarbon group containing an alkoxy silyl group or a
halogenated silyl group, and said acrylic resin having an average
molecular weight (in terms of polystyrene) of 1,000 to 50,000;
Component (E): an organosiloxane comprising a hydrolyzed
polycondensate of; 5 to 30,000 parts by weight of a silica compound
represented by the general formula
and/or colloidal silica, 100 parts by weight of a silica compound
represented by the general formula:
and 0 to 60 parts by weight of a silica compound represented by the
general formula:
wherein R.sup.5 and R.sup.6 indicate a monovalent hydrocarbon group
and said weight-average molecular weight being adjusted to 800 or
more in terms of polystyrene; and
Component (F): a photocatalyst.
23. The process for producing a functional coated product according
to claim 22, wherein, in the above-mentioned acryl-modified
silicone resin coating material, 1 to 94 parts by weight of
Component (B) and 5 to 35 parts by weight of Component (D) are
formulated in 1 to 94 parts by weight of Component (A), based on
the solid content of the whole condensate (provided that the total
amount of Components (A), (B) and (D) comes to 100 parts by
weight).
24. The process for producing a functional coated product according
to claim 22, which further contains a pigment.
25. The process for producing a functional coated product according
to claim 22, wherein said substrate is selected from the group
consisting of a metallic substrate, an organic substrate and an
organic coating substrate in which either of the above substrates
has a coating formed from an organic substance on the surface
thereof.
26. A process for producing a functional coating material
comprising the following steps: forming a first coating layer by
applying an acryl-modified silicone resin coating material
containing the following components (A), (B), (C) and (D) to
surface of a substrate, forming a semi-cured layer by semi-curing
the first coating layer, forming a second coating layer by applying
a functional coating material containing the following components
(A), (B), (C) and (F) to surface of said semi-cured layer, and
curing said semi-cured layer and said second coating layer;
Component (A): a silica-dispersed organosilane oligomer solution
obtained by partially hydrolyzing a hydrolyzable organosilane
represented by the general formula
wherein R.sup.1 indicates a monovalent hydrocarbon group having 1
to 8 carbon atoms, which may be the same or different, m indicates
an integer of 0 to 3, and X indicates a hydrolyzable group in
colloidal silica dispersed in an organic solvent, water or a mixed
solvent of them, under the condition that 0.001 to 0.5 mol of water
is used based on 1 mol equivalent of the above-mentioned
hydrolyzable group (X);
Component (B): a polyorganosiloxane represented by the average
compositional formula
wherein R.sup.2 indicates a monovalent hydrocarbon group having 1
to 8 carbon atoms, which may be the same or different, a and b
separately satisfy the following condition:
which contains a silanol group in the molecule structure and has an
average molecular weight (in terms of polystyrene) of 700 to
20,000;
Component (C): a curing catalyst;
Component (D): an acrylic resin of copolymer of first
(meth)acrylate represented by the general formula (III)
in which R.sup.3 is a hydrogen atom or a methyl group, and R.sup.4
is a hydrocarbon group having 1 to 9 carbon atoms, the second
(meth)acrylate of the general formula (III) in which R.sup.3 is a
hydrogen atom or a methyl group, and R.sup.4 is at least one group
selected from the group consisting of an epoxy group, a glycidyl
group, and a hydrocarbon group containing at least either of the
above, and the third (meth)acrylate of the general formula (III) in
which R.sup.3 is a hydrogen atom or a methyl group, and R.sup.4 is
a hydrocarbon group containing an alkoxy silyl group or a
halogenated silyl group, and said acrylic resin having an average
molecular weight (in terms of polystyrene) of 1,000 to 50,000;
.[.Component (E): an organosiloxane comprising a hydrolyzed
polycondensate of; 5 to 30,000 parts by weight of a silica compound
represented by the general formula:
and/or colloidal silica, 100 parts by weight of a silica compound
represented by the general formula:
and 0 to 60 parts by weight of a silica compound represented by the
general formula:
wherein R.sup.5 and R.sup.6 indicate a monovalent hydrocarbon group
and said weight-average molecular weight being adjusted to 800 or
more in terms of polystyrene;.]. and
Component (F): a photocatalyst.
Description
This application is the national phase under 35 U.S.C. .sctn.371 of
prior PCT International Application No. PCT/JP97/04559 which has an
International filing date of Dec. 11, 1997 which designated the
United States of America, the entire contents of which are hereby
incorporated by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a functional coated product having
photocatalytic activity and a process for producing the same and
the use thereof.
2. Description of the Prior Art
When a photocatalyst is added to a coating material, the resulting
coating is irradiated by ultraviolet light to exhibits a
decomposing effect of organic substances, deodorizing effect,
antifungal effect, etc.
As a coating material having such photocatalytic function, for
example, a photocatalytic organic paint in which photocatalytic
particles are dispersed in organic resin is known. However, the
photocatalytic organicpaint has a drawback that the coating is
deteriorated due to ultraviolet rays and photocatalytic
function.
An inorganic paint, in which photocatalytic particles are dispersed
in an inorganic composition such as a silicate, a phosphate or a
zirconate, is known as a coating material having photocatalytic
function. These inorganic paints have much better durability than
that of photocatalytic organic paints, however, it is necessary to
conduct baking at a high temperature of 200.degree. C. or more.
Therefore, the range of usage is limited, and it was not suitable
for applying them directly to a construction material or plastic
which has inferior heat resistance. Further, the silicate inorganic
paint has also a drawback that an alkali was eluted to cause a
whitening phenomenon easily.
In Japanese Patent Publication Laid-Open No. 57470/1987, an
inorganic paint in which a metal alkoxide is contained is
disclosed. This inorganic paint is cured at a temperature of not
more than 200.degree. C., however, the coating does not have
flexibility and there was a problem that crack easily occurred.
Recently, with a necessity to apply a paint to various materials, a
low-temperature curing paint keeping its photocatalytic performance
even if it is used for a long time, having durability in the
coating itself has been desired.
In Japanese Patent Publication Laid-Open No. 67835/1996, an
antifungal inorganic paint containing a photocatalyst, which is a
component having a photocatalytic function as an anti-fungus agent,
is proposed. However, when a photocatalyst was supported on a
substrate, there was a problem concerning the limitation of the
substrate or adhesion properties. Further, there was a tendency
that the photocatalyst was precipitated in the paint, and the
performance of the photocatalyst was not easily exhibited.
Therefore, in Japanese Patent Publication Laid Open No.
141503/1996, the improvement in a method for forming an inorganic
coating having photocatalyst on the surface thereof and high
photocatalytic performance is suggested. This coating has high
adhesion to an inorganic substrate, however, it has poor adhesion
to the surface of plastic or a material coated with an organic
substance. Further, a coating of the above-mentioned inorganic
coating lacks in smoothness on the surface, therefore there was a
drawback that dirt is easily adhered.
Further, when a paint containing a photocatalyst is directly
applied to the surface of an organic substrate or a substrate
coated with an organic substance, there was a problem that said
substrate was easily deteriorated due to the action of the
photocatalyst.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a functional
coated product which has excellent adhesion properties to various
substrates, hardly causes the deterioration of the substrate and a
coating due to the action of a photocatalyst and also has high
photocatalytic function, and a process for producing the same and
the use thereof.
The functional coated product of the present invention has the
first coating layer comprising a cured coating made of an
acryl-modified silicone resin coating material, and the second
coating layer comprising a cured coating made of a functional
coating material (1) or (2) below. The present invention also
provides a production method of the functional coated product and
use thereof.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The functional coated product of the present invention has a first
coating layer comprising a cured coating made of an acryl-modified
silicone resin coating material, and a second coating layer
comprising a cured coating made of a functional coating material
(1) or (2).
A process for producing a functional coated product of the present
invention which comprises the following steps:
forming a first coating layer by applying an acryl-modified
silicone resin coating material to surface of a substrate,
forming a semi-cured layer by semi-curing the first coating
layer,
forming a second coating layer by applying a functional coating
material (1) or (2) to the semi-cured first coating layer, and
curing said semi-cured layer and said second coating layer.
The acryl-modified silicone resin coating material contains the
following components (A), (B), (C) and (D).
The functional coating material (1) contains the following
components (E) and (F).
The functional coating material (2) contains the following
components (A), (B), (C), and (F).
Component (A): a silica-dispersed organosilane oligomer solution
obtained by partially hydrolyzing a hydrolytic organosilane
represented by the general formula
(wherein R.sup.1 indicates a substituted or non-substituted
monovalent hydrocarbon group having 1 to 8 carbon atoms, which may
be the same or different, m indicates an integer of 0 to 3, and X
indicates a hydrolytic group)
in an organic solvent, water or colloidal silica dispersend in a
mixed solvent thereof, under the condition that 0.001 to 0.5 mol of
water is used based on 1 mol equivalent of the above-mentioned
hydrolytic group (X);
Component (B): a polyorganosiloxane represented by the average
compositional formula:
(wherein R.sup.2 indicates a substituted or non-substituted
monovalent hydrocarbon group having 1 to 8 carbon atoms, which may
be the same or different, a and b separately satisfy the following
condition:
which contains a silanol group in its molecule;
Component (C): a curing catalyst;
Component (D): an acrylic copolymer resin of three (meth)acrylate
components represented by the general formula (III):
(wherein R.sup.3 is a hydrogen atom and/or a methyl group),
comprising the first (meth)acrylate component in which R.sup.4 is a
substituted or non-substituted hydrocarbon group having 1 to 9
carbon atoms, the second methacrylate in which R.sup.4 is at least
one group selected from the group consisting of an epoxy group, a
glycidyl group and a hydrocarbon group containing at least either
of those groups, and the third methacrylate in which R.sup.4 is a
hydrocarbon group containing an alkoxy silyl group and/or a
halogenated silyl group); and said acrylic copolymer resin has an
average molecular weight of 1,000 to 50,000 (in terms of
polystyrene).
In the present specification, (meth)acrylate indicates either
acrylate or methacrylate or both of them.
Component (E): an organosiloxane comprising a hydrolytic
polycondensate comprising a mixture of
(E1) 5 to 30,000 parts by weight of a silica compound represented
by the general formula:
and/or colloidal silica,
(E2) 100 parts by weight of a silica compound represented by the
general formula:
(E3) 0 to 60 parts by weight of a silica compound represented by
the general formula:
(wherein R.sup.5 and R.sup.6 indicate a monovalent hydrocarbon
group) and said weight-average molecular weight being adjusted to
800 or more in terms of polystyrene; and
Component (F): a photocatalyst.
In the above-mentioned acryl-modified silicone resin coating
material, it is preferred that 1 to 94 parts by weight of Component
(B) and 5 to 35 parts by weight of Component (D) are formulated in
1 to 94 parts by weight of Component (A), based on the solid
content of the whole condensate (provided that the total amount of
Components (A), (B) and (D) comes to 100 parts by weight).
The above-mentioned acryl-modified silicone resin coating material
may contain a pigment.
It is preferred that the above-mentioned substrate is selected from
the group consisting of a metallic substrate, an organic substrate
and a substrate coated with an organic substance in which either
one of the above substrates has a coating formed from an organic
substance on the surface thereof.
The coated product of the present invention can be used for, for
example, a member related to building construction, particularly,
an outdoor member related to building construction, a gate for a
building, and a member to be used for that purpose (e.g., a gate
pier, etc.), a wall for a building and a member to be used for that
purpose, a window (e.g., a lighting window, etc.), and a member to
be used for that purpose (e.g., a window frame, etc.), an
automobile, mechanical equipment, particularly, outdoor mechanical
equipment, a member for highway-related construction,
(particularly, a traffic-control sign), a post for public notice,
particularly, an outdoor post for public notice, an indoor or
outdoor lighting fixture and a member to be used for that purpose
(e.g., a resin material, a metal material, etc.), by equipping it
with at least a part of the above-mentioned materials.
Silica compounds (E1) to (E3), which are used as a raw material of
Component (E) of the functional coating material (1), can be
represented by the general formula
Herein R.sup.5 and R.sup.6 indicate a monovalent hydrocarbon group,
and n indicates an integer of 0 to 2.
R.sup.6 is not specifically limited, but may be, for example, a
substituted or nonsubstituted monovalent hydrocarbon group having 1
to 8 carbon atoms. Examples thereof include alkyl groups such as
methyl groups, ethyl groups, propyl groups, butyl groups, pentyl
groups, hexyl groups, heptyl groups or octyl groups; cycloalkyl
groups such as cyclopentyl groups or cyclohexyl groups; aralkyl
groups such as 2-phenylethyl groups, 2-phenylpropyl groups,
3-phenylpropyl groups; aryl groups such as phenyl groups or tolyl
groups; alkenyl groups such as vinyl groups or allyl groups;
halogen-substituted hydrocarbon groups such as chloromethyl groups
or .gamma.-chloropropyl groups or 3,3,3-trifluoropropyl groups;
substituted hydrocarbon groups such as .gamma.-methacryloxypropyl
groups, .gamma.-glycidyloxypropyl groups, 3,4-epoxycyclohexylethyl
groups or .gamma.-mercaptopropyl groups. Among them, alkyl groups
and phenyl groups having 1 to 4 carbon atoms are preferred because
they are easily synthesized or easily available.
R.sup.5 is not specifically limited, but alkyl groups having 1 to 4
carbon atoms are used as a main material.
Particularly, examples of the tetraalkoxysilane (in which n=0)
include tetramethoxysilane, tetraethoxysilane and the like.
Examples of the organotrialkoxysilane (in which n=1) include
methyltrimethoxysilane, methyltriethoxysilane,
methyltriisopropoxysilane, phenyltrimethoxysilane,
phenyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, etc.
Further, examples of the diorganodialkoxysilane (in which n=2)
include dimethyldimethoxysilane, dimethyldiethoxysilane,
diphenyldimethoxysilane, diphenyldiethoxysilane,
methylphenyldimethoxysilane and the like.
These R.sup.5 and R.sup.6 may be the same or different among silica
compounds (E1) to (E3).
The above-mentioned organosiloxane (E) can be prepared, for
example, by diluting the raw materials (E1) to (E3) with a suitable
solvent, adding the necessary amount of water and a catalyst as a
curing agent thereto, and conducting hydrolysis and
polycondensation to prepare a prepolymer. At this occasion, the
weight-average molecular weight of the resulting prepolymer is
adjusted to 800 or more, preferably 850 or more, more favorably 900
or more, in terms of polystyrene. At this occasion, it is adjusted
so that the upper limit of the molecular weight is not more than
50,000, preferably 45,000, more favorably 40,000. If the
distribution of molecular weight of the prepolymer (the
weight-average molecular weight (Mw)) is less than 800, the cure
shrinkage at the time of the polycondensation of the functional
coating material is large, and therefore, crack is liable to occur
on the coating after curing. Further, if the molecular weight is
more than 50,000, the time for the curing reaction is required,
which may result in an insufficient hardness of the coating.
The amount of raw materials (E1) to (E3) to be used at the time of
preparing organosiloxane (E) is 5 to 30,000 parts by weight
(preferably 10 to 25,000 parts by weight, more favorably 20 to
20,000 parts by weight) of (E1), 0 to 60 parts by weight
(preferably 0 to 40 parts by weight, more favorably 0 to 30 parts
by weight) of (E3), based on 100 parts by weight of (E2). If the
amount of (E1) used is less than the above range, there is a
problem that the desired hardness of the cured coating is not
obtained (the hardness is lowered). On the other hand, if it is
more than the above range, the crosslinking density of the cured
coating is too high, therefore, there is a problem that crack is
liable to occur. Further, if the amount of (E3) used is more than
the above range, there is a problem that the desired hardness of
the cured coating is not obtained (the hardness is lowered).
Colloidal silica which can be used as a material (E1) is not
specifically limited. For example, water-dispersed or non-aqueous
organic solvent (e.g., alcohol)-dispersed colloidal silica can be
used. In general, such colloidal silica contains 20 to 50% by
weight of silica as a solid content. From this value, the amount of
silica to be formulated can be determined. Further, when using
water-dispersed colloidal silica, water existing as a component
other than the solid content can be used as a curing agent as
described bellow. Water-dispersed colloidal silica is usually made
from water-glass, but it can be easily obtained as a commercially
available product. Furthermore, organic solvent-dispersed colloidal
silica can be easily prepared by replacing the water in the
above-mentioned water-dispersed colloidal silica with an organic
solvent. Such organic solvent-dispersed colloidal silica can be
easily obtained as a commercially available product. In the organic
solvent-dispersed colloidal silica, the kind of the organic
solvent, in which colloidal silica is dispersed, is not
specifically limited. Examples thereof include lower aliphatic
alcohols such as methanol, ethanol, isopropanol, n-butanol or
isobutanol; ethylene glycol derivatives such as ethylene glycol,
ethylene glycol monobutyl ether or ethylene acetate glycol
monoethyl ether; diethylene glycol derivatives such as diethylene
glycol or diethylene glycol monobutyl ether; and diacetone
alcohols, etc. One or two or more solvents selected from the above
groups can be used. Together with these hydrophilic organic
solvents, toluene, xylene, ethyl acetate, butyl acetate, methyl
ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime and the
like can also be used.
Further, water is used as a curing agent at the time of the
hydrolytic polycondensation reaction. The amount of water is
preferably 0.01 to 3.0 mol, more favorably 0.3 to 1.5 mol, based on
1 mol equivalent of OR.sup.5 groups of silica compounds (E1) to
(E3).
A diluting solvent to be used at the time of the hydrolytic
polycondensation reaction of raw materials (E1) to (E3) is not
specifically limited. For example, those which were described as a
dispersing solvent of colloidal silica can be used.
Further, a pH value of the above-mentioned organosiloxane (E) is
not specifically limited. It is preferred to adjust it in the range
between 3.8 and 6. If the pH value is within this range, it is
possible to use organosiloxane (E) stably within the
above-mentioned molecular weight. When the pH value is out of the
above range, the stability of organosiloxane (E) is deteriorated,
therefore, the available term after a paint is prepared is limited.
Herein, a method of adjusting a pH value is not specifically
limited. For example, if the pH value is less than 3.8 at the time
of mixing raw materials of organosiloxane (E), the pH value is
adjusted to within the above-mentioned range using a basic reagent
such as ammonia. If the pH value exceeds 6, it may be adjusted
using an acidic reagent such as hydrochloric acid. Further,
depending on the pH value, the molecular weight remains small and
the reaction does not proceed, therefore, it takes a long time to
reach the above-mentioned range of the molecular weight. In that
case, organosiloxane (E) may be heated to accelerate the reaction.
Further, after making the reaction proceed using an acidic reagent
to reduce the pH value, the pH value may be increased to the
predetermined value using a basic reagent.
It is not necessary that a functional coating material (1) contains
a curing catalyst when it is cured by heating; however, the
functional coating material (1) may optionally contain such a
catalyst in order to accelerate the heat-curing of an applied
coating or to cure the applied coating at a normal temperature by
accelerating the polycondensation reaction of organosiloxane (E).
The curing catalyst is not specifically limited. Examples thereof
include alkyl titanates; metal salts of carboxylic acid such as tin
octylate, dibutyltin dilaurate or dioctyltin dimaleate; amine salts
such as dibutylamine-2-hexoate, dimethylamine acetate or
ethanolamine acetate; quaternary ammonium salts of carboxylic acid
such as tetramethylammonium acetate; amine salts such as
tetraethylpentamine; amine-type silane coupling agents such as
N-.beta.-aminoethyl-.gamma.-aminopropyltrimethoxysilane or
N-.beta.-aminoethyl-.gamma.-aminopropylmethyldimethoxysilane; acids
such as p-toluenesulfonic acid, phthalic acid or hydrochloric acid;
aluminum compounds such as aluminum chelate; alkali metal salts
such as lithium acetate, potassium acetate, lithium formate, sodium
formate, potassium phosphate or potassium hydroxide; titanium
compounds such as tetraisopropyl titanate, tetrabutyl titanate or
titanium tetraacetyl acetonate; halogenated silanes such as methyl
trichlorosilane, dimethyldichlorosilane or
trimethylmonochlorosilane. However, in addition to them, other
curing catalysts may be contained as long as they are useful for
the acceleration of the condensation reaction of organosiloxane
(E).
When the functional coating material (1) also contains a curing
catalyst (C), it is preferable to use not more than 25% by weight,
more favorably not more than 20% by weight of the curing catalyst,
based on the solid content of the whole condensate of
organosiloxane (E). If it is more than 45% by weight, storage
stability of the coating solution may be deteriorated.
The photocatalyst to be used as Component (F) for functional
coating materials (1) and (2) (a photocatalyst (F)) is not
specifically limited. Examples thereof include oxides such as
titanium oxide, zinc oxide, tin oxide, zirconium oxide, tungsten
oxide, chromium oxide, molybudenum oxide, iron oxide, nickel oxide,
ruthenium oxide, cobalt oxide, copper oxide, manganese oxide,
germanium oxide, lead oxide, cadmium oxide, vanadium oxide, niobium
oxide, tantalum oxide, rhodium oxide or rhenium oxide. Among them,
titanium oxide, zinc oxide, tin oxide, zirconium oxide, tungsten
oxide, iron oxide, niobium oxide are preferred because they show
activity even if the bake-curing is conducted at a low temperature
of not more than 100.degree. C. The particularly preferred is
titanium oxide. If the transparency of the coating is needed, it is
preferred that the average diameter of the primary particle is not
more than 50 .mu.m, more favorably not more than 5 .mu.m, most
favorably not more than 0.5 .mu.m. One photocatalyst may be used
for the photocatalyst (F). Also, two or more catalyst may be used
in combination thereof.
It is known that a photocatalyst generates active oxygen
(photocatalytic properties) when ultraviolet is irradiated in the
atmosphere. The active oxygen can oxidize and decompose organic
substances. Therefore, utilizing the properties of such a catalyst,
a self-cleaning effect of the decomposition of dirt originating in
carbon, which is adhered to a coated product, (e.g., a carbon
component contained in the exhaust gas of an automobile, nicotine
of tobacco); a deodorizing effect of the decomposition of a
malodorous component represented by an amine compound and an
aldehyde compound; and an antifungal effect of the prevention of
the generation of bacteria represented by Escherichia coli and
Staphylococcus aureus and the like can be obtained. Further, dirt
such as water repellant organic substances adhered to the surface
of a coating is decomposed and removed by the photocatalyst (F).
Thereby, there is an effect that wettability of the coating to
water is improved. This effect is exhibited regardless of the size
of the coating thickness or the amount of the photocatalyst
contained therein.
The photocatalyst (F) may be the one in which a metal is
incorporated. The metal to be incorporated is not specifically
limited. Examples thereof include gold, silver, copper, iron, zinc,
nickel, cobalt, platinum, ruthenium, palladium, rhodium, cadmium
and the like. Among them, one or two or more can be suitably used.
By the incorporation of the metal, the charge separation of the
photocatalyst (F) is accelerated. Therefore, the photocatalytic
function is exhibited more effectively. The photocatalyst (F) in
which a metal is incorporated has an oxidizing ability in the
presence of light. By this oxidizing performance, the deodorizing
effector anti-fungal effect is exhibited. Further, a clay
crosslinking material in which the photocatalyst (F) is
incorporated between layers. By introducing the photocatalyst
between the layers, fine particles are incorporated in the
photocatalyst (F) to improve the photocatalytic performance.
The method for dispersing the photocatalyst (F) in the functional
coating material (1) or (2) is not specifically limited.
A silica-dispersed organosilane oligomer solution (A) to be used as
Component (A) in the acryl-modified silicone resin coating material
or the functional coating material (2) is a main component of a
base polymer having a hydrolytic group (X) as a functional group
which is involved with the curing reaction at the time of forming a
cured coating. This can be obtained, for example, by adding one or
two or more hydrolytic organosilane compounds represented by the
general formula (I) to the colloidal silica dispersed in an organic
solvent or water (a mixture of the organic solvent and water may be
included) and partially hydrolyzing the hydrolytic organosilane,
under the condition that 0.001 to 0.5 mol of water (water which may
be contained in the colloidal silica beforehand and/or added
separately.) is used based on 1 mol equivalent of the
above-mentioned hydrolytic group (X).
R.sup.1 represented by the above-mentioned general formula (I) in
the hydrolytic organosilane is not specifically limited as long as
it is substituted or nonsubstituted hydrocarbon group having 1 to 8
carbon atoms. R.sup.1 may be the same or different. Examples
thereof include alkyl groups such as methyl groups, ethyl groups,
propyl groups, butyl groups, pentyl groups, hexyl groups, heptyl
groups or octyl groups; cycloalkyl groups such as cyclopentyl
groups or cyclohexyl groups; aralkyl groups such as 2-phenylethyl
groups, 2-phenylpropyl groups, 3-phenylpropyl groups; aryl groups
such as phenyl groups or tolyl groups; alkenyl groups such as vinyl
groups or allyl groups; halogen-substituted hydrocarbon groups such
as chloromethyl groups or .gamma.-chloropropyl groups or
3,3,3-trifluoropropyl groups; substituted hydrocarbon groups such
as .gamma.-methacryloxypropyl groups, .gamma.-glycidyloxypropyl
groups, 3,4-epoxycyclohexylethyl groups or .gamma.-mercaptopropyl
groups. Among them, alkyl groups having 1 to 4 carbon atoms and
phenyl groups are preferred because they are easily synthesized or
easily available.
In the above-mentioned general formula (I), the hydrolytic group X
is not specifically limited. For example, an alkoxy group, an
acetoxy group, an oxime group, an enoxy group, an amino group, an
aminoxy group, an amide group and the like are included. Among
them, an alkoxy group is preferred because it is easily available
and a silica-dispersed organosilane oligomer solution (A) is easily
prepared.
Examples of the above-mentioned hydrolytic organosilane include
those which are represented by the above general formula (I)
wherein m is an integer of 0 to 3, i.e., such as those having a
mono-, di-, tri- or tetra-functionality. Concrete examples thereof
include alkoxysilanes, acetoxysilanes, oximesilanes, enoxysilanes,
aminosilanes, aminoxysilanes, amidesilanes and the like. Among
them, the preferred are alkoxysilanes because they are easily
available and a silica-dispersed organosilane oligomer solution (A)
is easily prepared.
Among alkoxysilnes, particularly, examples of tetraalkoxysilanes
wherein m=0 include tetramethoxysilane, tetraethoxysilane and the
like. Examples of the organotrialkoxysilane wherein m=1 include
methyltrimethoxysilane, methyltriethoxysilane,
methyltriisopropoxysilane, phenyltrimethoxysilane,
phenyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane and
the like. Further, examples of the diorganodialkoxysilane wherein
m=2 include dimethyldimethoxysilane, dimethyldiethoxysilane,
diphenyldimethoxysilane, diphenyldiethoxysilane, methyl phenyl
dimethoxysilane and the like. Examples of the triorganoalkoxysilane
wherein m=3 include trimethylmethoxysilane, trimethylethoxysilane,
trimethylisopropoxysilane, dimethylisobutylmethoxysilane and the
like. Further, those which are generally referred to as silane
coupling agents are included in alkoxysilanes.
Among these hydrolytic organosilanes represented by the
above-mentioned general formula (I), 50 mole % or more, preferably
60 mol % or more, more favorably 70 mol % or more, may be those
having a tri-functionality wherein m=1. If it is less than 50 mol
%, the sufficient coating hardness cannot be obtained, and also,
the dry curability tends to be inferior.
Colloidal silica contained in Component (A) has an effect of
enhancing hardness of cured coating of the coating material and
improving smoothness and crack-arresting ability. The colloidal
silica is not specifically limited. For example, those mentioned as
a raw material (E1) of organosiloxane (E) can be used. When using
water-dispersed colloidal silica, water, which is present as a
component other than the solid content, can be used for the
hydrolysis of the above-mentioned hydrolytic organosilane. Also, it
can be used as a curing agent of the coating material.
In Component (A), colloidal silica is contained, as a silica
content, preferably in an amount of 5 to 95% by weight, more
favorably 10 to 90% by weight, most favorably 20 to 80% by weight,
based on the solid content of the whole condensate of organosilane
(I). When the content is less than 5% by weight, the desired
coating hardness is not likely to be obtained. On the other hand,
when it exceeds 95% by weight, uniform dispersion of silica is
difficult, which may cause various problems such as the gelation of
Component (A), or the frequent occurrence of crack in the cured
coating because it is too hard.
Further, in the present specification, the formulation ratio of
Component (A) in the coating material is a value including a
dispersion medium of colloidal silica.
The amount of water to be used at the time of preparing a
silica-dispersed organosilane oligomer solution (A) is 0.001 to 0.5
mol, preferably 0.01 to 0.4 mol, based on 1 mol equivalent of the
hydrolytic group (X) that the above-mentioned hydrolytic
organosilane has. If the amount of water to be used is less than
0.001 mol, a sufficiently partially hydrolyzed compound is not
obtained. If it exceeds 0.5 mol, the stability of the partially
hydrolyzed compound is deteriorated. Herein, the above-mentioned
amount of water used in the partial hydrolytic reaction of the
hydrolytic organosilane is the amount of water which is separately
added when using the colloidal silica containing no water (e.g.,
the colloidal silica in which an organic solvent alone is used as a
dispersion medium). When using colloidal silica containing water
(e.g., the colloidal silica in which water alone or a mixture of
water and an organic solvent is used as a dispersion medium), the
above-mentioned amount of water is the amount of water which is
contained in the colloidal silica beforehand plus at least the
amount of water which is contained in the colloidal silica along
with the separately added water. If the amount of water contained
in the colloidal silica beforehand alone satisfies the
above-mentioned amount to be used, it is not necessary to add water
separately. However, if the amount of water contained in the
colloidal silica beforehand alone does not satisfy the
above-mentioned amount to be used, it is necessary to add water
separately until the amount of water satisfies the above-mentioned
amount to be used. In that case, the amount of the above-mentioned
water to be used is the total amount of the water contained in the
colloidal silica beforehand and the water which is added
separately. Further, even if the water contained in the colloidal
silica alone satisfies the above-mentioned amount to be used, water
may be added separately. In that case, the amount of the
above-mentioned water to be used is also the total amount of the
water contained in the colloidal silica beforehand and the water
which is added separately. However, water is added separately so
that the total amount does not exceed the above-mentioned upper
limit (0.5 mol based on 1 mol equivalent of the hydrolytic group
(X)).
The method for conducting partial hydrolysis of hydrolytic
organosilane is not specifically limited. For example, hydrolytic
organosilane and colloidal silica may be mixed (when no water is
contained or the necessary amount of water is not contained in the
colloidal silica, water is added to that). In that case, partial
hydrolytic reaction proceeds at room temperature. In order to
accelerate the partial hydrolytic reaction, the mixture may be
optionally heated (e.g., at 60 to 100.degree. C.) or a catalyst may
be used. This catalyst is not specifically limited. One or two or
more organic acids and inorganic acids, such as hydrochloric acid,
acetic acid, halogenated silane, chloroacetic acid, citric acid,
benzoic acid, dimethylmalonic acid, formic acid, propionic acid,
glutaric acid, glycolic acid, maleic acid, malonic acid,
toluenesulfonic acid or oxalic acid, can be used.
It is preferred that a pH value of Component (A) is from 2.0 to
7.0, more favorably 2.5 to 6.5, most favorably 3.0 to 6.0, in order
to obtain its performance stably for a long period of time. If the
pH value is out of this range, particularly, when the amount of
water to be used is 0.3 mol or more, based on 1 mol equivalent of
the hydrolytic group (X), the performance of Component (A) is not
maintained and it is remarkably deteriorated. If the pH value of
Component (A) is out of the above-mentioned range, e.g., if it is
in the acidic side from this; range, a basic reagent such as
ammonia or ethylenediamine may be added to adjust the pH value. If
it is in the basic side from this range, an acidic reagent such as
hydrochloric acid, nitric acid or acetic acid may be added to
adjust the pH value. However, the adjusting method is not
specifically limited.
A silanol group-containing polyorganosiloxane (B) to be used as the
Component (B) in an acryl-modified silicone resin coating material
and a functional coating material (2) is a crosslinking agent for
forming a three-dimensional crosslinking structure in a cured
coating by the condensation reaction with Component (A), which is a
base polymer having a hydrolytic group serving as a functional
group in the curing reaction. Component (B) has an effect of
absorbing the distortion due to the cure shrinkage of Component (A)
and preventing the occurrence of crack.
R.sup.2 in the above-mentioned average compositional formula (II)
representing (B) is not specifically limited, and the same groups
as R.sup.1 in the above-mentioned formula (I) are exemplified.
Preferred examples thereof include substituted hydrocarbon groups
such as alkyl groups having 1 to 4 carbon atoms, phenyl groups,
vinyl groups, .gamma.-glycidyloxypropyl groups,
.gamma.-methacryloxypropyl groups, .gamma.-aminopropyl groups or
3,3,3-trifluoropropyl groups. More favorably, methyl groups and
phenyl groups are included. Further, in the above-mentioned formula
(II), a and b are numbers which separately satisfy the
above-mentioned condition. If a is less than 0.2 or b is more than
3, there is trouble such as the occurrence of crack in the cured
coating. Further, if a is more than 2 and less than 4, or b is less
than 0.0001, the curing does not proceed favorably.
The silanol group-containing polyorganosiloxane (B) is not
specifically limited. For example, it can be obtained by
hydrolyzing, for example, methyltrichlorosilane,
dimethyldichlorosilane, phenyltrichlorosilane,
diphenyldichlorosilane, or a mixture of one or 2 or more
alkoxysilanes corresponding to the above-mentioned compounds, using
a large amount of water according to a known method. The
polyorganosiloxane thus obtained is adjusted so that it has an
average-molecular weight (Mw) in terms of polystyrene of 700 to
20,000, preferably 750 to 18,000, more favorably 800 to 16,000.
In order to obtain the silanol group-containing polyorganosiloxane
(B), when an alkoxysilane is hydrolyzed according to a known
method, the small amount of alkoxy groups which are not hydrolyzed
may remain. Namely, polyorganosiloxane containing both silanol
groups and the very small amount of alkoxy groups is sometimes
obtained. In the present invention, such polyorganosiloxane may be
used.
A curing agent (C) to be used as Component (C) in an acryl-modified
silicone resin coating material and a functional coating material
(2) accelerates the condensation reaction of Component (A) with
Component (B) to cure the coating. Examples of the curing catalyst
(C) include all of those which may be optionally contained in the
functional coating material (1) mentioned above. However, the
curing catalyst (C) is not specifically limited as long as it is
useful for the acceleration of the condensation reaction of
Component (A) with Component (B), in addition to the
above-mentioned catalysts.
Acrylic resin (D) contained in the acryl-modified silicone resin
coating material, which is to be used as Component (D), has an
effect of improving the toughness of the cured coating made of the
acryl-modified silicone resin coating material. Thereby, the
occurrence of crack is prevented and it makes it possible to
thicken the coating. Further, the acrylic resin (D) is incorporated
into a crosslinking condensate of Component (A) and Component (B),
which is to be a three-dimensional bone structure of the cured
coating made of the acryl-modified silicone resin coating material,
to make the crosslinking condensate acryl-modified. When the
above-mentioned crosslinking condensate is acryl-modified, the
adhesion properties between the cured coating made of the
acryl-modified silicone resin coating material and the substrate
are improved. Both the cured coating made of the acryl-modified
silicone resin coating material and that made of the functional
coating material (1) or 2) are silicone resin cured products having
a polysiloxane structure, therefore, the adhesion properties
between both of the coatings are high. For that reason, between the
cured coating of the functional coating material (1) or (2) and the
substrate, a cured coating made of the acryl-modified silicone
resin coating material having high adhesion properties to them is
to be interposed, which eventually improves the adhesion properties
between the cured coating of the functional coating material (1) cr
(2) and the substrate. Further, the acryl-modified silicone resin
shows high weathering resistance and durability, therefore, it is
not influenced by a photocatalyst contained in the functional
coating materials (1) and (2), which are on the upper layer.
Examples of the first (meth)acrylate in the above-mentioned formula
(III), which is one of the compositional monomers of the acrylic
resin (D), include the ones in which R.sup.4 is represented by at
least one substituted or nonsubstituted monovalent hydrocarbon
group having 1 to 9 carbon atoms, for example, alkyl groups such as
methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl
group, i-butyl group, sec-butyl group, tert-butyl group, pentyl
group, hexyl group, heptyl group or octyl group; cycloalkyl groups
such as cyclopentyl group or cyclohexyl group; aralkyl groups such
as 2-phenylethyl group, 2-phenylpropyl group or 3-phenylpropyl
group; aryl groups such as phenyl group or tolyl group; halogenated
hydrocarbon groups such as chloromethyl group, .gamma.-chloropropyl
group or 3,3,3-trifluoropropyl group; hydroxy hydrocarbon groups
such as 2-hydroxyethyl group. The preferred are ethyl group, propyl
group and butyl group. The first (meth)acrylate in the
above-mentioned formula (III) may be a mixture thereof.
Examples of the second (meth)acrylate in the above-mentioned
general formula (III), which is another compositional monomers of
the acrylic resin (D), include the ones in which R.sup.4 is
represented by a group selected from the group consisting of epoxy
groups, glycidyl groups and hydrocarbon groups (e.g.,
.gamma.-glycidyloxypropyl groups, etc.) containing at least either
of the above. The preferred are epoxy groups and glycidyl groups.
The second (meth) acrylate in the above-mentioned formula (III) may
be a mixture thereof.
Examples of the third (meth)acrylate in the above-mentioned general
formula (III), which is one more another compositional monomers of
the acrylic resin (D), include the ones in which R.sup.4 is
represented by a hydrocarbon group containing an alkoxysilyl group
and/or a halogenated silyl group, the hydrocarbon group being
exemplified by trimethoxysilylpropyl group,
dimethoxymethylsilylpropyl group, monomethoxydimethylsilylpropyl
group, triethoxysilylpropyl group, diethoxymethylsilylpropyl group,
ethoxydimethylsilylpropyl group, trichlorosilylpropyl group,
dichloromethylsilylpropyl group, chlorodimethylsilylpropyl group,
chlorodimethoxysilylpropyl groupsb and dichloromethoxysilylpropyl
groups. The preferred are trimethoxysilylpropyl groups,
dimethoxysilylpropyl group and triethoxysilylpropyl group. The
third (meth)acrylate in the above-mentioned formula (III) may be a
mixture thereof.
The acrylic resin (D) is a (meth)acrylate copolymer of at least
three kinds of monomers comprising at least one of the first
(meth)acrylates, at least one of the second (meth) acrylates and
the at leastr one of third (meth)acrylates. The acrylic resin (D)
may be a copolymer further containing one or two or more
methacrylates selected from the above-mentioned first, second and
third methacrylates, or it may also be a copolymer further
containing one or two or more methacrylates selected from those
other than the above-mentioned methacrylates.
The above-mentioned first (meth)acrylate is an essential component
for improving the toughness of the cured coating of the
acryl-modified silicone resin coating material. Further, it also
has an effect of improving the compatibility between Component (A)
and Component (B). In order to obtain a greater effect of them, it
is preferred that the substituted or nonsubstituted hydrocarbon
group of R.sup.4 has a volume at least to some degree. Therefore,
the number of carbon atoms is preferably 2 or more.
The second (meth)acrylate is an essential component for improving
the adhesion properties between the cured coating made of the
acryl-modified silicone resin coating material and the
substrate.
The third (meth)acrylate forms a chemical bond between the acrylic
resin (D) and Components (A) and (B) at the time of curing the
coating made of the acryl-modified silicone resin coating material.
Thereby, the acrylic resin (D) is set in the cured coating.
Further, the third (meth)acrylate also has an effect of improving
the compatibility between the acrylic resin (D) and Components (A)
and (B).
The molecular weight of the acrylic resin (D) greatly relies on the
compatibility between the acrylic resin (D) and Components (A) and
(B). When the weight-average molecular weight of the acrylic resin
(D) exceeds 50,000 in terms of polystyrene, phase separation
occurs, and the whitening of the coating may occur. Accordingly, it
is preferred that the weight-average molecular weight of the
acrylic resin (D) is not more than 50,000 in terms of polystyrene.
Further, it is preferred that the lower limit of the weight-average
molecular weight of the acrylic resin (D) is 1,000 in terms of
polystyrene. If the molecular weight is less than 1,000, the
toughness of the coating is deteriorated, and crack is liable to
occur, which is not preferred.
It is preferred that the second (meth)acrylate is contained in the
copolymer of the acrylic resin (D) in a monomer molar ratio of 2%
or more. If it is less than 2%, the adhesion properties of the
coating tends to be insufficient.
It is preferred that the third (meth)acrylate is contained in the
copolymer in a monomer molar ratio of 2 to 50%. If it is less than
2%, the compatibility between the acrylic resin (D) and Components
(A) and (B) is poor and the whitening of the coating may occur. On
the other hand, if it is more than 50%, the bonding density is too
high, and therefore there tends to be no apparent improvement in
the toughness, an improvement of which is an original object of the
acrylic resin.
The synthesis of the acrylic resin (D) can be conducted, for
example, by a solution polymerization method in an organic solvent,
an emulsion polymerization method, a radical polymerization method,
a suspension polymerization method, an anion polymerization method,
a cation polymerization method or the like. However it is not
limited to the above.
In the radical polymerization method using solution polymerization,
it is conducted according to a known method. For example, the
above-mentioned first, second third (meth)acrylate monomers are
dissolved in an organic solvent in a reaction container. Further, a
radical polymerizing agent is added to that. Then, the mixture is
heated under a nitrogen atmosphere and reacted. The organic solvent
to be used is not specifically limited. Examples thereof include
toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone,
methyl isobutyl ketone, ethylene glycol monobutyl ether, diethylene
glycol monobutyl ether, ethylene acetate glycol monoethyl ether and
the like. Further, the radical polymerizing agent is not
specifically limited. For example, cumene hydroperoxide, tert-butyl
hydroperoxide, dicumyl peroxide, di-tert-butyl peroxide, benzoyl
peroxide, acetyl peroxide, lauroyl peroxide,
azobisisobutyronitrile, hydrogen peroxide-Iron.sup.2+ salt,
persulfate-NaHSO.sub.3, cumene hydroperoxide-Iron.sup.2+ salt,
benzoyl peroxidedimethylaniline, peroxide-triethyl aluminum and the
like are used. In order to control the molecular weight, a chain
transfer agent can be added. The chain transfer agent is not
specifically limited. Examples thereof include quinones such as
monoethyl hydroquinone or p-benzoquinone; thiols such as
mercaptoacetic acid-ethyl ester, mercaptoacetic acid-n-butyl ester,
mercaptoacetic acid-2-ethyl hexyl ester, mercaptocyclohexane,
mercaptocyclopentane or 2-mercaptoethanol; thiophenols such as
di-3-chlorobenzene thiol, p-toluene thiol or benzene thiol; thiol
derivatives such as .gamma.-mercaptopropyltrimethoxysilane;
phenylpycrylhydrazine; diphenylamine; tert-butyl catechol, etc.
The formulation ratio of the photocatalyst (F) in the functional
coating material (1) is not specifically limited because the
photocatalytic performance is exhibited regardless of the amount of
the photocatalyst. For example, it is preferable to use 90 to 10
parts by weight, more favorably, 50 to 10 parts by weight, based on
10 to 90 parts by weight of the resin solid content of the whole
condensate of organosiloxane (E), provided that the total of the
resin solid content of (E) and the amount of (F) comes to 100 parts
by weight. If the amount of the photocatalyst (F) is less than 10
parts by weight, sufficient photocatalytic performance is not
likely to be obtained. If it is more than 90 parts by weight, the
coating which is fragile and has no smoothness tends to be
obtained.
The formulation ratio of the photocatalyst (F) in the functional
coating material (2) is not specifically limited because the
photocatalytic performance is exhibited regardless of the amount of
the photocatalyst. For example, it is preferable to use 90 to 10
parts by weight, more favorably, 50 to 10 parts by weight, based on
10 to 90 parts by weight of the resin solid content of the whole
condensate of the total of Components (A) and (B), provided that
the total of the resin solid content of Components (A) and (B) and
the amount of (F) comes to 100 parts by weight. If the amount of
the photocatalyst (F) is less than 10 parts by weight, there tends
to be obtained no sufficient photocatalytic performance. If it is
more than 90 parts by weight, the coating which is fragile and has
no smoothness tends to be obtained.
The formulation ratio of Components (A) and (B) in the functional
coating material (2) is not specifically limited. For example,
preferably, 99 to 1 parts by weight of component (B) is used with 1
to 99 parts by weight of Component (A), more favor ably, 95 to 5
parts by weight of Component (B) is used with 5 to 95 parts by
weight of Component (A), most favorably, 90 to 10 parts by weight
of Component (B) is used with 10 to 90 parts by weight of Component
(A) (provided that the total of Components (A) and (B) comes to 100
parts by weight). If Component (A) is less than 1 part by weight,
the cold-curing properties are poor, or a coating having
insufficient hardness is likely to be obtained. On the other hand,
if Component (A) is more than 99 parts by weight, the curability of
the coating is unstable, or there tends to occur crack on the
coating.
The formulation ratio of Component (C) in the functional coating
material (2) is not specifically limited. For example, it is
preferable to use 0.0001 to 10 parts by weight, more favorably
0.005 to 8 parts by weight, most favorably 0.007 to 5 parts by
weight, based on 100 parts by weight of the total of the solid
content of the whole condensate of Components (A) and (B). If
Component (C) is less than 0.0001 parts by weight, the coating is
not likely to be cured at a normal temperature. On the other hand,
if it is more than 10 parts by weight, the heat resistance or
weathering resistance of the cured coating tends to be
deteriorated.
The formulation ratio of Component (C) in the acryl-modified
silicone resin coating material is not specifically limited. For
example, it is preferable to use 0.001 to 10 parts by weight, more
favorably, 0.005 to 8 parts by weight, most favorably 0.007 to 5
parts by weight, based on 100 parts by weight of the total of the
solid content of the whole condensate of Components (A), (B) and
(C). If Component (C) is less than 0.001 parts by weight, the
coating is not likely to be cured at a normal temperature. On the
other hand, if it is more than 10 parts by weight, the heat
resistance or weathering resistance of the cured coating tends to
be deteriorated.
The formulation ratio of Components (A), (B) and (D) in the
acryl-modified silicone resin coating material is not specifically
limited. For example, when based on the solid content of the whole
condensate, preferably, 94 to 1 parts by weight of Component (B)
and 5 to 35 parts by weight of Component (D) are used with 1 to 94
parts by weight of Component (A), more favorably, 95 to 5 parts by
weight of Component (B) and 5 to 35 parts by weight of Component
(D) are used with 5 to 95 parts by weight of Component (A), most
favorably, 94 to 10 parts of Component (B) and 5 to 35 parts by
weight of Component (D) are used with 10 to 94 parts by weight of
Component (A) (provided that the total of Components (A), (B) and
(D) comes to 100 parts by weight). If Component (A) is less than 1
part by weight, the cold-curing properties are poor, or there tends
to obtain no coating having sufficient hardness. On the other hand,
if it is more than 94 parts by weight, the curing properties are
unstable or crack is liable to occur on the coating. Further, if
Component (D) is less than 5 parts by weight, there tends to be
obtained no sufficient toughness or adhesion properties. If
Component (D) is more than 35 parts by weight, there is high
possibility that the deterioration of the coating may be
accelerated due to the photocatalyst in the upper layer.
In the functional coating material (1), a cured coating is formed
by the condensation reaction of hydrolytic groups contained in
Component (E), by heating at a low temperature or by adding a
curing catalyst and leaving them to stand at a normal temperature.
Accordingly, the functional coating material (1) is hardly
influenced by humidity even if it is cured at a normal temperature.
Further, if heat treatment is conducted, condensation reaction can
be accelerated without using a curing catalyst and a cured coating
can be formed.
In the functional coating material (2), a cured coating is formed
by the condensation reaction of a hydrolytic group in the
organosilane oligomer, which is contained in Component (A), with a
silanol group contained in Component (B), in the presence of a
curing catalyst (C), by leaving them to stand at a normal
temperature or by heating at a low temperature. Accordingly, the
functional coating material (2) is hardly influenced by humidity
even if it is cured at a normal temperature. Further, the
condensation reaction is accelerated by heat treatment, thus, a
cured coating can also be formed.
In the acryl-modified silicone resin coating material, a cured
coating is formed by the condensation reaction of a hydrolytic
group in the organosilane oligomer, which is contained in Component
(A) and a hydrolytic group contained in acrylic resin (D) with a
silanol group contained in Component (B), in the presence of a
curing catalyst (C), by leaving them to stand at a normal
temperature or by heating at a low temperature. Accordingly, the
acryl-modified silicone resin coating material is hardly influenced
by humidity even if it is cured at a normal temperature. Further,
the condensation reaction is accelerated by heat treatment, thus, a
cured coating can also be formed.
The acryl-modified silicone resin coating material may optionally
contain a pigment. The pigment to be used is not specifically
limited. Examples thereof include organic pigments such as carbon
black, quinacridone, naphthol red, Cyanine blue, Cyanine green or
Ransa yellow; and inorganic pigments such as titanium oxide, barium
sulfate, red oxide or composite metal oxide. One or two or more
selected from the above may also be used in combination. The method
for the dispersion of the pigment is not specifically limited, and
it may be conducted by a conventional method, for example, by
dispersing pigment powder directly using a Dyno mill, a paint
shaker, etc. In that case, it is possible to use a dispersing
agent, a dispersing additive, a thickening agent, a coupling agent
and the like. The amount of the pigment to be added is not
specifically limited because the opacifying properties differ
depending on the kind of the pigment. For example, it is preferable
to use 5 to 80 parts by weight, more favorably 10 to 60 parts by
weight, based on 100 parts by weight of the total of the solid
content of the whole condensate of Components (A), (B) and (D). If
the amount of the pigment to be added is less than 5 parts by
weight, the opacifying properties tend to be deteriorated. If it is
more than 80 parts by weight, the smoothness of the coating may be
deteriorated.
Further, a levelling agent, a dye, metal powder, glass powder, an
anti-fungus agent, an anti-oxidizing agent, an antistatic agent, an
ultraviolet absorber and the like may be contained in an inorganic
coating material composition as long as they do not adversely
affect the effect of the prevent invention.
The respective functional coating materials (1), (2) and the
acryl-modified silicone resin coating material may be optionally
diluted with various organic solvents because of easy handling.
Further, the dilute solution diluted with the above solvents may be
used. The kind of the organic solvent can be suitably selected
according to mono-valent hydrocarbon groups contained in Components
(A), (B), (D) or (E), or to the size of the molecular weight of
Components (A), (B), (D) or (E). Such an organic solvent is not
specifically limited. Examples thereof include lower aliphatic
alcohols such as methanol, ethanol, isopropanol, n-butanol or
isobutanol; ehtylene glycol derivatives such as ethylene glycol,
ethylene glycol monobutyl ether or ethylene acetate glycol
monoethyl ether; diethylene glycol derivatives such as diethylene
glycol or diethylene glycol mono butyl ether; and toluene, xylene,
hexane, heptane, ethyl acetate, butyl acetate, methyl ethyl ketone,
methyl isobutyl ketone, methyl ethyl ketoxime, diacetone alcohol,
etc. One or two or more selected from the above can be used in
combination. The dilution ratio of the organic solvent is not
specifically limited, and it may be suitably decided at need.
The method for applying the respective coating materials to the
substrate is not specifically limited. For example, various
conventional coating methods such as brushing, spraying, dipping,
flow-coating, roll coating, curtain coating, knife coating or spin
coating can be selected.
The method for curing the respective coating materials, which are
applied to the substrate, is not specifically limited and it may be
conducted by known methods. Further, the temperature when curing is
not specifically limited, and the temperature in the wide range
between a normal temperature and a heated temperature can be taken,
according to the desired cured coating performance, whether the
curing catalyst is used or not, and the heat resistance of the
photocatalyst, etc.
The thickness of the cured coating formed from the functional
coating materials (1) or (2) is not specifically limited, because
the photocatalytic performance is exhibited regardless of its
thickness. For example, the thickness of about 0.01 to 10 .mu.m may
be acceptable, but it is preferred that the thickness thereof is
0.05 to 5 .mu.m, more favorably 0.05 to 2 .mu.m, in order to adhere
and maintain the cured coating stably for a long period of time and
also to prevent crack or peeling.
The thickness of the cured coating formed from the acryl-modified
silicone resin coating material is not specifically limited. For
example, the thickness of about 0.1 to 100 .mu.m may be acceptable,
but it is preferred that the thickness thereof is 0.5 to 50 .mu.m,
in order to restrain deterioration of the substrate caused by the
photocatalyst, to adhere and maintain the cured coating stably for
a long period of time and also to prevent crack or peeling.
The process for producing the functional coated product of the
present invention is not specifically limited. For example, the
process of the present invention is preferred.
The process of the present invention is conducted, for example, as
follows:
First, the acryl-modified silicone coating material is applied to
the surface of the substrate as the first, coating layer, and then
the first coating layer is semi-cured. After that, the functional
coating material (1) or (2) is applied to the surface of this
semi-cured coating layer. That is, while the first coating layer is
semi-cured, the functional coating material (1) or (2) is applied
to that. At this time, if the first coating layer is completely
cured before applying the functional coating material (1) or (2),
the functional coating material (1) or (2) is peeled off due to the
completely cured first coating layer, and therefore a coating
cannot be formed. Further, if the functional coating material (1)
or (2) is applied while the first coating layer is still wet, the
first coating layer causes lifting (the adhesion properties between
the first coating layer and the substrate cannot be obtained).
In the present specification "semi-curing" indicates "tack free
drying" prescribed in JIS-K5400-1990. It means the condition such
that no scratch is marked on the surface of the coating when the
center of the coating is gently rubbed with a fingertip. Further,
"complete curing" indicates "hard drying" prescribed in
JIS-K5400-1990. It means the condition such that no depression due
to a fingerprint is marked on the surface of the coating and the
movement of the coating is not felt, and also no scratch is marked
even when the center of the coating is rubbed fast with the
fingertip repeatedly. Furthermore, "the coating layer is still wet"
means the condition such that the fingertip is stained when the
center of the coating is gently touched with the fingertip.
As mentioned above, after the second coating layer is formed by
applying the functional coating material (1) or (2) to the surface
of the semi-cured layer made of the acryl-modified silicone resin
coating material, these semi-cured coating layer and second coating
layer are cured.
Further, the process for obtaining the functional coated product of
the present invention is not limited to the production process of
the present invention.
The substrate to be used in the present invention is not
specifically limited. For example, when using a metallic substrate,
an organic substrate and a substrate coated with an organic
substance in which either one of the above substrates has a coating
formed from an organic substance on the surface thereof, the effect
of the improvement in the adhesion properties between the substrate
and the coating or the prevention of the deterioration of the
substrate is exhibited more clearly. Therefore, the preferred is a
substrate selected from the group consisting of a metallic
substrate, an organic substrate and a substrate coated with an
organic substance in which either one of the above substrates has a
coating formed from an organic compound on the surface thereof.
However, it should not be construed that the substrate is limited
to them. For example, an inorganic substrate other than the
metallic substrate and a substrate coated with an organic substance
having a coating formed with an organic substance on the surface of
the inorganic substrate other than the metallic substrate may also
be used.
The inorganic substrate other than the metallic substrate is not
specifically limited. Examples thereof include a glass substrate,
enamel, a water-glass ornamental plate, an inorganic construction
material such as an inorganic cured material, ceramic and the
like.
The metallic material is not specifically limited. Examples thereof
include non-ferrous metal [e.g., aluminum (JIS-H4000, etc.),
aluminum alloy (duralumin, etc.), copper, zinc, etc.], iron, steel
[e.g., rolled steel (JIS-G3101, etc.), hot-dip zinc-coated steel
(JIS-G3302), (rolled) stainless steel (JIS-G4304, G4305, etc.),
etc.], tinplate (JIS-G3303, etc.), and the whole range of other
metal (including alloy).
The glass material is not specifically limited. Examples thereof
include sodium soda glass, Pyrex glass, quartz glass, no-alkali
glass and the like.
The above-mentioned enamel is formed by coating the surface of the
metal with an enamel glass agent by means of baking. Examples of
the substrate include, a mild steel plate, a steel plate, cast
iron, aluminum and the like. However, it is not limited to them.
Concerning the enamel agent, conventional ones may be used and it
is not specifically limited.
The above-mentioned water-glass ornamental plate indicates an
ornamental plate obtained, for example, by applying sodium silicate
to a cement substrate such as slate, followed by baking.
The inorganic cured material is not specifically limited. Examples
thereof include the whole range of substrates obtained by
cure-molding inorganic materials such as a fiber reinforced cement
plate (JIS-A5430, etc.), a ceramic siding (JIS-A5422, etc.), a
cemented excelsior board (JIS-A5404, etc.), pulp cement flat sheet
(JIS-A5414, etc.), slate/excelsior cemented laminated plate
(JIS-A5426, etc.) a gypsum board product (JIS-A6901, etc.), a clay
roof tile (JIS-A5208, etc.), a thick slate (JIS-A5402), a ceramic
tile (JIS-A5209, etc.), a concrete block for construction
(JIS-A5406, etc.), terrazzo (JIS-A5411, etc.), prestressed concrete
double T slab (JIS-A5412, etc.), an ALC panel (JIS-A5416, etc.), a
hollow prestressed concrete panel (JIS-A6511, etc.) or a common
brick (JIS-R1250, etc.).
The ceramic material is not specifically limited. Examples thereof
include alumina, zirconia, silicon carbide, silicon nitride and the
like.
The organic substrate is not specifically limited. Examples thereof
include plastic, wood, timber, paper and the like.
The plastic is not specifically limited. Examples thereof include
thermosetting or thermoplastic plastics such as polycarbonate
resin, acrylic resin, ABS resin, vinyl chloride resin, epoxy resin
or phenol resin, and fiber reinforced plastic (FRP) obtained by
reinforcing the above plastics with glass fiber, nylon fiber,
carbon fiber, etc.
The organic coating forming a substrate coated with an organic
substance is not specifically limited. Examples thereof include a
cured coating made of a coating material containing organic resin
such as acrylic resin, alkyd resin, polyester resin, epoxy resin,
urethane resin, acrylsilicone resin, chlorinated rubber resin,
phenolic resin or melamine resin.
The form of the substrate is not specifically limited. Examples
thereof include a film-shaped, sheet-shaped, plate-shaped,
fiber-shaped substrate and the like. Further, the substrate may be
a molded material made of the materials of these shapes or a
compositional material a part of which has at least one of the
molded materials of the above shapes or the compositional
materials.
The substrate may be formed from the above-mentioned various
materials alone, or it may be a composite material comprising at
least two of the above-mentioned various materials or a laminated
material comprising the lamination of at least two of the
above-mentioned various materials.
The functional coated product of the present invention can be
suitably used for the following use, by means of providing at least
a part of various materials or products, using various effects
originating in the excellent photocatalytic action.
A material or article related to building construction such as a
sheathing material (e.g., a material for outside wall, a roof tile
such as a flat roof tile, a clay roof tile or a metal roof tile), a
rainwater guttering such as a resin rainwater guttering (e.g., a
PVC rainwater guttering) or a metal rainwater guttering (e.g., a
stainless steel rainwater guttering, etc.), a gate and a material
to be used for that (e.g., a gate door leaf, a gate pier, a gate
fence, etc.), a fence and a material to be used for that, a garage
door leaf, a home terrace, a door, a stanchion, a carport, a cycle
port, a sign post, a delivery post, a wiring apparatus such as a
switchboard/switch, a gas meter, an interphone, a main body and a
camera lens portion of a video intercom, an electric lock, an
entrance pole, a porch, an air outlet of a ventilating fan or glass
for building construction, a window (an open able window, e.g., a
lighting window, a sky lighting, a louver, etc.) and a material to
be used for that (e.g., a window frame, a weather door, a blind,
etc.) an automobile, a railway rolling stock, an aircraft, a marine
structure, machine equipment, a material for highway-related
construction (e.g., a sound barrier, an interior material for a
tunnel, various display equipment, a guardrail, a car stop, a
railing, a signboard and a signpost of a traffic-control sign, a
traffic light, a post cone, etc.), a post for public notice, an
outdoor or indoor lighting fixture and a material to be used for
that (e.g., a glass material, a resin material, a metallic
material, a ceramic material, etc.), glass for solar battery,
agricultural-use vinyl sheets and green house, an outdoor air
conditioning unit, an antenna for VHF, UHF, BS, CS, etc.
Further, according to the present invention, the first coating
layer and the second coating layer may be directly formed on at
least a part of the above-mentioned materials or articles. However,
it is not limited to them. For example, the functional coated
product of the present invention wherein a base film material is
used, namely, the functional coating comprising the first coating
layer and the second coating layer formed on the surface of the
base film material, may be pasted on at least a part of various
materials or articles. Examples of such a film substrate include
polyethylene terephthalate (PET) resin poly butylene-terephthalate
(PBT) resin, PVC resin, acrylic resin, fluorine plastics,
polypropylene (PP) resin, composite resin thereof and the like, but
it is not specifically limited.
EXAMPLES
The present invention is explained in detail by the following
Examples and Comparative Examples. It is, of course, not the
intention hereby to limit the invention. In Examples and
Comparative Examples, "part", "%" and "ppm" are all indicate "part
by weight", "% by weight" and "ppm by weight", respectively, unless
otherwise stated. Further, the measurement of the molecular weight
was conducted by means of GPC (gel permeation chromatography) using
a measuring apparatus, HLC8020 manufactured by Toso Co., Ltd., to
make a calibration curve with standard polystyrene.
EXAMPLES
First, functional coating materials (1), (2), acryl-modified
silicone resin coating materials and Comparative coating materials
were prepared.
Preparation of a Functional Coating Material (1) and a Comparative
Coating Material
Preparation Example 1-1
Into a flask equipped with a stirrer, a warming jacket, a
condenser, a dropping funnel and a thermometer were charged 100
parts of methyltrimethoxysilane, 20 parts of tetraethoxysilane, 105
parts of IPA-ST (colloidal silica sol dispersed in isopropanol: a
particle diameter of 10 to 20 nm, a solid content of 30%, a water
content of 0.5% manufactured by Nissan Kagaku Kogyo Co.), 30 parts
of dimethyldimethoxysilane, 100 parts of isopropanol. Thereafter,
100 ppm of hydrochloric acid based on the solid content of the
whole condensate (30%) of this solution, and water of 3% on the
basis of the above silicon alkoxide, were added to this solution
mixture for hydrolysis at 25.degree. C. for 30 minutes while
stirring the mixture. After cooling, the silicone coating solution
having an average molecular weight of about 1,700 was obtained. To
this were added 0.2 parts of lithium formate as a curing catalyst
and titanium oxide as a photocatalyst (STS-01 manufactured by
Ishihara Sangyo Co., an average particle diameter of 7 nm, a solid
content of 30%) so that the weight ratio of the resin solid content
of the silicone coating solution to the photocatalyst (resin solid
content/photocatalyst) was 80/20. Then, the mixture was diluted
with methanol so that the whole solid content was 10% to give a
functional coating material (1-1).
Preparation Examples 1-2 to 1-5
Functional coating materials (1-2) to (1-5) were obtained in the
same manner as in Example 1, except that the amount of the
photocatalyst which was added was changed such that the resin solid
content/photocatalyst weight ratio was 60/40, 50/50, 40/60 and
20/80, respectively. Further, the average molecular weight of the
organosiloxane was about 1,700 ((1-2) to (1-5)).
Comparative Preparation Example 1
The comparative functional coating material (1) was obtained in the
same manner as in Preparation Example 1, except that no
photocatalyst was used. The average molecular weight of the
organosiloxane was about 1,700.
Preparation of Functional Coating Material (2) and Comparative
Coating Material
Prior to the preparation of a coating material, Component (A) and
Component (B), which are to be used in the preparation, were
prepared by the following method.
Preparation Example A-1
Into a flask equipped with a stirrer, a warming jacket, a condenser
and a thermometer were charged 100 parts of IPA-ST (colloidal
silica sol dispsesed in isoprppanol: a particle diameter of 10 to
20 nm, a solid content of 30%, a water content of 0.5% manufactured
by Nissan Kagaku Kogyo Co.), 68 parts of methyltrimethoxysilane and
2.2 parts of water were charged. Then, the hydrolysis was conducted
at 65.degree. C. for 5 hours while stirring the mixture. After
cooling, Companent (A-1) was obtained. The solid content of the
whole condensate of this component was 37% when it was left to
stand at room temperature for 48 hours.
Conditions of the Preparation of A-1
The amount of water based on 1 mol of a hydrolytic groups
(mol).sub.4 0.1.
The amount of silica contained in Component (A-1) 47.3%
The amount of hydrolytic organosilane in which m=1 (mol %) 100 (mol
%)
Preparation Example B-1
A solution in which 220 parts (1 mol) of methyltriisopropoxysilane
was dissolved in 150 parts of toluene was charged into a flask
equipped with a stirrer, a warming jacket, a condenser, a dropping
funnel and a thermometer. To this was added dropwise 108 parts of a
1% solution of hydrochloric acid over 20 minutes to conduct the
hydrolysis of methyltriisopropoxysilane at 60.degree. C. under
stirring. Forty minutes after the completion of the dropping, the
stirring was terminated. The reaction mixture was poured from the
flask into a separating funnel, followed by standing. Then, the
reaction mixture was separated into two layers. The mixed solution
of water and isopropyl alcohol in the underlayer, which contained
hydrochloric acid in a small amount, was removed by separation.
Then, hydrochloric acid remaining in the residual resin solution of
toluene was removed by washing with water. Further, toluene was
removed under reduced pressure. Thereafter, the residue was diluted
with isopropyl alcohol to obtain a 40% isopropyl alcohol solution
of a silanol group-containing polyorganosiloxane having a
weight-average molecular weight of about 2,000. This was used as
Component (B-1).
Preparation Example 2-1
Component (A-1) and Component (B-1) obtained above were mixed with
the following curing catalysts (C-1) and (C-2) in the following
ratio. To this was added as a photocatalyst titanium oxide
(manufactured by Ishihara Sangyo Co. STS-02, an average particle
diameter of 7 nm and a solid content of 30%) so that the weight
ratio of the total resin solid content of Components (A-1) and
(B-1) to the photocatalyst was 80/20. Thereafter, the mixture was
diluted with methanol so that the total solid content was 10% to
obtain a functional coating material (2-1).
Component (A-1): 50 parts (solid content: 18.5 parts) Component
(B-1): 50 parts (solid content: 20 parts) Component (C-1):
N-.beta.-aminoethyl-.gamma.-aminopropylmethyl Dimethoxysilane: 2
parts Component (C-2): dibutiltin dilaurate 0.4 parts
Preparation Examples 2-2 to 2-5
The functional coating materials (2-2) to (2-5) were obtained in
the same manner as in Preparation Example 2-1, except that the
amount of the photocatalyst which was added was changed such that
the resin solid content/photocatalyst weight ratio was 60/40,
50/50, 40/60 and 20/80, respectively.
Comparative Preparation Example (2)
The comparative coating material (2) was obtained in the same
manner as in Preparation Example 2-1, except that no photocatalyst
was used.
Preparation of Acryl-Modified Silicone Resin Coating Material and
Comparative Coating Material
Prior to the preparation of a coating material, Component (A),
Component (B) and Component (D), which were to be used in the
preparation, were prepared by the following method.
Preparation Example A-2
Into a flask equipped with a stirrer, a warming jacket, a condenser
and a thermometer were charged 100 parts of MA-ST (colloidal silica
sol dispersed in methanol: a particle diameter of 10 to 20 nm, a
solid content of 30%, a water content of 0.5% manufactured by
Nissan Kagaku Kogyo Co.), 68 parts of methyltrimethoxysilane, 49.5
parts of phenyltrimethoxysilane, 16.0 parts of water and 0.1 parts
of acetic anhydride. Then, the hydrolysis was conducted at
60.degree. C. for 5 hours while stirring the mixture. After
cooling, Companent (A-2) was obtained. The solid content of the
whole condensate of this component was 41% when it was allowed to
stand for 48 hours at room temperature.
Conditions of the Preparation of A-2
The amount of water based on 1 mol of hydrolytic groups (mol):
0.4
The amount of silica contained in Component (A-2): 31.3%
The amount of hydrolytic organosilane in which m=1: 100 (mol %)
Preparation Example B-2
Into a flask equipped with a stirrer, a warming jacket, a
condenser, a dropping funnel and a thermometer were charged 1,000
parts of water and 50 parts of acetone. Further, the hydrolysis was
conducted while adding dropwise a solution, in which 44.8 parts
(0.3 mol) of methyltrichlorosilane and 84.6 parts (0.4 mol) of
phenyltrichlorosilane were dissolved in 200 parts of toluene, to
the mixture under stirring at 60.degree. C. Forty minutes after the
completion of the dropping, the stirring was terminated. The
reaction mixture was poured from the flask into a separating
funnel, and then left to stand. Then, the reaction mixture was
separated into two layers. Aqueous hydrochloric acid in the
under-layer was removed by separation. Then, water and hydrochloric
acid remaining in the toluene solution of the residual
organopolysiloxane was removed together with the excess amount of
toluene by means of reduced-pressure stripping to obtain a 60%
toluene solution of silanol group-containing polyorganosiloxane
having a weight-average molecular weight of about 3,000. This was
used as Component (B-2). It was confirmed that this silanol
group-containing polyorganosiloxane in Component (B-2) and
Component (B-1) satisfied the above-mentioned average compositional
formula
Preparation Example D-1
In a flask equipped with a stirrer, a warming jacket, a condenser,
a dropping funnel, a nitrogen-introducing/discharging opening and a
thermometer, a solution in which 0.025 parts (0.15 mmol) of
azobisisobutyronitrile was dissolved in 3 parts of toluene was
added dropwise to a reaction solution in which 5.69 parts (40 mmol)
of n-butylmethacrylate (BMA), 1.24 parts (5 mmol) of
trimethoxysilylpropylmethacrylate (SMA), 0.71 parts (5 mmol) of
glycidyl methacrylate (GMA) and further 0.784 parts (4 mmol) of
.gamma.-mercaptopropyltrimethoxysilane as a chain transfer agent
were dissolved in 8.49 parts of toluene under a nitrogen
atmosphere. The mixture was reacted at 70.degree. C. for 2 hours.
By this, a polymer having a weight-average molecular weight of
1,000 was obtained. This acrylic resin solution was used as
Component (D-1) without any further treatment.
Conditions of the Preparation of D-1
The molar ratio of monomers BMA/SMA/GMA = 8.0/1.0/1.0 The
weight-average molecular weight 1.000 The solid content 40%
Preparation Example D-2
In a flask equipped with a stirrer, a warming jacket, a condenser,
a dropping funnel, a nitrogen-introducing/discharging opening and a
thermometer, a solution in which 0.025 parts (0.15 mmol) of
azobisisobutyronitrile was dissolved in 3 parts of toluene was
added dropwise to a reaction solution in which 0.71 parts (5 mmol)
of n-butylmethacrylate (BMA), 0.62 parts (2.5 mmol) of
trimethoxysilylpropylmethacrylate (SMA), 6.04 parts (42.5 mmol) of
glycidyl methacrylate (GMA) and further 0.196 parts (1 mmol) of
.gamma.-mercaptopropyltrimethoxysilane as a chain transfer agent
were dissolved in 8.06 parts of toluene under a nitrogen
atmosphere. The mixture was reacted at 70.degree. C. for 2 hours.
By this, a polymer having a weight-average molecular weight of
3,000 was obtained. This acrylic resin solution was used as
Component (D-2) without any further treatment.
Condition of the Preparation of D-2
The molar ratio of monomers BMA/SMA/GMA = 1.0/0.5/8.5 The
weight-average molecular weight 3.000 The solid content 40%
Preparation Example D-3
In a flask equipped with a stirrer, a- warming jacket, a condenser,
a dropping funnel, a nitrogen-introducing/discharging opening and a
thermometer, a solution in which 0.025 parts (0.15 mmol) of
azobisisobutyronitrile was dissolved in 3 parts of toluene was
added dropwise to a reaction solution in which 6.05 parts (42.5
mmol) of n-butylmethacrylate (BMA), 0.62 parts (2.5 mmol) of
trimethoxysilylpropylmethacrylate (SMA), 0.71 parts (5 mmol) of
glycidyl methacrylate (GMA) and further 0.098 parts (0.5 mmol) of
.gamma.-mercaptopropyltrimethoxysilane as a chain transfer agent
were dissolved in 8.06 parts of toluene under a nitrogen
atmosphere. The mixture was reacted at 70.degree. C. for 2 hours.
By this, a polymer having a weight-average molecular weight of
5,000 was obtained. This acrylic resin solution was used as
Component (D-3) without any further treatment.
Conditions of the Preparation of D-3
The molar ratio of monomers BMA/SMA/GMA = 8.5/6.5/1.0 The
weight-average molecular weight 5.000 The solid content 40%
Preparation Example D-4
In a flask equipped with a stirrer, a warming jacket, a condenser,
a dropping funnel, a nitrogen-introducing/discharging opening and a
thermometer, a solution in which 0.025 parts (0.15 mmol) of
azobisisobutyronitrile was dissolved in 3 parts of toluene was
added dropwise to a reaction solution in which 3.20 parts (22.5
mmol) of n-butylmethacrylate (BMA), 1.24 parts (5 mmol) of
trimethoxysilylpropylmethacrylate (SMA), 3.20 parts (22.5 mmol) of
glycidyl methacrylate (GMA) and further 0.784 parts (4 mmol) of
.gamma.-mercaptopropyltrimethoxysilane as a chain transfer agent
were dissolved in 8.46 parts of toluene under a nitrogen
atmosphere. The mixture was reacted at 70.degree. C. for 2 hours.
By this, a polymer having a weight-average molecular weight of
1,000 was obtained. This acrylic resin solution was used as
Component (D-4) without any further treatment. Conditions of the
preparation of D-4
The molar ratio of monomers BMA/SMA/GMA = 4.5/1.0/4.5 The
weight-average molecular weight 1.000 The solid content 40%
Preparation Example 3
Component (A-2), Component (B-2) and Component (D-1) obtained above
were mixed with the following curing catalysts (C-1) and (C-2) in
the following ratio. Thereafter, the mixture was diluted with
isopropyl alcohol so that the solid content was 25% to obtain the
functional coating material (1).
Component (A-2): 50 parts (solid content: 20.5 parts) Component
(B-2): 50 parts (solid content: 30 parts) Component (C-1):
N-.beta.-aminoethyl-.gamma.-aminopropylmethyldimethoxy- silane 2
parts Component (C-2): dibutyltin dilaurate 0.4 parts Component
(D-1): 20.25 parts (solid content: 8.1 parts)
Preparation Example 4
The acryl-modified silicone resin coating material (2) was obtained
in the same manner as in Preparation Example 3, except that the
formulation ratio of Components (A-2), (B-2), (C-1), (C-2) and
(D-1) was changed as follows. Component (A-2): 50 parts (solid
content: 20.5 parts) Component (B-2): 50 parts (solid content: 30
parts) Component (C-1): 2 parts Component (C-2): 0.4 parts
Component (D-1): 6 parts (solid content: 2.4 parts)
Preparation Example 5
The acryl-modified silicone resin coating material (3) was obtained
in the same manner as in Preparation Example 3, except that the
formulation ratio of Components (A-2), (B-2), (C-1), (C-2) and
(D-1) was changed as follows. Component (A-2): 50 parts (solid
content: 20.5 parts) Component (B-2): 50 parts (solid content: 30
parts) Component (C-1): 2 parts Component (C-2): 0.4 parts
Component (D-1): 53 parts (solid content: 20 parts)
Comparative Preparation Example 3
The comparative coating material (3) was obtained in the same
manner as in Preparation Example 3, except that no Component (D-1)
was used.
Preparation Example 6
The acryl-modified silicone resin coating material (4) was obtained
in the same manner as in Preparation Example 3, except that
Components (A-2) and (B-2) were changed to Components (A-1) and
(B-1), respectively, and that the formulation ratio of the
respective components was as follows. Component (A-1): 10 parts
(solid content: 3.7 parts) Component (B-1): 10 parts (solid
content: 4 parts) Component (C-1): 3 parts Component (C-2): 0.4
parts Component (D-1): 180 parts (solid content: 72 parts)
Preparation Example 7
The acryl-modified silicone resin coating material (5) was obtained
in the same manner as in Preparation Example 3, except that
Components (A-2) and (B-2) were changed to Components (A-1) and
(B-1), respectively, and that the formulation ratio of the
respective components was as follows. Component (A-1): 50 parts
(solid content: 18.5 parts) Component (B-1): 50 parts (solid
content: 20 parts) Component (C-1): 3 parts Component (C-2): 0.4
parts Component (D-1): 50 parts (solid content: 20 parts)
Preparation Example 8
The acryl-modified silicone resin coating material (6) was obtained
in the same manner as in Preparation Example 3, except that
Components (A-2), (B-2) and (D-1) were changed to Components (A-1),
(B-1) and (D-2), respectively, and that the formulation ratio of
the respective components was as follows. Component (A-1): 10 parts
(solid content: 3.7 parts) Component (B-1): 10 parts (solid
content: 4 parts) Component (C-1): 2 parts Component (C-2): 0.4
parts Component (D-2): 80 parts (solid content: 32 parts)
Preparation Example 9
The acryl-modified silicone resin coating material (7) was obtained
in the same manner as in Preparation Example 3, except that
Components (A-2), (B-2) and (D-1) were changed into Components
(A-1), (B-1) and (D-2), respectively, and that the formulation
ratio of the respective components was as follows. Component (A-1):
10 parts (solid content: 3.7 parts) Component (B-1): 10 parts
(solid content: 4 parts) Component (C-1): 3 parts Component (C-2):
0.4 parts Component (D-2): 180 parts (solid content: 72 parts)
Preparation Example 10
The acryl-modified silicone resin coating material (8) was obtained
in the same manner as in Preparation Example 3, except that
Components (A-2), (B-2) and (D-1) were changed to Components (A-1),
(B-1) and (D-3), respectively, and that the formulation ratio of
the respective components was as follows. Component (A-1): 10 parts
(solid content: 3.7 parts) Component (B-1): 10 parts (solid
content: 4 parts) Component (C-1): 3 parts Component (C-2): 0.4
parts Component (D-3): 180 parts (solid content: 72 parts)
Preparation Example 11
The acryl-modified silicone resin coating material (9) was obtained
in the same manner as in Preparation Example 3, except that
Components (A-2), (B-2) and (D-1) were changed to Components (A-1),
(B-1) and (D-4), respectively, and that the formulation ratio of
the respective components was as follows. Component (A-1): 10 parts
(solid content: 3.7 parts) Component (B-1): 10 parts (solid
content: 4 parts) Component (C-1): 3 parts Component (C-2): 0.4
parts Component (D-4): 180 parts (solid content: 72 parts)
Examples 1 to 10 and Comparative Examples 1 and 2
Using a PC (polycarbonate) plate (50 mm.times.50 mm.times.2.5 mm)
as a substrate, the first applied layer was formed by means of
spray coating with the acryl-modified silicone resin coating
material (1) prepared in Preparation Example 3 so that the cured
coating thickness was 1 .mu.m. Then, the coating was cured at
60.degree. C. for 15 minutes. After that, the setting time was
provided for 10 minutes. After the completion of the setting time,
the center of the coated surface was strongly pinched with a thumb
and an index finger to form depressions on the coated surface due
to a fingerprint. Also, the movement of the coating was felt.
However, even if the center of the coating was gently rubbed with a
fingertip, no scratch was formed on the coated surface. From this
results, it was confirmed that the first coating layer-was a
semi-cured condition.
The second coating layer was formed by means of spray coating with
the functional coating materials (1-1) to (1-5), (2-1) to (2-5) or
comparative coating materials (1) and (2) so that the cured coating
thickness was 0.5 .mu.m. After that, the second coating layer was
allowed to stand at room temperature for one week to obtain
functional coated products (1) to (10) and a comparative coated
products (1) and (2).
Concerning the functional coated products (1) to (10) and
comparative coated products (1) and (2), tests for coating
properties and for preventive properties for deterioration were
conducted by the following evaluation method.
Evaluation on Coating Properties
Adhesion Properties
Adhesion properties to the substrate were evaluated by the peeling
test using adhesive tape having a pattern of squares (cellophane
tape was used).
Surface Hardness
It was conducted according to hardness test using a pencil (based
on JIS-K5400).
Photocatalytic Action
Into a 300 ml container containing a sample, 50 ppm of acetaldehyde
was injected. Black light (10 W) was irradiated to the container
for 60 minutes to measure the ratio of the removed aldehyde (%) by
means of gas chromatography (GC14A manufactured by Shimazu
Seisakusho K.K.).
Wettability to Water
It was evaluated by measuring the contact angle formed by water and
the coating. The contact angle was measured when the coating was in
the initial stage after preparation, and after the coating was
irradiated by UV light for 24 hours using an UV-irradiation device
(HANDY UV300 manufactured by OAK FACTORY).
Evaluation on the Deterioration of a Substrate and a Coating
Light was irradiated with a Sunshine Weatherometer (according to
JIS-K5400) for 2,500 hours to observe a substrate and a coating.
Those which showed no change were evaluated to be good.
Evaluation results were shown in Tables 1 and 2. As shown in these
tables, in the second coating layer, the more the content of
titanium oxide, which was used as a photocatalyst, the better
photocatalytic performance was exhibited. However, the hardness is
somewhat deteriorated if the ratio of titanium oxide is 80% or
more. Further, the adhesion properties between the substrate and
the first coating layer, those between the first coating layer and
the second coating layer were good. Further, concerning the
functional coated products (1) to (10), sufficient photocatalytic
performance was exhibited although the second coating layer
containing the photocatalyst was cured at room temperature.
Concerning wettability of the coating, after the irradiation of UV
light, every functional coated product had a contact angle of a few
degree regardless of the amount of the photocatalyst contained in
the coating layer, which showed high wettability. Furthermore,
concerning the functional coated products (1) to (10) having a
coating layer containing the photocatalyst, although a PC plate,
which is easily subjected to the deterioration due to the
photocatalyst, was used, the deterioration of the substrate was
sufficiently prevented by interposing a coating layer made of the
acryl-modified silicone resin coating material between the coating
containing the photocatalyst and the substrate. Further, the
deterioration of the coating was not observed, either.
Comparative Example 3
A comparative coated product (3) was obtained in the same manner as
in Example 1, except that the second coating layer was formed only
with titanium oxide instead of forming a cured coating of the
functional coating material.
Concerning the comparative coated product (3), the evaluation on
coating properties and deterioration of the substrate and the
coating were conducted according to the above-mentioned method.
The results thereof were shown in Table 3. As shown in this table,
photocatalytic performance was very good, however, the coating of
the second coating layer was fragile because the second coating
layer comprises sol only. Therefore, the first coating layer and
the second coating layer were not adhered. Also, it was not easy to
measure the hardness. Concerning the deterioration of the
substrate, yellowing was seen on the PC plate.
Comparative Example 4
A comparative coated product (4) was obtained in the same manner as
in Example 3, except that the first coating layer was formed with a
cured coating made of a comparative coating material (3) containing
no Component (D), instead of forming a cured coating made of the
acryl-modified silicone resin coating material (1).
Concerning the comparative coated product (4), the evaluation on
coating properties and deterioration of the substrate and the
coating were conducted according to the above-mentioned method.
The results thereof were shown in Table 3. As shown in this table,
adhesion properties between the substrate and the first coating
layer were not obtained. There was no problems concerning the
deterioration of the substrate and the coating.
Comparative Example 5
A comparative coated product (5) was obtained in the same manner as
in Example 3, except that the functional coating material (1-3) was
directly applied to the surface of the substrate without using the
acryl-modified silicone resin coating material and that the curing
was conducted.
Concerning the comparative coated product (5), the evaluation on
coating properties and deterioration of the substrate and the
coating were conducted according to the above-mentioned method.
The results thereof were shown in Table 3. As shown in this table,
adhesion properties between the substrate and the cured coating of
the functional coating material were not obtained. Further, the
substrate was deteriorated due to the action of the photocatalyst
contained in the cured coating of the functional coating
material.
Comparative Example 6
A comparative coated product (6) was obtained in the same manner as
in Comparative Example 1, except that the comparative functional
coating material (1) was directly applied to the surface of the
substrate without using the acryl-modified silicone resin coating
material and that the curing was conducted.
Concerning the comparative coated product (6), the evaluation on
coating properties and deterioration of the substrate and the
coating were conducted according to the above-mentioned method.
The results thereof were shown in Table 3. As shown in this table,
the deterioration of the substrate and the coating was not
observed, however, adhesion properties between the substrate and
the cured coating formed with the coating material were not
obtained.
Examples 11 to 13
Examples of Colored Coating
Functional coated products (11) to (1.3) were obtained in the same
manner as in Example 3, except that the first coating layer was
formed with enamel obtained by adding the following pigments (1) to
(3) to the acryl-modified silicone resin coating material (1),
instead of the acryl-modified silicone resin coating material (1)
which was used for forming the first coating layer.
Pigment 1: White pigment (manufactured by Ishihara Sangyo Co.,
Ltd.) P.W.C.40
Pigment 2: Yellow pigment (manufactured by Dainichi Seika Co.,
Ltd.) P.W.C.40
Pigment 3: Black pigment (manufactured by Dainichi Seika Co., Ltd.)
P.W.C.40
P.W.C.: Pigment Weight Concentration (Weight % in the solid
content)
Examples 14 to 16
Examples of Colored Coating
Functional coated products (14) to (16) were obtained in the same
manner as in Example 8, except that the first coating layer was
formed with enamel obtained by adding the above-mentioned pigments
(1) to (3) to the acryl-modified silicone resin coating material
(1), instead of the acryl-modified silicone resin coating material
(1) which was used for forming the first coating layer.
Concerning the functional coated products (11) to (16), the
evaluation on coating properties and deterioration of the substrate
and the coating were conducted according to the above-mentioned
method.
The results thereof were shown in Table 4. As shown in this table,
there was no problem concerning the coating properties and the
deterioration of the substrate and the coating, even if the first
coating layer was coated by means of enamel coating.
Example 17
A functional coated product (17) was obtained in the same manner as
in Example 3, except that the thickness of the cured coating of the
second coating layer was changed to 0.1 .mu.m.
Example 18
A functional coated product (18) was obtained in the same manner as
in Example 8, except that the thickness of the cured coating of the
second coating layer was changed to 0.1 .mu.m.
Comparative Example 7
A comparative coated product (7) was obtained in the same manner as
in Comparative Example 1, except that the thickness of the second
coating layer was changed to 0.1 .mu.m.
Concerning the functional coated products (17), (18) and
comparative coated product (7), the evaluation on coating
properties and deterioration of the substrate and the coating were
conducted according to the above-mentioned method.
The results thereof were shown in Table 5. As shown in this table,
the cured coating of the functional coating material containing the
photocatalyst of the functional coated products (17) and (18) had a
contact angle of a few degrees, after the irradiation of
ultraviolet light to show high wettability, in spite of a small
layer thickness. On the other hand, the coating of Comparative
coated product (7), in which a silicone coating material containing
no photocatalyst was used, did not show this performance.
Example 19
A functional coated product (19) was obtained in the same manner as
in Example 3, except that the acryl-modified silicone resin coating
material (2), which was obtained in Preparation Example 4, was used
instead of the acryl-modified silicone coating resin material
(1).
Example 20
A functional coated product (20) was obtained in the same manner as
in Example 3, except that the acryl-modified silicone resin coating
material (3), which was obtained in Preparation Example 5, was used
instead of the acryl-modified silicone coating resin material
(1).
Concerning the functional coated products (19) and (20), the
evaluation on coating properties and deterioration of the substrate
and the coating were conducted according to the above-mentioned
method.
The results thereof were shown in Table 6. As shown in this table,
there was no problem concerning adhesion properties between the
substrate and the first coating layer end those between the first
coating layer and the second coating layer. There was no problem
concerning other performance, either.
Example 21
A functional coated product (21) was obtained in the same manner as
in Example 3, except that a PVC plate having the same size as that
of the PC plate was used as a substrate.
Example 22
A functional coated product (22) was obtained in the same manner as
in Example 8, except that a PVC plate having the same size as that
of the PC plate was used as a substrate.
Comparative Example 8
A comparative coated product (8) was obtained in the same manner as
in Example 3, except that a PVC plate having the same size as that
of the PC plate was used as a substrate and that the functional
coating material (1-3) was directly applied to the surface of this
PVC plate without using the acryl-modified silicone resin coating
material.
Example 23
A functional coated product (23) was obtained in the same manner as
in Example 3, except that a plate coated with an organic substance
having the same size as that of the PC plate (in which an acrylic
coating PERMALOCK (manufactured by Rock Paint Co.) was applied in a
thickness of 10 .mu.m to an inorganic substrate made of a stainless
steel plate) was used as a substrate.
Example 24
A functional coated product (24) was obtained in the same manner as
in Example 8, except that a plate coated with an organic substance
having the same size as that of the PC plate (in which an acryl
coating PERMALOCK (manufactured by Rock Paint Co.) was applied in a
thickness of 10 .mu.m to an inorganic substrate made of a stainless
steel plate) was used as a substrate.
Comparative Example 9
A comparative coated product (9) was obtained in the same manner as
in Example 3, except that a plate coated with an organic substance
having the same size as that of the PC plate (in which an acrylic
coating PERMALOCK (manufactured by Rock Paint Co.) was applied in a
thickness of 10 .mu.m to an inorganic substrate made of a stainless
steel plate) was used as a substrate and that the functional
coating material (1-3) was directly applied to the surface of this
plate coated with the organic substance and curing was
conducted.
Concerning the functional coated products (21) to (24) and
comparative coated products (8) and (9), the evaluation on coating
properties and deterioration of the substrate and the coating were
conducted according to the above-mentioned method.
The results thereof were shown in Table 7. As shown in this table,
the functional coated products (21) to (24) in Examples, in which
the first coating layer was formed with the cured coating of the
acryl-modified coating material, showed no problem in adhesion
properties, and the deterioration of the substrate and the coating
was not observed. Also, other performance was good. On the other
hand, the coparative coated products (8) and (9) in Comparative
Examples showed poor adhesion properties, further, the
deterioration of the substrate due to the photocatalyst was
observed.
Example 25
A functional coated product (25) was obtained in the same manner as
in Example 3, except that a stainless steel plate having the same
size as that of the PC plate was used as a substrate.
Example 26
A functional coated product (26) was obtained in the same manner as
in Example 8, except that a stainless steel plate having the same
size as that of the PC plate was used as a substrate.
Comparative Example 10
A comparative coated product (10) was obtained in the same manner
as in Example 3, except that a stainless steel plate having the
same size as that of the PC plate was used as a substrate and that
the functional coating material (1-3) was directly applied to the
surface of this stainless steel plate without applying the
acryl-modified silicone resin coating material and the curing was
conducted.
Concerning the functional coated products (25) and (26) and
Comparative coated product (10), the evaluation on coating
properties and deterioration of the substrate and the coating were
conducted according to the above-mentioned method.
The results thereof were shown in Table 8. As shown in this table,
there was no problem concerning the deterioration of the substrate
because an inorganic substrate was used in every coated product.
However, the comparative coated product (10) was poor in adhesion
properties, because the first coating layer made of a cured coating
of the acryl-modified silicone resin coating material was not
formed.
Example 27
A functional coated product (27) was obtained in the same manner as
in Example 3, except that a glass plate having the same size as
that of the PC plate was used as a substrate.
Example 28
A functional coated product (28) was obtained in the same manner as
in Example 8, except that a glass plate having the same size as
that of the PC plate was used as a substrate.
Example 29
A functional coated product (29) was obtained in the same manner as
in Example 3, except that a tile having the same size as that of
the PC plate was used as a substrate.
Example 30
A functional coated product (30) was obtained in the same manner as
in Example 8, except that a tile having the same size as that of
the PC plate was used as a substrate.
Example 31
A functional coated product (31) was obtained in the same manner as
in Example 3, except that an enamel plate having the same size as
that of the PC plate was used as a substrate.
Example 32
A functional coated product (32) was obtained in the same manner as
in Example 8, except that an enamel plate having the same size as
that of the PC plate was used as a substrate.
Concerning the functional coated products (27) to (32), the
evaluation on coating properties and deterioration of the substrate
and the coating were conducted according to the above-mentioned
method.
The results thereof were shown in Tables 8 and 9. As shown in these
tables, there was no problem concerning the deterioration of the
substrate because an inorganic substrate was used in every coated
product. Also, there was no problem concerning other
performance.
Comparative Example 11
A comparative coated product (11) was obtained in the same manner
as in Example 3, except that the acryl-modified silicone resin
coating material (1), which was applied to the surface of the PC
plate, was baked at 150.degree. C. for 30 minutes to conduct
complete curing (the ratio of the cured acryl-modified silicone
resin coating material was 100% by weight, which was obtained in
the same manner as in Example 3), and then the functional coating
material (1-3) was applied to the surface thereof.
However, the coating of the functional coating material (1-3) could
not be formed because the functional coating material (1-3) on the
completely cured layer was repelled.
Comparative Example 12
A comparative coated product (12) was obtained in the same manner
as in Example 3, except that the acryl-modified silicone resin
coating material (1), which was applied to the surface of the PC
plate, was left to stand for 10 minutes at room temperature and
then the functional coating material (1-3) was applied to the
surface thereof, while the applied acryl-modified silicone resin
coating material (1) was in a wet condition.
Concerning the comparative functional coated product (12), the
evaluation on coating properties and deterioration of the substrate
and the coating were conducted according to the above-mentioned
method.
The results thereof were shown in Table 10. As shown in this table,
sufficient adhesion properties were not obtained between the
substrate and the first coating layer.
Examples 33 to 37
Functional coated products (33) to (37) were obtained in the same
manner as in Example 3, except that a tile having the same size as
that of the PC plate was used as a substrate and that the first
coating layer was formed with acryl-modified silicone resin coating
materials (4) to (8) instead of the acryl-modified silicone resin
coating material (1).
Example 38
A functional coated product (38) was obtained in the same manner as
in Example 8, except that a tile having the same size as that of
the PC plate was used as a substrate and that the first coating
layer was formed with an acryl-modified silicone resin coating
material (9) instead of the acryl-modified silicone resin coating
material (1).
Comparative Example 13
A comparative coated product (13) was obtained in the same manner
as in Example 8, except that a tile having the same size as that of
the PC plate was used as a substrate, that the first coating layer
was formed with a commercially available epoxy-type primer (EPORO Z
PRIMER, manufactured by ISAMU PAINT CO.) instead of the
acryl-modified silicone resin coating material (1), and that the
thickness of the cured coating of the first coating layer was
changed to 8 .mu.m.
Comparative Example 14
A comparative coated product (14) was obtained in the same manner
as in Example 8, except that a tile having the same size as that of
the PC plate was used as a substrate, that the first coating layer
was formed with an acryl-modified silicone resin coating material
(7) instead of the acryl-modified silicone resin coating material
(1), and that the second coating layer was formed with the
comparative coating material (1) instead of the functional coating
material (2-3).
In order to study the durability of the coating and the influence
on the first coating layer due to the photocatalytic ability, the
following accelerated weathering evaluation was conducted with the
above-mentioned Sunshine Weatherometer, as for the functional
coated products (29), (30), (33) to (38) and comparative coated
products (13) and (14). Further, the reason why the tile was used
as a substrate of the coated product was because the tile has less
weathering deterioration. Therefore, it is possible to examine the
durability of the coating itself clearly.
The test time was 4,000 hours, and the adhesion properties and
degree of discoloration of the coating was examined. Further, the
adhesion properties and degree of discoloration of the coating was
also examined halfway, 2,500 hours after the test.
The adhesion properties were examined according to the
above-mentioned method.
The degree of discoloration was conducted according to the color
difference (.DELTA.E) prescribed in JIS-Z8730. In general, it is
said that a person's eye can confirm the discoloration when
.DELTA.E is 3 or more. Further, it is said that the irradiation for
4,000 hours by the Sunshine Weatherometer corresponds to exposure
outdoors for 10 years.
Evaluation results are shown in Tables 11 and 12.
As shown in Tables 11 and 12, concerning the functional coated
products (29), (30) and (33) to (38), the discoloration was more
serious, particularly after 4,000 hours, when the ratio of
Component (D) was increased. However, it does not seem to cause any
problems on the practical use, except for the case where high
durability is required. Particularly, in the functional coated
product (36) in Example 36, poor adhesion occurred in some parts
between the first coating layer and the second coating layer 4,000
hours later. However, the deterioration was not observed 2,500
hours later.
Further, the comparative coated product (13), in which the
commercially available epoxy-type primer was used, showed
remarkable deterioration in the coating performance. Concerning the
coated product in Comparative Example 14, the degree of
discoloration of the coating was reduced though the first coating
layer was formed from the same material as that of the functional
coated product (36) in Example 36, because the photocatalyst was
not contained in the second coating layer.
Example 39
EPORO E PRIMER (manufactured by ISAMU PAINT, CO.) was applied to
about 5 m.sup.2 of a concrete side wall (no coated) of a path in
the premise of the head office of Matsushita Electric Works, Ltd.
(Kadoma, Osaka) as a prime coat, in order to prevent the elution of
an alkaline component in the concrete, under predetermined
conditions. After drying for 24 hours, colored coating was
conducted with the pigment-containing acryl-modified silicone resin
coating material prepared in Example 11, so that the thickness of
the cured coating was about 30 .mu.m. After it was left to stand
for 5 hours at room temperature, it was confirmed that the cured
coating was a semi-cured condition. Then, the functional coating
material (2-3) prepared in Preparation Example 2-3 was applied
thereto so that the thickness of the cured coating was about 0.5
.mu.m. All the coating was conducted using a hand roller.
After exposure for about 3 months, there was no dirt on the coated
side wall and it maintained the condition in the beginning of the
coating.
Example 40
An acryl-modified coating material (1) prepared in Preparation
Example 3 was applied to a road traffic sign ((width) 600
mm.times.(length) 350 mm, an one-way sign) and a pole in the
premise of the head office of Matsushita Electric Works, Ltd.
(Kadoma, Osaka), after wiping off the dirt with ethanol, so that
the thickness of the cured coating was about 5 .mu.m. After it was
left to stand for 5 hours at room temperature, it was confirmed
that the cured coating was a semi-cured condition. Then, the
functional coating material (1-3) prepared in Preparation Example
1-3 was applied thereto so that the thickness of the cured coating
was about 0.5 .mu.m. All the coating was conducted by means of
brushing.
After exposure for about 3 months, there was no dirt on the coated
side wall and it maintained the condition in the beginning of the
coating.
Example 41
The first coating layer and the second coating layer were formed on
a reflective tape for a road traffic sign (manufactured by Sumitomo
3M Co.) and on a post cone for a road (manufactured by Nippon
Mectron Co.) in the same manner as in Example 3. The reflective
tape was pasted on the post cone, followed by exposure for about 3
months at the side of the road in the premise of the head office of
Matsushita Electric Works, Ltd. (Kadoma, Osaka). There was no dirt
on the post cone and it maintained the condition in the beginning
of the coating.
Example 42
The acryl-modified silicone resin coating material (1) prepared in
Example 3 was applied to an outer wall (about 10 m.sup.2) of the
main building in the premise of the head office of Matsushita
Electric Works, Ltd. (Kadoma, Osaka), so that the thickness of the
cured coating was about 8 .mu.m. After it was left to stand for 4
hours at room temperature, it was confirmed that the cured coating
was a semi-cured condition. Then, the functional coating material
(1-3) prepared in Preparation Example 1-3 was applied thereto so
that the thickness of the cured coating was about 0.5 .mu.m. All
the coating was conducted using a hand roller. After exposure for
about 3 months, there was no dirt on the coated building and it
maintained the condition in the beginning of the coating.
Example 43
The acryl-modified coating material (1) prepared in Preparation
Example 3 was applied to a glass having a size of 1 m.sup.2 (a
thickness of 6 mm) of the research laboratory (east side, the
second floor) in the premise of the head office of Matsushita
Electric Works, Ltd., after wiping off the dirt with ethanol, so
that the thickness of the cured coating was about 1 .mu.m. After it
was left to stand for 2 hours at room temperature, it was confirmed
that the cured coating was a semi-cured condition. Then, the
functional coating material (2-3) prepared in Preparation Example
2-3 was applied thereto so that the thickness of the cured coating
was about 0.5 .mu.m. All the coating was conducted by means of flow
coating.
After exposure for about 3 months, there was no dirt on the coated
building and it maintained the condition in the beginning of the
coating.
Example 44
The acryl-modified coating material (1) prepared in Preparation
Example 3 was applied to the whole apparatus of the road light
(YA32020 for sidewalk, manufactured by Matsushita Electric Works,
Ltd.) including front glass, a pole, an outer surface of a
reflective plate, etc., in the premise of the head office of
Matsushita Electric Works, Ltd., after wiping off the dirt with
ethanol, so that the thickness of the cured coating was about 1
.mu.m. After it was left to stand for 2 hours at room temperature,
it was confirmed that the cured coating was a semi-cured condition.
Then, the functional coating material (1-3) prepared in Preparation
Example 1-3 was applied thereto so that the thickness of the cured
coating was about 0.5 .mu.m. All the coating was conducted with a
sponge roller.
After exposure for about 3 months, there was no dirt on the coated
front glass, the pole, the reflective plate, etc. and it maintained
the condition in the beginning of the coating.
Example 45
The acryl-modified coating material (1) prepared in Preparation
Example 3 was applied to an auto body (TOFOTA SPRINTER, the 1990
model), after wiping off the dirt with ethanol, so that the
thickness of the cured coating was about 1 .mu.m. After it was left
to stand for 2 hours at room temperature, it was confirmed that the
cured coating was a semi-cured condition. Then, the functional
coating material (1-3) prepared in Preparation Example 1-3 was
applied thereto so that the thickness of the cured coating was
about 0.5 .mu.m. All the coating was conducted with a sponge
roller.
After exposure for about 3 months, there was no dirt on the coated
auto body and it maintained the condition in the beginning of the
coating.
Example 46
EPORO E PRIMER (manufactured by ISAMU PAINT, CO.) was applied to a
cement-type facing material (manufactured by Matsushita Electric
Works, Ltd., a multi-sizing brick tile pattern) as a prime coat, in
order to prevent the elution of an alkaline component, under
predetermined conditions. After drying for 24 hours, colored
coating was conducted with the pigment-containing acryl-modified
silicone resin coating material prepared in Example 11, so that the
thickness of the cured coating was about 30 .mu.m. After it was
left to stand for 5 hours at room temperature, it was confirmed
that the cured coating was a semi-cured condition. Then, the
functional coating material (2-3) prepared in Preparation Example
2-3 was applied thereto so that the thickness of the cured coating
was about 0.5 .mu.m. All the coating was conducted by means of
airless spray.
After exposure for about 3 months, there was no dirt on the facing
material and it maintained the condition in the beginning of the
coating.
Example 47
Half of the area of a reflective plate (a steel plate coated with
white melamine) for a Fuji-type fluorescent lighting apparatus
(20W), (FA22063 manufactured by Matsushita Electric Works, Ltd.),
was applied in the same manner as in Example 3, except that the
second coating layer was dried at 90.degree. C. for 15 minutes. All
the coating was conducted by means of airless spray. The
fluorescent lighting apparatus, including the reflective plate
coated in that way, was equipped in the cookery of the internal
cafeteria in the premise of the head office of Matsushita Electric
Works, Ltd. (Kadoma, Osaka), and it was observed. About three
months later, the coated portion had less dirt compared with the
other portion.
Example 48
EPORO E PRIMER (manufactured by ISAMU PAINT, CO.) was applied to
about 1 m.sup.2 of a concrete electric-light pole (no coated) in
the premise of the head office of Matsushita Electric Works, Ltd.
(Kadoma, Osaka) as a prime coat, in order to prevent the elution of
an alkaline component in the concrete, under predetermined
conditions. After drying for 24 hours, colored coating was
conducted with the pigment-containing acryl-modified silicone resin
coating material prepared in Example 11, so that the thickness of
the cured coating was about 30 .mu.m. After it was left to stand
for 5 hours at room temperature, it was confirmed that the cured
coating was a semi-cured condition. Then, the functional coating
material (1-3) prepared in Preparation Example (1-3) was applied
thereto, so that the thickness of the cured coating was about 0.5
.mu.m. All the coating was conducted using a hand roller.
After exposure for about 3 months, there was no dirt on the coated
electric-light pole and it maintained the condition in the
beginning of the coating.
Example 49
The acryl-modified silicone resin coating material (1) prepared in
preparation Example 3 was applied to a protection fence (a
galvanized steel plate) in the premise of the head office of
Matsushita Electric Works, Ltd. (Kadoma, Osaka), after wiping off
the dirt with ethanol, so that the thickness of the cured coating
was about 1 .mu.m. After it was left to stand for one hour at room
temperature, it was confirmed that the cured coating was a
semi-cured condition. Then, the functional coating material (1-3)
prepared in Preparation Example (1-3) was applied thereto, so that
the thickness of the cured coating was about 0.5 .mu.m. All the
coating was conducted using a hand roller.
After exposure for about 3 months, there was no dirt on the coated
protection fence and it maintained the condition in the beginning
of the coating.
TABLE 1 Comp. Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 1 Coated product
Func.*.sup.1 (1) Func. (2) Func. (3) Func. (4) Func. (5)
Comp.*.sup.2 (1) Substrate PC plate PC plate PC plate PC plate PC
plate PC plate First coating layer Coating Acryl- Acryl- Acryl-
Acryl- Acryl- Acryl- material Modified modified modified modified
modified modified Silicone silicone silicone silicone silicone
silicone Resin (1) resin (1) resin (1) resin (1) resin (1) resin
(1) Coating 1 1 1 1 1 1 thickness (.mu.m) Second coating layer
Coating Func. Func. Func. Func. Func. Comp. material (1-1) (1-2)
(1-3) (1-4) (1-5) (1) Resin solid content/ 80/20 60/40 50/50 40/60
20/80 100/0 photocatalyst (weight ratio) Coating Thickness (.mu.m)
0.5 0.5 0.5 0.5 0.5 0.5 Photocatalytic action 10 40 47 56 79 0
Adhesion properties Between substrate and 100/100 100/100 100/100
100/100 100/100 100/100 first coating layer Between first coating
100/100 100/100 100/100 100/100 100/100 100/100 layer and second
coating layer Hardness Contact Angle 5 H 4 H 4 H 3 H 2 H 6 H
Initial stage 75.degree. 73.degree. 72.degree. 60.degree.
50.degree. 75.degree. After UV irradiation <10.degree.
<10.degree. <10.degree. <10.degree. <10.degree.
75.degree. Deterioration of coating None None None None None None
Deterioration of substrate None None None None None None *.sup.1
Func.: Functional (same below) *.sup.2 Comp.: Comparative (same
below)
TABLE 2 Comp. Ex. 6 Ex. 7 Ex. 8 Ex. 9 Ex. 10 Ex. 2 Coated product
Func. (6) Func. (7) Func. (8) Func. (9) Func. (10) Comp. (2)
Substrate PC plate PC plate PC plate PC plate PC plate PC plate
First coating layer Coating Acryl- Acryl- Acryl- Acryl- Acryl-
Acryl- material modified modified modified modified modified
modified silicone silicone silicone silicone silicone silicone
resin (1) resin (1) resin (1) resin (1) resin (1) resin (1) Coating
1 1 1 1 1 1 thickness (.mu.m) Second coating layer Coating Func.
Func. Func. Func. Func. Comp. material (2-1) (2-2) (2-3) (2-4)
(2-5) (2) Resin solid content/ 80/20 60/40 50/50 40/60 20/80 100/0
photocatalyst (weight ratio) Coating thickness (.mu.m) 0.5 0.5 0.5
0.5 0.5 0.5 Photocatalytic action 8 36 44 55 72 0 Adhesion
properties Between substrate and 100/100 100/100 100/100 100/100
100/100 100/100 first coating layer Between first coating 100/100
100/100 100/100 100/100 100/100 100/100 layer and second coating
layer Hardness Contact Angle 4 H 4 H 4 H 3 H 2 H 5 H Initial stage
80.degree. 78.degree. 78.degree. 74.degree. 65.degree. 80.degree.
After UV irradiation <10.degree. <10.degree. <10.degree.
<10.degree. <10.degree. 80.degree. Deterioration of coating
None None None None None None Deterioration of substrate None None
None None None None
TABLE 3 Comp. Comp. Comp. Comp. Ex. 3 Ex. 4 Ex. 5 Ex. 6 Coated
product Comp. (3) Comp. (4) Comp. (5) Comp. (6) Substrate PC plate
PC plate PC plate PC plate First coating layer Coating Acryl- Comp.
(3) -- -- material modified silicone resin (1) Coating 1 1 -- --
thickness (.mu.m) Second coating layer Coating Titanium Func. Func.
Comp. material oxide (1-3) (1-3) (1) Resin solid content/ -- 50/50
50/50 100/0 photocatalyst (weight ratio) Coating thickness (.mu.m)
0.5 0.5 0.5 0.5 Photocatalytic action 100 48 48 0 Adhesion
properties Between substrate and 100/100 50/100 -- -- first coating
layer Between first coating 20/100 98/100 -- -- layer and second
coating layer Between substrate and -- -- 30/100 40/100 second
coating layer Hardness Contact Angle <2 B 4 H 4 H 6 H Initial
stage 49.degree. 71.degree. 72.degree. 76.degree. After UV
irradiation <10.degree. <10.degree. <10.degree. 75.degree.
Deterioration of coating None None None None Deterioration of
substrate Some None None None (Discolor- ation)
TABLE 4 Ex. 11 Ex. 12 Ex. 13 Ex. 14 Ex. 15 Ex. 16 Coated product
Func. (11) Func. (12) Func. (13) Func. (14) Func. (15) Func. (16)
Substrate PC plate PC plate PC plate PC plate PC plate PC plate
First coating layer Coating Acryl- Acryl- Acryl- Acryl- Acryl-
Acryl- material modified modified modified modified modified
modified silicone silicone silicone silicone silicone silicone
resin (1) + resin (1) + resin (1) + resin (1) + resin (1) + resin
(1) + Pigment Pigment Pigment Pigment Pigment Pigment 1 2 3 1 2 3
Coating thickness (.mu.m) 1 1 1 1 1 1 Second coating layer Coating
Func. Func. Func. Func. Func. Func. material (1-3) (1-3) (1-3)
(2-3) (2-3) (2-3) Resin solid content/ 50/50 50/50 50/50 50/50
50/50 50/50 photocatalyst (weight ratio) Coating thickness (.mu.m)
0.5 0.5 0.5 0.5 0.5 0.5 Photocatalytic action 47 49 47 44 46 47
Adhesion properties Between substrate and 100/100 100/100 100/100
100/100 100/100 100/100 first coating layer Between first coating
100/100 100/100 100/100 100/100 100/100 100/100 layer and second
coating layer Hardness Contact Angle 4 H 4 H 4 H 4 H 4 H 4 H
Initial stage 70.degree. 71.degree. 71.degree. 78.degree.
78.degree. 78.degree. After UV irradiation <10.degree.
<10.degree. <10.degree. <10.degree. <10.degree.
<10.degree. Deterioration of coating None None None None None
None Deterioration of substrate None None None None None None
TABLE 5 Ex. 17 Ex. 18 Comp. Ex. 7 Coated product Func. (17) Func.
(18) Comp. (7) Substrate PC plate PC plate PC plate First coating
layer Coating Acryl- Acryl- Acryl- material modified modified
modified silicone silicone silicone resin (1) resin (1) resin (1)
Coating thickness (.mu.m) 1 1 1 Second coating layer Coating Func.
Func. Comp. material (1-3) (2-3) (1) Resin solid content/ 50/50
50/50 100/0 photocatalyst (weight ratio) Coating thickness (.mu.m)
0.1 0.1 0.1 Photocatalytic action 33 30 0 Adhesion properties
Between substrate and 100/100 100/100 100/100 first coating layer
Between first coating 100/100 100/100 100/100 layer and second
coating layer Hardness Contact Angle 4 H 4 H 5 H Initial stage
74.degree. 78.degree. 75.degree. After UV irradiation
<10.degree. <10.degree. 75.degree. Deterioration of coating
None None None Deterioration of substrate None None None
TABLE 6 Ex. 19 Ex. 20 Coated product Func. (19) Func. (20)
Substrate PC plate PC plate First coating layer Coating
Acryl-modified Acryl-modified material silicone silicone resin (2)
resin (3) Coating thickness (.mu.m) 1 1 Second coating layer
Coating Func. Func. material (1-3) (2-3) Resin solid content/ 50/50
50/50 photocatalyst (weight ratio) Coating thickness (.mu.m) 0.5
0.5 Photocatalytic action 48 46 Adhesion properties Between
substrate and 100/100 100/100 first coating layer Between first
coating 100/100 100/100 layer and second coating layer Hardness
Contact Angle 4 H 4 H Initial stage 70.degree. 79.degree. After UV
irradiation <10.degree. <10.degree. Deterioration of coating
None None Deterioration of substrate None None
TABLE 7 Comp. Comp. Ex. 21 Ex. 22 Ex. 8 Ex. 23 Ex. 24 Ex. 9 Coated
product Func. (21) Func. (22) Comp. (8) Func. (23) Func. (24) Comp.
(9) Substrate PVC plate PVC plate PVC plate Organic- Organic-
Organic- coated coated coated First coating layer Coating Acryl-
Acryl- -- Acryl- Acryl- -- material modified modified modified
modified silicone silicone silicone silicone resin (1) resin (1)
resin (1) resin (1) Coating thickness (.mu.m) 1 1 -- 1 1 -- Second
coating layer Coating Func. Func. Func. Func. Func. Func. material
(1-3) (2-3) (1-3) (1-3) (2-3) (1-3) Resin solid content/ 50/50
50/50 50/50 50/50 50/50 50/50 photocatalyst (weight ratio) Coating
thickness (.mu.m) 0.5 0.5 0.5 0.5 0.5 0.5 Photocatalytic action 49
47 48 48 46 48 Adhesion properties Between substrate and 100/100
100/100 -- 100/100 100/100 -- first coating layer Between first
coating 100/100 100/100 -- 100/100 100/100 -- layer and second
coating layer Between substrate and -- -- 25/100 -- -- 30/100
second coating layer Hardness Contact Angle 4 H 4 H 4 H 4 H 4 H 3 H
Initial stage 70.degree. 80.degree. 72.degree. 72.degree.
78.degree. 72.degree. After UV irradiation <10.degree.
<10.degree. <10.degree. <10.degree. <10.degree.
<10.degree. Deterioration of coating None None None None None
None Deterioration of substrate None None None None None None
TABLE 8 Comp. Ex. 25 Ex. 26 Ex. 10 Ex. 27 Ex. 28 Coated pro- Func.
(25) Func. (26) Comp. Func. (27) Func. (28) duct Sub- Stainless
Stainless (10) Glass Glass strate plate plate Stainless plate plate
plate First coating layer Coating Acryl- Acryl- -- Acryl- Acryl-
material modified modified modified modified silicone silicone
silicone silicone resin (1) resin (1) resin (1) resin (1) Coating 1
1 -- 1 1 thickness (.mu.m) Second coat- ing layer Coating Func.
Func. Func. Func. Func. material (1-3) (2-3) (1-3) (1-3) (2-3)
Resin solid 50/50 50/50 50/50 50/50 50/50 content/ photocatalyst
(weight ratio) Coating 0.5 0.5 0.5 0.5 0.5 thickness (.mu.m)
Photocataly- 47 47 45 47 46 tic action Adhesion properties Between
100/100 100/100 -- 100/100 100/100 substrate and first coating
layer Between 100/100 100/100 -- 100/100 100/100 first coating
layer and second coat- ing layer Between -- -- 30/100 -- --
substrate and second coat- ing layer Hardness 4 H 4 H 4 H 4 H 4 H
Contact Angle Initial stage 69.degree. 78.degree. 70.degree.
78.degree. 79.degree. After UV <10.degree. <10.degree.
<10.degree. <10.degree. <10.degree. irradiation
Deterioration None None None None None of coating Deterioration
None None None None None of substrate
TABLE 9 Ex. 29 Ex. 30 Ex. 31 Ex. 32 Coated product Func. (29) Func.
(30) Func. (31) Func. (32) Substrate Tile Tile Enamel Enamel plate
plate First coating layer Coating Acryl- Acryl- Acryl- Acryl-
material modified modified modified modified silicone silicone
silicone silicone resin (1) resin (1) resin (1) resin (1) Coating
thickness (.mu.m) 1 1 1 1 Second coating layer Coating Func. Func.
Func. Func. material (1-3) (2-3) (1-3) (2-3) Resin solid content/
50/50 50/50 50/50 50/50 photocatalyst (weight ratio) Coating
thickness (.mu.m) 0.5 0.5 0.5 0.5 photocatalytic action 46 46 46 48
Adhesion properties Between substrate and 100/100 100/100 100/100
100/100 first coating layer Between first coating 100/100 100/100
100/100 100/100 layer and second coating layer Between substrate
and -- -- -- -- second coating layer Hardness Contact Angle 4 H 4 H
4 H 4 H Initial stage 70.degree. 80.degree. 79.degree. 79.degree.
After UV irradiation <10.degree. <10.degree. <10.degree.
<10.degree. Deterioration of coating None None None None
Deterioration of substrate None None None None
TABLE 10 Comp. Ex. 11 Comp. Ex. 12 Coated product Comp. (11) Comp.
(12) Substrate PC plate PC plate First coating layer Coating Acryl-
Acryl- material modified modified silicone silicone resin (1)*1
resin (1)*2 Coating thickness (.mu.m) 1 1 Second coating layer
Coating Func. Func. material (1-3) (1-3) Resin solid content/ 50/50
50/50 photocatalyst (weight ratio) Coating thickness (.mu.m) 0.5
Photocatalytic action Impossible 44 to form second coating layer
Adhesion properties Between substrate and 80/100 first coating
layer Between first coating 100/100 layer and second coating layer
Hardness Contact Angle 3 H Initial stage 72.degree. After UV
irradiation <10.degree. Deterioration of coating Impossible to
None form second coating layer Deterioration of substrate None *1:
After application, baked at 150.degree. C. for 30 minutes. *2:
After application, left to stand at room temperature for 10
minutes.
TABLE 11 Ex. 29 Ex. 30 Ex. 33 Ex. 34 Ex. 35 Ex. 36 Coated product
Func. (29) Func. (30) Func. (33) Func. (34) Func. (35) Func. (36)
substrate Tile Tile Tile Tile Tile Tile First coating layer Coating
material Acryl- Acryl- Acryl- Acryl- Acryl- Acryl- modified
modified modified modified modified modified silicone silicone
silicone silicone silicone silicone resin (1) resin (1) resin (4)
resin (5) resin (6) resin Coating thickness (.mu.m) 1 1 1 1 1 1
Second coating layer Coating material Func. Func. Func. Func. Func.
Func. (1-1) (2-3) (1-3) (1-3) (1-3) (1-3) Resin solid content/
50/50 50/50 50/50 50/50 50/50 50/50 photocatalyst (weight ratio)
Coating thickness (.mu.m) 0.5 0.5 0.5 0.5 0.5 0.5 Photocatalytic
action 46 46 46 46 46 46 Evaulation of accelerated weathering test
Adhesion properties Between substrate and first coating layer 2,500
hrs. 100/100 100/100 100/100 100/100 100/100 100/100 4,000 hrs.
100/100 100/100 100/100 100/100 100/100 100/100 Between first
coating layer and second coating layer 2,500 hrs. 100/100 100/100
100/100 100/100 100/100 100/100 4,000 hrs. 100/100 100/100 100/100
100/100 100/100 90/100 Discoloration degree .DELTA. 2,500 hrs. 0.2
0.3 1.8 0.6 3.0 3.5 4,000 hrs. 0.5 0.6 5.5 1.0 8.0 10.5
TABLE 12 Comp. Comp. Ex. 37 Ex. 38 Ex. 13 Ex. 14 Coated product
Func. (37) Func. (38) Comp. (13) Comp. substrate Tile Tile Tile
(14) Tile First coating layer Coating material Acryl- Acryl-
Commercially Acryl- modified modified available modified silicone
silicone expoxy type silicone resin (8) resin (9) primer resin (7)
Coating thickness 1 1 8 1 (.mu.m) Second coating layer Coating
material Func. Func. Func. Comp. (1-1) (2-3) (2-3) (1) Resin solid
con- 50/50 50/50 50/50 100/0 tent/photocatalyst (weight ratio)
Coating thickness 0.5 0.5 0.5 0.5 (.mu.m) Photocatalytic 46 46 46 0
action Evaulation of accelerated weather- ing test Adhesion
properties Between substrate and first coating layer 2,500 hrs.
100/100 100/100 100/100 100/100 4,000 hrs. 100/100 100/100 50/100
100/100 Between first coat- ing layer and second coating layer
2,500 hrs. 100/100 100/100 90/100 100/100 4,000 hrs. 100/100
100/100 20/100 100/100 Discoloration degree .DELTA. 2,500 hrs. 2.1
2.6 5.4 2.3 4,000 hrs. 6.0 7.0 30.0 5.7
EFFECT OF THE INVENTION
The functional coated product of the present invention is excellent
in adhesion properties of the coating to various substrates for
prime coat, and the deterioration of the substrate and the coating
due to photocatalytic action hardly occurs. Further, the smoothness
on the surface of the coating is high and therefore, it hardly has
dirt and also has high photocatalytic action.
In the functional coated product of the present invention, the
cured coating made of the acryl-modified silicone resin coating
material is interposed, as the first coating layer, between the
substrate and the cured coating made of the functional coating
material containing a photocatalyst, the substrate is not directly
influenced by the photocatalytic action, even if the substrate is
an organic substrate or a substrate coated with an organic
substance. Therefore, the deterioration of the substrate due to the
photocatalytic action hardly occurs. Further, by the interposition
of the first coating layer comprising the cured coating of the
above-mentioned acryl-modified silicone resin coating material, the
adhesion properties of the above-mentioned functional coating
material to the substrate is improved.
The functional coating material and an acryl-modified silicone
resin coating material to be used in the present invention are both
inorganic coating materials, therefore, the coating thereof is
hardly deteriorated even if it receives the photocatalytic
action.
When the functional coated product of the present invention is
irradiated by ultraviolet light, dirt such as water-repellant
organic substances is decomposed by the action of the photocatalyst
contained in the second coating layer, so that wettability of the
coating to water is improved, in addition to the effect of
decomposition and deodorization of organic substances, the
antifungal effect, the antimycotic effect, etc. This performance is
exhibited regardless of the thickness of the coating and the amount
of the photocatalyst contained therein. If the wettability of the
coating to water is high, a defrosting effect, an stainproof effect
due to washing action by rain-water in the outdoor use, etc. are
exhibited. Accordingly, the functional coated product of the
present invention also has other performance such as the prevention
of moisture condensation on the window glass, etc. in winter, or
the stainproof effect of architectural structure, road structure,
automobiles, vehicles, etc.
The functional coated product of the present invention shows
desirable performance, even if a pigment is dispersed into the
acryl-modified silicone resin coating material which forms the
first coating layer. Therefore, it is possible to color the coating
with an optional color.
In the functional coating material of the present invention, it is
possible to control coating properties such as photocatalytic
performance, hardness or surface conditions of the coating,
depending on the use, by changing the ratio of the amount of the
resin to that of the photocatalyst.
The coating material to be used for the functional coated product
of the present invention can be used under dry-curing conditions or
the temperature in the wide range, because it is possible to
conduct not only heat-curing but also cold curing. Therefore, it is
possible to apply a coating not only to a substrate having a
configuration which is not easily uniformly heated, a substrate
having a large size or a substrate having poor heat resistance,
etc., but also to a place where heating is not easily conducted,
for example, when coating operations are conducted outdoors.
Accordingly, its industrial value is high.
According to the production method of the present invention, the
application for forming the second coating layer is conducted while
the first coating layer is in a semi-cured condition. Therefore, it
is possible to conduct the coating process for a short period of
time, by selecting temperature conditions, etc. Thus, according to
the production method of the present invention, a functional coated
product having the above-mentioned excellent performance can be
obtained easily and effectively.
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