JP2006068685A - Laminated body having visible light-active photocatalyst layer and coating film of visible light-active photocatalyst - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated body which has a visible light-active photocatalyst layer having: a satisfactory photocatalytic action in an environment poor in light having a spectral component of <400 nm but rich in visible light, for example, in an indoor environment or in the inside of a car having UV-blocking glass; and excellent transparency, and the organic base material of which is prevented from being deteriorated. <P>SOLUTION: The laminated body is composed of an organic base material, an intermediate layer formed on the organic base material and the photocatalyst layer formed on the intermediate layer. The photocatalyst layer is formed from a visible light-active photocatalyst composition containing an oxide semiconductor (a) having visible light-active photocatalytic activity, a titanium compound (b) having a specified structure and a silane compound (c) having a specified structure. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a laminate having a visible light photocatalyst layer exhibiting a photocatalytic action by visible light, and more particularly to a laminate having an intermediate layer between an organic substrate and a visible light photocatalyst layer.

  Active research has been conducted on oxide semiconductors having visible light photocatalytic activity, and many oxide semiconductor fine particles exhibiting photocatalytic action with visible light have been proposed. Moreover, in order to immobilize the semiconductor fine particles at a relatively low temperature, a coating material using a siloxane resin as a binder is also provided, but the haze when the dry coating film is 0.1 μm exceeds 2, It is often inferior in transparency.

Patent Documents 1 and 2 propose photocatalytic coating compositions. Further, a cured body comprising a substrate, an undercoat layer formed on the substrate using the undercoat coating composition, and a photocatalyst layer formed on the undercoat layer using the photocatalyst coating composition, Proposed. However, when new semiconductor fine particles that have been specially treated to exhibit photocatalytic activity under visible light are used as photocatalyst fine particles, the surface characteristics of the semiconductor fine particles are different, and conventional coating compositions are thickened and gelled. In some cases, sufficient dispersion stability could not be ensured, and a transparent coating film having a haze of 2 or less when the dried coating film was 0.1 μm could not be obtained. In particular, when the content of semiconductor fine particles exhibiting a photocatalytic action with visible light exceeds 25% in the solid content, the decrease in transparency becomes significant, and a more transparent coating film has been demanded.
JP 2001-192616 A JP 2002-371234 A

  The present invention is intended to solve the problems associated with the prior art as described above, and is in an environment with a small amount of spectral components of less than 400 nm and a large amount of visible light, for example, in an indoor environment or a vehicle interior having an ultraviolet cut glass. An object of the present invention is to provide a laminate having a visible light photocatalyst layer exhibiting sufficient photocatalytic action and excellent in transparency, and further preventing deterioration of an organic base material.

The laminate according to the present invention is a laminate comprising an organic base material, an intermediate layer provided on the organic base material, and a photocatalyst layer provided on the intermediate layer,
The photocatalytic layer is
(A) an oxide semiconductor having visible light photocatalytic activity,
(B) The following formula (1)
R ¹ _m Ti (OR ² ) _4-m (1)
(In the formula, R ¹ represents an organic group having 1 to 8 carbon atoms, and when two or more exist, they may be the same or different, and R ² represents an alkyl group having 1 to 6 carbon atoms, It represents an organic group selected from the group consisting of an acyl group having 1 to 6 carbon atoms and a phenyl group, and when there are a plurality of them, they may be the same or different, and R ¹ and R ² are the same Or m may be an integer of 0 to 3)
And at least one titanium compound selected from the group consisting of a titanium acylate represented by the above formula (1) and a derivative thereof, and (c) the following formula (2)
R ³ _n Si (OR ⁴ ) _4-n (2)
(In the formula, R ³ represents a monovalent organic group having 1 to 8 carbon atoms, and when a plurality of R ³ are present, they may be the same or different, and R ⁴ has 1 to 5 carbon atoms. Represents an alkyl group or an acyl group having 1 to 6 carbon atoms, and when there are a plurality of them, they may be the same or different, and R ³ and R ⁴ may be the same or different; n is an integer of 0 to 3)
It is a layer formed from the visible light photocatalyst composition containing the at least 1 sort (s) of silane compound selected from the group which consists of the organosilane represented by these, and its derivative (s).

The visible light photocatalyst composition further has (d) a Si—O bond, a weight average molecular weight of 300 to 100,000, and a side chain and / or a terminal represented by the following formula (3):
_{^{- (R 5 O) p -}} (R 6 O) q -R 7 (3)
(Wherein R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 5 carbon atoms, R ⁷ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and p and q are p + q Is a number from 2 to 50)
It is preferable to contain the organosiloxane oligomer containing the structure represented by these.

The laminate according to the present invention is a laminate comprising an organic base material, an intermediate layer provided on the organic base material, and a photocatalyst layer provided on the intermediate layer,
The photocatalytic layer is
(A) an oxide semiconductor having visible light photocatalytic activity,
(B) The following formula (1)
R ¹ _m Ti (OR ² ) _4-m (1)
(In the formula, R ¹ represents an organic group having 1 to 8 carbon atoms, and when two or more exist, they may be the same or different, and R ² represents an alkyl group having 1 to 6 carbon atoms, It represents an organic group selected from the group consisting of an acyl group having 1 to 6 carbon atoms and a phenyl group, and when there are a plurality of them, they may be the same or different, and R ¹ and R ² are the same Or m may be an integer of 0 to 3)
And at least one titanium compound selected from the group consisting of a titanium alcoholate represented by the formula (1) and a titanium acylate represented by the formula (1) and a derivative thereof, and (d) a Si-O bond. Having a weight average molecular weight of 300 to 100,000, and having a side chain and / or a terminal represented by the following formula (3)
_{^{- (R 5 O) p -}} (R 6 O) q -R 7 (3)
(Wherein R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 5 carbon atoms, R ⁷ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and p and q are p + q Is a number from 2 to 50)
The layer formed from the visible light photocatalyst composition containing the organosiloxane oligomer containing the structure represented by these may be sufficient.

  The titanium compound (b) is at least one titanium selected from a titanium alcoholate condensate, a titanium alcoholate chelate condensate, a titanium acylate condensate, and a titanium acylate chelate condensate. A compound is preferred.

The oxide semiconductor (a) is preferably at least one oxide semiconductor selected from sulfur-doped titanium oxide and oxygen-deficient titanium oxide.
The intermediate layer has the following formula (2)
R ³ _n Si (OR ⁴ ) _4-n (2)
(In the formula, R ³ represents a monovalent organic group having 1 to 8 carbon atoms, and when a plurality of R ³ are present, they may be the same or different, and R ⁴ has 1 to 5 carbon atoms. Represents an alkyl group or an acyl group having 1 to 6 carbon atoms, and when there are a plurality of them, they may be the same or different, and R ³ and R ⁴ may be the same or different; n is an integer of 0 to 3)
For at least one silane compound selected from the group consisting of organosilanes and derivatives thereof, and a silyl group-containing polymer having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group A layer formed from the coating composition is preferred.

The visible light photocatalyst coating film according to the present invention is a film composed of the laminate, and the organic base material is a film having a thickness of 1000 μm or less.
The molded body according to the present invention has the visible light photocatalyst coating film on the surface thereof. Moreover, the molded object which concerns on this invention may consist of the said laminated body.

  According to the present invention, a photocatalyst layer that exhibits sufficient photocatalytic activity and has excellent transparency even in an environment with a small amount of spectral components of less than 400 nm and a large amount of visible light, for example, an indoor environment or a vehicle interior having an ultraviolet cut glass. Can be obtained. Moreover, the laminated body which has such a photocatalyst layer can be used conveniently for the wide use using photocatalytic performance, such as organic substance decomposition | disassembly.

<Visible light photocatalyst composition>
The visible light photocatalyst composition used in the present invention is:
(1) A composition containing an oxide semiconductor (a), a titanium compound (b), and a silane compound (c) (hereinafter also referred to as “first visible light photocatalyst composition”),
(2) a composition containing an oxide semiconductor (a), a titanium compound (b) and an organosiloxane oligomer (d) (hereinafter also referred to as “second visible light photocatalyst composition”), or (3) oxidation A composition containing a physical semiconductor (a), a titanium compound (b), a silane compound (c), and an organosiloxane oligomer (d) (hereinafter also referred to as “third visible light photocatalyst composition”).

  These visible light photocatalyst compositions have photocatalytic activity under irradiation with visible light of 400 nm or more. Moreover, the said visible light photocatalyst composition may contain the catalyst (f) for accelerating | stimulating the hydrolysis and condensation reaction of a silane compound (c) or an organosiloxane oligomer (d) as needed. Moreover, the stability improver (g), filler (h), and other additives may be contained.

Hereinafter, each component of the visible light photocatalyst composition used in the present invention will be described in detail.
(A) Oxide semiconductor having visible light photocatalytic activity:
The oxide semiconductor having visible light photocatalytic activity used in the present invention (hereinafter referred to as “oxide semiconductor (a)”) is particularly a metal oxide semiconductor that exhibits photocatalytic action under visible light irradiation of 400 nm or more. Without limitation, for example, oxide semiconductors such as titanium oxide, tin oxide, zinc oxide, strontium titanate, tungsten oxide, zirconium oxide, niobium oxide, iron oxide, copper oxide, iron titanate, nickel oxide, bismuth oxide, The thing which modified | denatured so that a photocatalytic action might be expressed with visible light is mentioned. Specific examples include brookite-type titanium oxide, ion-implanted titanium oxide, plasma-treated titanium oxide, oxygen-deficient titanium oxide, nitrogen-doped titanium oxide, and sulfur-doped titanium oxide.

Among these, at least one oxide semiconductor selected from sulfur-doped titanium oxide and oxygen-deficient titanium oxide is preferably used in that it has excellent photocatalytic activity under visible light irradiation. Such an oxide semiconductor (a) can be produced by a conventionally known method. For example, sulfur-doped titanium oxide is disclosed in JP 2004-143032 A, and oxygen-deficient titanium oxide is disclosed in JP 2001-2001. It can be produced by the method described in JP-A-212457.

  These oxide semiconductors (a) have an absorbance at 400 nm measured by diffuse reflection spectrum measurement of 0.05 or more, more preferably 0.07 or more, and particularly preferably 0.10 or more. The photocatalytic composition obtained by using the semiconductor (a) exhibits a photocatalytic effect effectively under visible light irradiation. The absorbance by the diffuse reflection spectrum measurement can be measured by, for example, a spectrophotometer V-570 manufactured by JASCO Corporation.

  The form of the oxide semiconductor (a) is not particularly limited. For example, the organic semiconductor system dispersed in a non-polar solvent such as powder, an aqueous sol or colloid dispersed in water, or a polar solvent such as alcohol or toluene. Examples include sol or colloid. When the oxide semiconductor (a) is an organic solvent-based sol or colloid, it may be further diluted with water or an organic solvent depending on its dispersibility, and the oxide semiconductor may be used to improve dispersibility. The surface of (a) may be treated. The form of the oxide semiconductor (a) is appropriately determined according to the desired properties of the coating film. When the oxide semiconductor (a) is in the form of sol or colloid, the solid content concentration is preferably more than 0% by weight and 40% by weight or less. The primary particle diameter of the oxide semiconductor (a) is preferably 200 nm or less, particularly preferably 100 nm or less. When the primary particle size exceeds 200 nm, the transparency is inferior, and the haze may exceed 2 when the coating film has a thickness of 0.1 μm.

  In the visible light photocatalyst composition, the oxide semiconductor (a) is 1% to 90% by weight, preferably 15 to 85% by weight, more preferably 25 to 80% by weight based on the total solid content of the composition. It is desirable to contain in the amount of%. If the amount of the oxide semiconductor (a) is less than the lower limit with respect to the total solid content of the visible light photocatalyst composition, the visible light photocatalytic action may not be exhibited, and if the upper limit is exceeded, a coating film is formed. When doing so, choking or the like may occur, and the film forming property may be inferior.

(B) Titanium compound:
The titanium compound (b) used in the present invention has the following formula (1)
R ¹ _m Ti (OR ² ) _4-m (1)
(In the formula, R ¹ represents an organic group having 1 to 8 carbon atoms, and when two or more exist, they may be the same or different, and R ² represents an alkyl group having 1 to 6 carbon atoms, It represents an organic group selected from the group consisting of an acyl group having 1 to 6 carbon atoms and a phenyl group, and when there are a plurality of them, they may be the same or different, and R ¹ and R ² are the same Or m may be an integer of 0 to 3)
And at least one titanium compound selected from the group consisting of the titanium acylate represented by the above formula (1) and the derivative thereof.

  Examples of the titanium alcoholate derivative include a hydrolyzate of the titanium alcoholate, a condensate of the titanium alcoholate, a chelate compound of the titanium alcoholate, a hydrolyzate of the chelate compound of the titanium alcoholate, and the titanium alcoholate. And a condensate of the above chelate compound.

  Further, the titanium acylate derivative includes a hydrolyzate of the titanium acylate, a condensate of the titanium acylate, a chelate compound of the titanium acylate, a hydrolyzate of the chelate compound of the titanium acylate, and the titanium. Examples include condensates of acylate chelate compounds.

In the above formula (1), R ¹ is an organic group having 1 to 8 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec- Alkyl groups such as butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group;
Acyl groups such as formyl group, acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group, trioyl group, caproyl group;
Examples thereof include a vinyl group, an allyl group, a cyclohexyl group, a phenyl group, an epoxy group, a glycidyl group, a (meth) acryloxy group, a ureido group, an amide group, a fluoroacetamide group, and an isocyanate group.

Furthermore, examples of R ¹ include substituted derivatives of the above organic groups. Examples of the substituent of the substituted derivative of R ¹ include a halogen atom, a substituted or unsubstituted amino group, a hydroxyl group, a mercapto group, an isocyanate group, a glycidoxy group, a 3,4-epoxycyclohexyl group, a (meth) acryloxy group, A ureido group, an ammonium base, etc. are mentioned. However, the number of carbon atoms of R ¹ composed of these substituted derivatives is preferably 8 or less including the carbon atoms in the substituent. When a plurality of R ¹ are present in the formula (1), they may be the same or different.

As R ² a carbon number of 1 to 6 alkyl groups, for example, a methyl group, an ethyl radical, n
-Propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-heptyl group and the like can be mentioned.

Examples of R ² which is an acyl group having 1 to 6 carbon atoms include formyl group, acetyl group, propionyl group, butyryl group, valeryl group, trioyl group, caproyl group and the like.
When a plurality of R ² are present in the formula (1), they may be the same or different from each other.

  The chelate compound of titanium alcoholate is selected from the group consisting of the titanium alcoholate and β-diketones, β-ketoesters, hydroxycarboxylic acid, hydroxycarboxylate, hydroxycarboxylic acid ester, ketoalcohol and aminoalcohol. It can be obtained by reacting with at least one compound (hereinafter also referred to as chelating agent). A chelate compound of titanium acylate can be obtained by reacting the titanium acylate with the chelating agent. Of these chelating agents, β-diketones or β-ketoesters are preferably used. More specifically, acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate-n-butyl, acetoacetate-sec-butyl, acetoacetate-t-butyl 2,4-hexane-dione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4-octane-dione, 2,4-nonane-dione, 5-methyl-hexane-dione, etc. Used.

  Specific examples of titanium alcoholate and titanium alcoholate chelate compounds include tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetra-t-butoxytitanium, and di-i-propoxybis (ethylacetoacetate). Titanium, di-i-propoxy bis (acetylacetate) titanium, di-i-propoxy bis (lactate) titanium, di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (tri Ethanolaminato) titanium, di-n-butoxy bis (acetylacetonato) titanium, tetrakis (2-ethylhexyloxy) titanium and the like.

Of these, tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetra-t-butoxytitanium, di-i-propoxybis (acetylacetonato) titanium, di-n-butoxybis (acetylacetonate) ) Titanium is preferred.

  Specific examples of titanium acylate and titanium acylate chelate compounds include dihydroxy / titanium dibutyrate, di-i-propoxy / titanium diacetate, bis (acetylacetonate) / titanium diacetate, and bis (acetylacetate). Nato) -titanium dipropionate, di-i-propoxy-titanium dipropionate, di-i-propoxy-titanium dimalonate, di-i-propoxy-titanium dibenzoylate, di-n-butoxy-zirconium diacetate , Di-i-propyl aluminum monomalonate and the like. Of these, dihydroxy titanium dibutyrate and di-i-propoxy titanium diacetate are preferred.

Titanium alcoholate hydrolyzate, titanium alcoholate chelate hydrolyzate, titanium acylate hydrolyzate, or titanium acylate chelate hydrolyzate is contained in titanium alcoholate or titanium acylate at least one of oR ² groups need only be hydrolysed, for example those in which one oR ² group is hydrolyzed, those two or more oR ² group is hydrolyzed, or a mixture thereof May be.

  Titanium alcoholate condensate, titanium alcoholate chelate condensate, titanium acylate condensate, and titanium acylate chelate condensate are titanium alcoholate, titanium alcoholate chelate, titanium acylate, respectively. The Ti—OH group in the hydrolyzate produced by hydrolysis of the rate and the chelate compound of titanium acylate is condensed to form a Ti—O—Ti bond. In the present invention, it is not necessary that all of the Ti—OH groups are condensed, and the condensate is obtained by condensing a small part of Ti—OH groups, and most (including all) Ti—OH groups. In addition, a mixture of a condensate in which a Ti—OR group and a Ti—OH group are mixed is also included.

In the present invention, it is preferable to use the condensate as the titanium compound (b) in order to control the reactivity and suppress the gelation, and the average condensation degree of the condensate is 2 to 20, that is, the condensation The product is more preferably a dimer to a 20-mer, and the average degree of condensation is preferably 2 to 10, that is, the condensate is particularly preferably a dimer to a 10-mer. This condensate is composed of titanium alcoholate, titanium alcoholate chelate compound, titanium acylate, and one compound selected from the group consisting of titanium acylate chelate compounds or a mixture of two or more titanium compounds. Those previously hydrolyzed and condensed may be used, or commercially available condensates may be used. In addition, a titanium alcoholate or a titanium acylate condensate may be used as it is, a product obtained by hydrolyzing a part or all of the OR ² group contained in the condensate, or the chelate obtained by chelating the condensate. You may use as a condensate of the chelate compound of titanium alcoholate or titanium acylate obtained by making it react with an agent.

  Examples of commercially available condensates of titanium alcoholate (from dimer to decamer) include A-10, B-2, B-4, B-7, and B-10 manufactured by Nippon Soda Co., Ltd. It is done. Such a titanium compound (b) may be used individually by 1 type, or 2 or more types may be mixed and used for it.

The amount of the titanium compound (b) used in the present invention is 1 to 100 parts by weight, preferably 2 to 90 parts by weight in terms of complete hydrolysis condensate, based on 100 parts by weight of the solid content of the oxide semiconductor (a). More preferably, the amount is 3 to 80 parts by weight. Here, the completely hydrolyzed condensate means that the OR ² group in the formula (1) is 100% hydrolyzed to become a Ti—OH group, and further, the Ti—OH group is completely condensed to form a Ti—O—Ti structure. Is what formed. These titanium compounds (b) adsorb or bind to the surface of the oxide semiconductor (a), improve the affinity of the oxide semiconductor (a) to the solvent, and reduce the dispersed particle size and dispersibility. It is thought that there is an action which raises.

(C) Silane compound:
The silane compound (c) used in the present invention has the following formula (2)
R ³ _n Si (OR ⁴ ) _4-n (2)
(In the formula, R ³ represents a monovalent organic group having 1 to 8 carbon atoms, and when a plurality of R ³ are present, they may be the same or different, and R ⁴ has 1 to 5 carbon atoms. Represents an alkyl group or an acyl group having 1 to 6 carbon atoms, and when there are a plurality of them, they may be the same or different, and R ³ and R ⁴ may be the same or different; n is an integer of 0 to 3)
At least one silane compound selected from the group consisting of an organosilane (hereinafter referred to as “organosilane (2)”) and derivatives thereof.

Examples of the organosilane (2) derivative include hydrolyzate of organosilane (2) and condensate of organosilane (2).
The silane compound (c) used in the present invention is at least one silane compound selected from the group consisting of organosilane (2), hydrolyzate of organosilane (2), and condensate of organosilane (2). Of these three silane compounds, only one silane compound may be used, any two silane compounds may be mixed, or all three silane compounds may be mixed. May be used.

In the above formula (2), R ³ is a monovalent organic group having 1 to 8 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group. Alkyl groups such as i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-heptyl group, n-octyl group and 2-ethylhexyl group;
Acyl groups such as formyl group, acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group, trioyl group, caproyl group;
Examples thereof include a vinyl group, an allyl group, a cyclohexyl group, a phenyl group, an epoxy group, a glycidyl group, a (meth) acryloxy group, a ureido group, an amide group, a fluoroacetamide group, and an isocyanate group.

Furthermore, examples of R ³ include substituted derivatives of the above organic groups. Examples of the substituent of the substituted derivative of R ³ include a halogen atom, a substituted or unsubstituted amino group, a hydroxyl group, a mercapto group, an isocyanate group, a glycidoxy group, a 3,4-epoxycyclohexyl group, a (meth) acryloxy group, A ureido group, an ammonium base, etc. are mentioned. However, the number of carbon atoms of R ³ composed of these substituted derivatives is preferably 8 or less including the carbon atoms in the substituent. When a plurality of R ³ are present in the formula (2), they may be the same or different.

As R ⁴ which is an alkyl group having 1 to 5 carbon atoms, for example, a methyl group, an ethyl group, n
-Propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group and the like can be mentioned, and as R ⁴ which is an acyl group having 1 to 6 carbon atoms Is
Examples include formyl group, acetyl group, propionyl group, butyryl group, valeryl group, caproyl group and the like. When a plurality of R ⁴ are present in the formula (2), they may be the same or different.

Specific examples of such organosilane (2) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, and tetra-n-butoxysilane;
Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n- Butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, Cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxy Silane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycid Cypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- Trialkoxysilanes such as (meth) acrylicoxypropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane;
Dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxy Silane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldi Ethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyl Diethoxysilane, diphenyl Silane, dialkoxy silanes such as diphenyl diethoxy silane;
Monoalkoxysilanes such as trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane;
Examples thereof include methyltriacetyloxysilane and dimethyldiacetyloxysilane.

  Of these, trialkoxysilanes and dialkoxysilanes are preferable, and methyltrimethoxysilane and methyltriethoxysilane are more preferable as trialkoxysilanes, and dimethyldimethoxysilane and dimethyldisilane are preferable as dialkoxysilanes. Ethoxysilane is preferred.

  As the organosilane (2) used in the present invention, the above organosilane (2) may be used alone or in combination of two or more. For example, trialkoxysilane alone or a mixture of trialkoxysilane 40 to 95 mol% and dialkoxysilane 60 to 5 mol% is particularly preferably used. By using dialkoxysilane and trialkoxysilane in combination, the resulting coating film can be softened and alkali resistance can be improved.

In the present invention, organosilane (2) may be used as it is as silane compound (c), but hydrolyzate and / or condensate of organosilane (2) can be used.

The hydrolyzate of organosilane (2) is sufficient if at least one of 1-4 OR ⁴ groups contained in organosilane (2) is hydrolyzed, for example, one OR ⁴ group. May be hydrolyzed, two or more OR ⁴ groups may be hydrolyzed, or a mixture thereof.

  The condensate of organosilane (2) is a product in which silanol groups in the hydrolyzate produced by hydrolysis of organosilane (2) are condensed to form Si—O—Si bonds. In the present invention, it is not necessary that all of the silanol groups are condensed, and the condensate may be one obtained by condensing a small part of silanol groups, one containing most (including all) silanol groups, And mixtures thereof.

  Such hydrolyzate and / or condensate of organosilane (2) can be produced by hydrolyzing and condensing organosilane (2) in advance. As will be described later, when preparing the visible light photocatalyst composition, hydrolyzate and / or condensate of organosilane (2) is prepared by hydrolyzing and condensing organosilane (2) and water. You can also This water may be added independently, or water contained in the oxide semiconductor (a), water (e1) or organic solvent (e2) described later may be used. The amount of water when added independently is usually 0.5 to 5 mol, preferably 0.7 to 3 mol, particularly preferably 0.7 to 2 mol, relative to 1 mol of organosilane (2). Is desirable.

  Such a condensate of organosilane (2) has a polystyrene-reduced weight average molecular weight (hereinafter referred to as “Mw”) by GPC method, preferably 300 to 100,000, more preferably 500 to 50,000. A condensate is used.

  When the condensate of organosilane (2) is used as the silane compound (c) in the present invention, it may be prepared from the above organosilane (2) or a commercially available condensate of organosilane. Commercially available condensates of organosilane include MKC silicate manufactured by Mitsubishi Chemical Corporation, ethyl silicate manufactured by Colcoat, silicone resin manufactured by Toray Dow Corning Silicone Co., Ltd., manufactured by GE Toshiba Silicone Co., Ltd. Silicone resin, silicone resin and silicone oligomer manufactured by Shin-Etsu Chemical Co., Ltd., hydroxyl group-containing polydimethylsiloxane manufactured by Dow Corning Asia Co., Ltd., silicone oligomer manufactured by Nihon Unicar Co., Ltd., and the like. These commercially available condensates of organosilane may be used as they are, or may be further condensed.

Such a silane compound (c) may be used individually by 1 type, or 2 or more types may be mixed and used for it.
In the first and third visible light photocatalyst compositions used in the present invention, the silane compound (c) is based on the solid content of the visible light photocatalyst composition obtained by removing the oxide semiconductor (a). Thus, it is desirably used in an amount of 5% by weight to 95% by weight, preferably 10% by weight to 90% by weight, more preferably 20% by weight to 80% by weight in terms of complete hydrolysis condensate. Here, the complete hydrolysis-condensation product means that the OR ⁴ group in the formula (2) is 100
% Hydrolyzed to form Si—OH groups, and further, Si—OH groups are completely condensed to form a siloxane structure. When the content of the silane compound (c) is less than the above lower limit, the formed coating film is brittle, and choking or the like may occur.

(D) Organosiloxane oligomer:
The organosiloxane oligomer (d) used in the present invention has a Si—O bond, has a weight average molecular weight of 300 to 100,000, and has the following formula (3) in the side chain and / or terminal.
_{^{- (R 5 O) p -}} (R 6 O) q -R 7 (3)
(Wherein R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 5 carbon atoms, R ⁷ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and p and q are p + q Is a number from 2 to 50)
The structure represented by these is contained.

  Examples of the functional group represented by the above formula (3) include polyoxyalkylene groups such as a polyoxyethylene group, a polyoxypropylene group, and a poly (oxyethylene / oxypropylene) group. When the organosiloxane oligomer (d) contains such a functional group, the polyoxyalkylene group portion in the functional group is easily adsorbed to the oxide semiconductor (a), and the dispersion stability of the oxide semiconductor (a) Is thought to improve.

The main chain of the organosiloxane oligomer (d) may be substituted with a hydroxyl group, a halogen atom, or a functional group containing an organic group having 1 to 15 carbon atoms.
Examples of the halogen atom include fluorine and chlorine.

  As an organic group having 1 to 15 carbon atoms, an alkyl group, acyl group, alkoxyl group, alkoxysilyl group, vinyl group, allyl group, acetoxyl group, acetoxysilyl group, cycloalkyl group, phenyl group, glycidyl group, (meth) acrylic Examples thereof include an oxy group, a ureido group, an amide group, a fluoroacetamide group, and an isocyanate group.

  Examples of the alkyl group having 1 to 15 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, and n-hexyl. Group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, heptadecyl group, octadecyl group, 2-ethylhexyl group, etc. It is done.

Examples of the acyl group having 1 to 15 carbon atoms include formyl group, acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group, and toluoyl group.
Examples of the alkoxyl group having 1 to 15 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

Examples of the alkoxysilyl group having 1 to 15 carbon atoms include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, and a butoxysilyl group.
These groups may be partially hydrolyzed / condensed or substituted derivatives. Substituents of substituted derivatives include, for example, halogen atoms, substituted or unsubstituted amino groups, hydroxyl groups, mercapto groups, isocyanate groups, glycidoxy groups, 3,4-epoxycyclohexyl groups, (meth) acryloxy groups, ureido groups, ammonium Examples include bases and ketoester groups.

  Of these, the organosiloxane oligomer (d) containing a structure in which a silicon atom of a silyl group is bonded to a hydrolyzable group and / or a hydroxyl group is particularly preferably used. For example, a chlorosilane condensate or an alkoxysilane condensate is used. Used. Such an organosiloxane oligomer (d) is immobilized by cocondensation with the titanium compound (b) and / or the silane compound (c) when the visible light photocatalyst composition used in the present invention is cured. A stable coating film can be obtained.

The weight average molecular weight (hereinafter also referred to as “Mw”) in terms of polystyrene by the GPC method of the organosiloxane oligomer (d) is 300 to 100,000, preferably 600 to 50,000. If the weight average molecular weight is less than the above lower limit, the resulting coating film may not have sufficient flexibility, and if it exceeds the above upper limit, the resulting coating composition may not have sufficient storage stability. is there.

  In the present invention, the organosiloxane oligomer (d) may be used alone or in combination of two or more. As an organosiloxane oligomer (d) in which two or more kinds are mixed, a mixture of an organosiloxane oligomer having Mw = 400 to 2,800 and an organosiloxane oligomer having Mw = 3,000 to 50,000, or 2 having different functional groups Mention may be made of mixtures of different organosiloxane oligomers.

  In the present invention, a commercially available organosiloxane oligomer can be used as the organosiloxane oligomer (d). For example, modified silicone oil manufactured by Toray Dow Corning Silicone Co., Ltd., GE Toshiba Silicone Co., Ltd. Modified silicone oil manufactured by Shin-Etsu Chemical Co., Ltd., modified silicone oil manufactured by Nihon Unicar Co., Ltd. and the like. These organosiloxane oligomers may be used as they are or after being condensed.

  In the second and third visible light photocatalyst compositions used in the present invention, the amount of the organosiloxane oligomer (d) is 1 to 200 parts by weight with respect to 100 parts by weight of the solid content of the oxide semiconductor (a), The amount is preferably 5 to 100 parts by weight, more preferably 10 to 80 parts by weight. When the amount of the organosiloxane oligomer (d) is less than the above lower limit, sufficient dispersion stability may not be obtained. When the amount exceeds the above upper limit, the content of the oxide semiconductor (a) decreases, and the photocatalytic activity is increased. The photocatalytic action may not be obtained due to the decrease.

(E) Water and / or organic solvent:
The visible light photocatalyst composition used in the present invention preferably contains water (e1) and / or an organic solvent (e2). As the organic solvent (e2), a known organic solvent can be used, and examples thereof include alcohols, aromatic hydrocarbons, ethers, ketones, and esters.

  More specifically, as alcohols, methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-hexyl alcohol, n-octyl alcohol, ethylene Glycol, diethylene glycol, triethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene monomethyl ether acetate, diacetone alcohol, and the like. As aromatic hydrocarbons, Benzene, toluene, xylene and the like, and ethers include tetrahydrofuran, dioxane and the like, Examples of tones include acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone and the like. Examples of esters include ethyl acetate, propyl acetate, butyl acetate, propylene carbonate, methyl lactate, ethyl lactate, normal propyl lactate, isopropyl lactate, 3 -Methyl ethoxypropionate, ethyl 3-ethoxypropionate and the like. These organic solvents may be used individually by 1 type, or 2 or more types may be mixed and used for them.

(F) Catalyst:
The visible light photocatalyst composition used in the present invention preferably contains a catalyst (f) in order to promote hydrolysis / condensation reaction of the silane compound (c), the organosiloxane oligomer (d) and the like. As the catalyst (f) used in the present invention, an acidic compound, an alkaline compound, a salt compound, an amine compound, an organometallic compound and / or a partial hydrolyzate thereof (hereinafter referred to as an organometallic compound and / or a partial hydrolyzate thereof are summarized. And “organic metal compounds”).

Examples of the acidic compound include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, alkyl titanic acid, p-toluenesulfonic acid, and phthalic acid, and among these, acetic acid is preferable.
Examples of the alkaline compound include sodium hydroxide and potassium hydroxide, and among these, sodium hydroxide is preferable.

Examples of the salt compound include naphthenic acid, octylic acid, nitrous acid, sulfurous acid, aluminate, and alkali metal salts such as carbonic acid.
Examples of the amine compound include ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperidine, piperazine, m-phenylenediamine, p-phenylenediamine, ethanolamine, triethylamine, 3-aminopropyl trimethoxy. Silane, 3-aminopropyl-triethoxysilane, 3- (2-aminoethyl) -aminopropyl-trimethoxysilane, 3- (2-aminoethyl) -aminopropyl-triethoxysilane, 3- (2-aminoethyl) ) -Aminopropyl-methyl-dimethoxysilane, 3-anilinopropyl-trimethoxysilane, alkylamine salts, and quaternary ammonium salts. Various modified amines used as a curing agent for epoxy resins can also be used. Of these, 3-aminopropyl / trimethoxysilane, 3-aminopropyl / triethoxysilane, and 3- (2-aminoethyl) -aminopropyl / trimethoxysilane are preferable.

Examples of the organometallic compounds include the following formula (4):
M (OR ⁸ ) _r (R ⁹ COCHCOR ¹⁰ ) _s (4)
(Wherein M represents at least one metal atom selected from the group consisting of zirconium, titanium and aluminum, and R ⁸ and R ⁹ are each independently a methyl group, an ethyl group, an n-propyl group, C1-C6 monovalent hydrocarbon group such as i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, phenyl group R ¹⁰ represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, or a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a sec-butoxy group, represents an alkoxyl group having 1 to 16 carbon atoms such as t-butoxy group, lauryloxy group and stearyloxy group, and r and s are each independently an integer of 0 to 4, and (r + s) = (M Valence Satisfy the relationship)
(Hereinafter referred to as “organometallic compound (4)”),
A tetravalent tin organometallic compound in which one or two alkyl groups having 1 to 10 carbon atoms are bonded to one tin atom (hereinafter referred to as “organotin compound”), or
These partial hydrolysates are exemplified.

Moreover, the above-described titanium compound (b) can be used as the organometallic compounds.
Examples of the organometallic compound (4) include tetra-n-butoxyzirconium, tri-n-butoxyethylacetoacetatezirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate). Organic zirconium compounds such as acetate) zirconium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium;
Organic titanium compounds such as tetra-i-propoxy titanium, di-i-propoxy bis (ethylacetoacetate) titanium, di-i-propoxy bis (acetylacetate) titanium, di-i-propoxy bis (acetylacetone) titanium ;
Tri-i-propoxyaluminum, di-i-propoxyethyl acetoacetate aluminum, di-i-propoxy acetylacetonate aluminum, i-propoxy bis (ethylacetoacetate) aluminum, i-propoxy bis (acetylacetonate) And organoaluminum compounds such as aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum, monoacetylacetonatobis (ethylacetoacetate) aluminum.

  Among these organometallic compounds (4) and partial hydrolysates thereof, tri-n-butoxy ethylacetoacetate zirconium, di-i-propoxy bis (acetylacetonato) titanium, di-i-propoxy ethylacetate Acetate aluminum, tris (ethyl acetoacetate) aluminum, or a partial hydrolyzate thereof is preferably used.

As an organic tin compound, for example,
(C ₄ H ₉ ) ₂ Sn (OCOC ₁₁ H ₂₃ ) ₂ ,
_{(C 4 H 9) 2 Sn} (OCOCH = CHCOOCH 3) 2,
_{(C 4 H 9) 2 Sn} (OCOCH = CHCOOC 4 H 9) 2,
(C ₈ H ₁₇ ) ₂ Sn (OCOC ₈ H ₁₇ ) ₂ ,
(C ₈ H ₁₇ ) ₂ Sn (OCOC ₁₁ H ₂₃ ) ₂ ,
_{(C 8 H 17) 2 Sn} (OCOCH = CHCOOCH 3) 2,
_{(C 8 H 17) 2 Sn} (OCOCH = CHCOOC 4 H 9) 2,
_{(C 8 H 17) 2 Sn} (OCOCH = CHCOOC 8 H 17) 2,
_{(C 8 H 17) 2 Sn} (OCOCH = CHCOOC 16 H 33) 2,
_{(C 8 H 17) 2 Sn} (OCOCH = CHCOOC 17 H 35) 2,
_{(C 8 H 17) 2 Sn} (OCOCH = CHCOOC 18 H 37) 2,
_{(C 8 H 17) 2 Sn} (OCOCH = CHCOOC 20 H 41) 2,

_{(C 4 H 9) Sn (} OCOC 11 H 23) 3,
(C ₄ H ₉ ) Sn (OCONa) ₃
Carboxylic acid type organotin compounds such as;
_{(C 4 H 9) 2 Sn} (SCH 2 COOC 8 H 17) 2,
_{(C 4 H 9) 2 Sn} (SCH 2 CH 2 COOC 8 H 17) 2,
_{(C 8 H 17) 2 Sn} (SCH 2 COOC 8 H 17) 2,
_{(C 8 H 17) 2 Sn} (SCH 2 CH 2 COOC 8 H 17) 2,
_{(C 8 H 17) 2 Sn} (SCH 2 COOC 12 H 25) 2,
_{(C 8 H 17) 2 Sn} (SCH 2 CH 2 COOC 12 H 25) 2,
_{(C 4 H 9) Sn (} SCOCH = CHCOOC 8 H 17) 3,
_{(C 8 H 17) Sn (} SCOCH = CHCOOC 8 H 17) 3,

Mercaptide-type organotin compounds such as
(C ₄ H ₉ ) ₂ Sn = S, (C ₈ H ₁₇ ) ₂ Sn = S,

Sulfide-type organotin compounds such as;
(C ₄ H ₉ ) SnCl ₃ , (C ₄ H ₉ ) ₂ SnCl ₂ ,
(C ₈ H ₁₇ ) ₂ SnCl ₂ ,

Chloride-type organotin compounds such as;
Reaction of organotin oxides such as (C ₄ H ₉ ) ₂ SnO, (C ₈ H ₁₇ ) ₂ SnO, and ester compounds such as silicates, dimethyl maleate, diethyl maleate and dioctyl phthalate Product;
Etc.

Such a catalyst (f) may be used singly or in combination of two or more, or may be used by mixing with a zinc compound or other reaction retarder.
The catalyst (f) may be blended in the step of preparing the visible light photocatalyst composition used in the present invention, may be blended in the visible light photocatalyst composition in the step of forming a coating film, and , You may mix | blend both in the preparation process of a visible light photocatalyst composition, and the formation process of a coating film.

The amount of the catalyst (f) used in the present invention is usually 10 moles or less, preferably 0.001 to 7 moles, more preferably 0.8 moles per mole of OR ⁴ group contained in the silane compound (c). 0
01-5 mol is desirable. When the amount of the catalyst (f) exceeds the above upper limit, the storage stability of the visible light photocatalyst composition may be lowered, or cracks may be generated in the coating film.

  The catalyst (f) promotes hydrolysis / condensation reaction of the silane compound (c), the organosiloxane oligomer (d), and the like. Therefore, by using the catalyst (f), for example, the molecular weight of the polysiloxane resin produced by the polycondensation reaction of the organosiloxane oligomer (d) is increased, and the curing rate of the resulting coating film is improved. A coating film excellent in durability and the like can be obtained, and the coating film can be made thicker, so that the painting work is facilitated.

(G) Stability improver:
The visible light photocatalyst composition used in the present invention may contain a stability improver (g) in order to improve storage stability and the like as necessary. The stability improver (g) used in the present invention is represented by the following formula (5).
R ¹¹ COCH ₂ COR ¹² (5)
(In the formula, R ¹¹ is methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group) R 1 represents a monovalent hydrocarbon group having 1 to 6 carbon atoms such as a group or a phenyl group, and R ¹² represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, or a methoxy group, an ethoxy group, n -Represents an alkoxyl group having 1 to 16 carbon atoms such as propoxy group, i-propoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, lauryloxy group, stearyloxy group)
At least one compound selected from the group consisting of β-diketones, β-ketoesters, carboxylic acid compounds, dihydroxy compounds, amine compounds and oxyaldehyde compounds.

  Examples of such a stability improver (g) include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate-n-butyl, acetoacetate-sec- Butyl, acetoacetate-t-butyl, hexane-2,4-dione, heptane-2,4-dione, heptane-3,5-dione, octane-2,4-dione, nonane-2,4-dione, 5 -Methylhexane-2,4-dione, malonic acid, oxalic acid, phthalic acid, glycolic acid, salicylic acid, aminoacetic acid, iminoacetic acid, ethylenediaminetetraacetic acid, glycol, catechol, ethylenediamine, 2,2-bipyridine, 1,10- Phenanthroline, diethylenetriamine, 2-ethanolamine, dimethylglyoxime, dithizone, methi Nin, such as salicylic aldehyde, and the like. Of these, acetylacetone and ethyl acetoacetate are preferred.

  Such a stability improver (g) is particularly preferably used when an organometallic compound is used as the titanium compound (b) or the catalyst (f). Moreover, a stability improver (g) may be used individually by 1 type, or may mix and use 2 or more types.

  By using the stability improver (g), the stability improver (g) is coordinated to the metal atom of the organometallic compound, and this coordination is achieved by the silane compound (c) or the organosiloxane oligomer (d). It is considered that the storage stability of the resulting visible light photocatalyst composition can be further improved by appropriately adjusting the promoting action of the organometallic compounds for the cocondensation reaction.

  The amount of the stability improver (g) used in the present invention is usually 2 moles or more, preferably 3 to 20 moles per mole of the organometallic compound of the organometallic compounds. When the amount of the stability improver (g) is less than the above lower limit, the visible light photocatalyst composition having a high solid content concentration may be insufficient in improving the storage stability of the resulting composition.

(H) Filler:
In the visible light photocatalyst composition used in the present invention, it is also preferable to add and disperse a filler as necessary in order to color the coating film to be obtained and to increase the thickness of the coating film.

  Fillers used in the present invention include water-insoluble organic pigments and inorganic content; ceramics, metals or alloys other than particulate, fibrous or scale-like pigments, and oxides, hydroxides and carbides of these metals , Nitrides and sulfides.

  Specifically, iron, copper, aluminum, nickel, silver, zinc, ferrite, carbon black, stainless steel, silicon dioxide, titanium oxide for pigments, aluminum oxide, chromium oxide, manganese oxide, iron oxide, zirconium oxide, cobalt oxide , Synthetic mullite, aluminum hydroxide, iron hydroxide, silicon carbide, silicon nitride, boron nitride, clay, diatomaceous earth, slaked lime, gypsum, talc, barium carbonate, calcium carbonate, magnesium carbonate, barium sulfate, bentonite, mica, zinc green , Chrome green, Cobalt green, Viridian, Guinea green, Cobalt chrome green, Shale green, Green earth, Manganese green, Pigment green, Ultramarine, Bitumen, Pigment blue, Rock ultramarine, Cobalt blue, Cerulean blue, Copper borate, Molybdenum blue , Copper sulfide, cobalt purple, mars purple, manga Purple, Pigment Violet, Lead Oxide, Calcium Leadate, Zinc Yellow, Lead Sulfide, Chrome Yellow, Ocher, Cadmium Yellow, Strontium Yellow, Titanium Yellow, Resurge, Pigment Yellow, Cuprous Oxide, Cadmium Red, Selenium Red, Chrome Vermilion , Bengala, zinc white, antimony white, basic lead sulfate, titanium white, lithopone, lead silicate, zircon oxide, tungsten white, lead, zinc white, bunchison white, lead phthalate, manganese white, lead sulfate, graphite, bone Black, diamond black, thermatomic black, vegetable black, potassium titanate whisker, molybdenum disulfide, and the like.

These fillers can be used alone or in admixture of two or more.
Moreover, the usage-amount of a filler has preferable 300 weight part or less with respect to 100 weight part of total solid of the visible light photocatalyst composition used for this invention.

(I) Other additives:
In the visible light photocatalyst composition used in the present invention, if necessary,
Known dehydrating agents such as methyl orthoformate, methyl orthoacetate, tetraethoxysilane;
Polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polycarboxylic acid type polymer surfactant, polycarboxylate, polyphosphate, polyacrylate, polyamide ester salt, polyethylene glycol, etc. A dispersant can be blended.

Moreover, in order to improve the coating property (it is also called film forming property) of the composition used for this invention, a leveling agent can be mix | blended. As such leveling agents, for example, BM1000 (trade name, hereafter the same) and BM1100 manufactured by BM-CHEMIE; EFKA 772 and EFKA 777 manufactured by EFKA Chemicals; Floren series manufactured by Kyoeisha Chemical Co., Ltd .; Sumitomo Fluorine leveling agents such as 3M's FC series; Toho Chemical's Fluoronal TF series;
BYK series from Big Chemie; Sshmego series from Sshmegmann; silicones such as Fuka 30, Fuka 31, Fuka 34, Fuka 35, Fuka 36, Fuka 39, Fuka 83, Fuka 86, and Fuka 88 from Fuka Chemicals Leveling agents;
Carfinol from Nissin Chemical Industry Co., Ltd .; Ether-type or ester-type leveling agents such as emulgen and homogenol from Kao Corporation.

By blending such a leveling agent, the finished appearance of the coating film is improved and a uniform thin film can be prepared.
In the present invention, the leveling agent is preferably used in an amount of 0.01 to 5% by weight, more preferably 0.02 to 3% by weight, based on the total composition.

  The method of blending the leveling agent may be blended in the step of preparing the visible light photocatalyst composition used in the present invention, or may be blended in the visible light photocatalyst composition in the step of forming the coating film. May be blended in both the step of preparing the visible light photocatalyst composition and the step of forming the coating film.

(Preparation method of visible light photocatalyst composition)
Specific examples of the method for preparing the visible light photocatalyst composition used in the present invention include the following methods.

(1) When the oxide semiconductor (a) is a powder:
To the oxide semiconductor (a), water (e1) and / or an organic solvent (e2), a titanium compound (b) and, if necessary, an organosiloxane oligomer (d) are added. The silane compound (c), water (e1) and / or the organic solvent (e2), and the catalyst (f) are added as necessary to cause hydrolysis and condensation.

(2) When the oxide semiconductor (a) is a sol:
The titanium compound (b) and, if necessary, the organosiloxane oligomer (d) are added to the sol of the oxide semiconductor (a) and stirred, and then the silane compound (c), water (e1) and / or organic solvent. (E2) and the catalyst (f) are added as necessary, and hydrolyzed and condensed.

  In the production methods (1) and (2), the components (b) to (f) may be added all at once or sequentially. In particular, it is preferable to sequentially add a component having low compatibility with the oxide semiconductor (a). Here, “collective addition” means adding one kind of component at a time, and “sequential addition” means adding one kind of component over an arbitrary time. Furthermore, when components (b) to (f) are added all at once, components (b) to (f) may be added all at once, but are compatible with the oxide semiconductor (a). In consideration of the above, each component may be added independently.

  Titanium compound (b) and organosiloxane oligomer (d) are adsorbed to oxide semiconductor (a) by adding titanium compound (b) and, if necessary, organosiloxane oligomer (d) to oxide semiconductor (a). And / or reacts to ensure dispersion stability of the oxide semiconductor (a). In particular, when the cohesive force of the oxide semiconductor (a) is strong and difficult to disperse, it is preferable to use the titanium compound (b) and the organosiloxane oligomer (d) in combination.

  Examples of the disperser used in the production method (1) include an ultrasonic disperser, a ball mill, a sand mill (bead mill), a homogenizer, an ultrasonic homogenizer, a nanomizer, a propeller mixer, and a high shear mixer.

In the production method (1), the secondary particle size (dispersed particle size) of the oxide semiconductor (a) is obtained by dispersing the oxide semiconductor (a) with a disperser in the presence of the titanium compound (b). Decreases. Further, when the organosiloxane oligomer (d) is used, the oxide semiconductor (a) is adsorbed with the structure represented by the above formula (3) of the organosiloxane oligomer (d), whereby the organosiloxane oligomer (d) To ensure dispersion stability.

  Then, by adding the silane compound (c) as necessary, the silane compound (c) plays the role of a binder, and even when the content of the oxide semiconductor (a) is high, the film is formed without choking. Can do.

  The total solid content concentration in the visible light photocatalyst composition used in the present invention can be appropriately set according to the type of substrate, the coating method, the thickness of the coating film, etc., for example, usually exceeding 0% by weight. 50 wt% or less, preferably 0.01 wt% or more and 20 wt% or less, more preferably 0.05 wt% or more and 10 wt% or less. When the total solid content exceeds the above upper limit, the storage stability may be lowered.

<Coating composition for undercoat>
The laminate according to the present invention has a deterioration preventing intermediate layer between the organic substrate and the photocatalyst layer in order to prevent deterioration of the organic substrate due to the photocatalytic action of the photocatalyst layer. The intermediate layer is not particularly limited as long as it can prevent deterioration of the organic base material. For example, the intermediate layer is formed using the following undercoat coating composition (hereinafter also referred to as “undercoat composition”). Can do.
(I) A composition containing the silane compound (c) and a silyl group-containing polymer having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group.
(Ii) containing the silane compound (c), a silyl group-containing polymer having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group, and at least one of colloidal silica and colloidal alumina. Composition.
(Iii) The silane compound (c), a silyl group-containing polymer having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group, and at least one of colloidal cerium oxide and colloidal zinc oxide. Containing composition.
(Iv) the silane compound (c), a silyl group-containing polymer having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group, at least one of colloidal silica and colloidal alumina, and colloidal A composition comprising at least one of cerium oxide and colloidal zinc oxide.

  The silane compound (c) used in the undercoat coating composition may be the same as or different from the silane compound (c) used in the visible light photocatalyst composition, but the intermediate layer and the photocatalyst layer are in close contact with each other. From the viewpoint of properties, it is preferable to use a silane compound composed of the same organosilane.

(Silyl group-containing polymer)
The silyl group-containing polymer having a silicon atom bonded to the hydrolyzable group and / or hydroxyl group (hereinafter, also simply referred to as “specific silyl group-containing polymer”) is bonded to the hydrolyzable group and / or hydroxyl group. The polymer preferably comprises a polymer having a silyl group having a silicon atom (hereinafter referred to as “specific silyl group”) at the terminal and / or side chain of the polymer molecular chain. When the specific silyl group-containing polymer is cured, the hydrolyzable group and / or hydroxyl group in the silyl group co-condenses with the silane compound (c), thereby providing excellent coating performance. It is an ingredient to bring. Content of the silicon atom in a specific silyl group containing polymer is 0.001-20 weight% normally with respect to the whole specific silyl group containing polymer, Preferably it is 0.01-15 weight%. A preferable specific silyl group is a group represented by the following formula (6).

(In the formula, X represents a hydrolyzable group such as a halogen atom, an alkoxyl group, an acetoxy group, a phenoxy group, a thioalkoxyl group, an amino group or a hydroxyl group, and R ¹³ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or An aralkyl group having 1 to 10 carbon atoms; i is an integer of 1 to 3)
The specific silyl group-containing polymer can be produced, for example, by the following methods (I) and (II).

  (I) A hydrosilane compound corresponding to the general formula (6) (hereinafter also simply referred to as “hydrosilane compound”) is converted into a vinyl polymer having a carbon-carbon double bond (hereinafter referred to as “unsaturated vinyl polymer”). And the addition reaction to the carbon-carbon double bond.

  (II) The following general formula (7)

(Wherein, X, R ^13, i have the same meanings as X, R ^13, i in the formula (6), R ¹⁴ represents an organic group having a polymerizable double bond)
A method of copolymerizing a silane compound represented by formula (hereinafter referred to as “unsaturated silane compound”) and another vinyl monomer.

  Examples of the hydrosilane compound used in the above method (I) include halogenated silanes such as methyldichlorosilane, trichlorosilane, and phenyldichlorosilane; methyldimethoxysilane, methyldiethoxysilane, phenyldimethoxysilane, Alkoxysilanes such as methoxysilane and triethoxysilane; acyloxysilanes such as methyldiacetoxysilane, phenyldiacetoxysilane and triacetoxysilane; amino such as methyldiaminoxysilane, triaminoxysilane and dimethylaminoxysilane Examples include xylsilanes. These hydrosilane compounds can be used alone or in admixture of two or more.

  The unsaturated vinyl polymer used in the method (I) is not particularly limited as long as it is not a polymer having a hydroxyl group. For example, the following methods (I-1) and (I-2) Or it can manufacture by these combinations.

  (I-1) After (co) polymerizing a vinyl monomer having a functional group (hereinafter referred to as “functional group (α)”), the functional group (α) in the (co) polymer By reacting a functional group capable of reacting with the functional group (α) (hereinafter referred to as “functional group (β)”) and an unsaturated compound having a carbon / carbon double bond, the side chain of the polymer molecular chain is reacted. A method for producing an unsaturated vinyl polymer having a carbon-carbon double bond.

  (I-2) A radical polymerization initiator having a functional group (α) (for example, 4,4′-azobis-4-cyanovaleric acid, etc.) is used, or both the radical polymerization initiator and the chain transfer agent are used. Using a compound having a functional group (α) (for example, 4,4′-azobis-4-cyanovaleric acid and dithioglycolic acid), a vinyl monomer is (co) polymerized to form a polymer molecule After synthesizing a (co) polymer having a functional group (α) derived from a radical polymerization initiator or chain transfer agent at one or both ends of the chain, the functional group (α) in the (co) polymer is synthesized. An unsaturated vinyl polymer having a carbon-carbon double bond at one or both ends of a polymer molecular chain by reacting an unsaturated compound having a functional group (β) and a carbon / carbon double bond. How to manufacture.

  Examples of the reaction between the functional group (α) and the functional group (β) in the methods (I-1) and (I-2) include an esterification reaction between a carboxyl group and a hydroxyl group, and a carboxylic anhydride group and a hydroxyl group. Ring-opening esterification reaction, carboxyl group and epoxy group ring-opening esterification reaction, carboxyl group and amino group amidation reaction, carboxylic acid anhydride group and amino group ring-opening amidation reaction, epoxy group Ring-opening addition reaction between a hydroxyl group and an amino group, urethanization reaction between a hydroxyl group and an isocyanate group, a combination of these reactions, and the like.

  Examples of vinyl monomers having a functional group (α) include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid; maleic anhydride, itaconic anhydride and the like. Unsaturated carboxylic acid anhydrides; hydroxyl groups such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, N-methylol (meth) acrylamide, 2-hydroxyethyl vinyl ether -Containing vinyl monomers; amino group-containing vinyl monomers such as 2-aminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 2-aminoethyl vinyl ether; 1,1,1-trimethylamine (meth) acrylimi 1-methyl-1-ethylamine (meth) acrylimide, 1,1-dimethyl-1- (2-hydroxypropyl) amine (meth) acrylimide, 1,1-dimethyl-1- (2′-phenyl-2) Amine-group-containing vinyl monomers such as' -hydroxyethyl) amine (meth) acrylimide, 1,1-dimethyl-1- (2'-hydroxy-2'-phenoxypropyl) amine (meth) acrylimide; glycidyl An epoxy group-containing vinyl monomer such as (meth) acrylate and allyl glycidyl ether can be used. These vinyl monomers having a functional group (α) can be used alone or in admixture of two or more.

Examples of other vinyl monomers copolymerizable with the vinyl monomer having a functional group (α) include styrene, α-methyl styrene, 4-methyl styrene, 2-methyl styrene, and 3-methyl styrene. 4-methoxystyrene, 2-hydroxymethylstyrene, 4-ethylstyrene, 4-ethoxystyrene, 3,4-dimethylstyrene, 3,4-diethylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chloro- Aromatic vinyl monomers such as 3-methylstyrene, 4-t-butylstyrene, 2,4-dichlorostyrene, 2,6-dichlorostyrene, 1-vinylnaphthalene;
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, amyl (meth) acrylate, i-amyl (meth) acrylate, hexyl (Meth) acrylate compounds such as (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, cyclohexyl methacrylate;
Divinylbenzene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) ) Acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra ( Polyfunctional monomers such as (meth) acrylates;
(Meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N′-methylenebisacrylamide, diacetone acrylamide, maleic acid amide, maleimide, etc. Acid amide compounds of
Vinyl compounds such as vinyl chloride, vinylidene chloride and fatty acid vinyl esters;
1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-neopentyl-1,3-butadiene, 2-chloro-1,3-butadiene, 2- Aliphatic conjugated dienes such as substituted linear conjugated pentadienes substituted with substituents such as cyano-1,3-butadiene, isoprene, alkyl groups, halogen atoms, cyano groups, linear and side chain conjugated hexadienes;
Vinyl cyanide compounds such as acrylonitrile and methacrylonitrile;
Fluorine atom-containing monomers such as trifluoroethyl (meth) acrylate and pentadecafluorooctyl (meth) acrylate;
4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1, Piperidine monomers such as 2,2,6,6-pentamethylpiperidine;
2- (2′-hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methacryloxyethylphenyl) -2H-benzotriazole UV-absorbing monomers such as 2-hydroxy-4- (methacryloyloxyethoxy) benzophenone and 2-hydroxy-4- (acryloyloxyethoxy) benzophenone;
Examples include dicaprolactone. These can be used alone or in combination of two or more.

  As an unsaturated compound having a functional group (β) and a carbon / carbon double bond, for example, a vinyl monomer similar to the vinyl monomer having a functional group (α), or the above hydroxyl group-containing vinyl type An isocyanate group-containing unsaturated compound obtained by reacting a monomer and a diisocyanate compound in an equimolar amount can be exemplified.

Further, as the unsaturated silane compound used in the method (II), CH ₂ ═CHSi
(CH ₃ ) (OCH ₃ ) ₂ , CH ₂ = CHSi (OCH ₃ ) ₃ , CH ₂ = CHSi (CH ₃ ) Cl ₂ , CH ₂ = CHSiCl ₃ , CH ₂ = CHCOO (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂ ,
_{CH 2 = CHCOO (CH 2)} 2 Si (OCH 3) 3, CH 2 = CHCOO (CH 2) 3 Si (CH 3) (OCH 3) 2, CH 2 = CHCOO (CH 2) 3 Si (OCH 3) ₃ , CH ₂ = CHCO
_{O (CH 2) 2 Si (} CH 3) Cl 2, CH 2 = CHCOO (CH 2) 2 SiCl 3, CH 2 = C
_{HCOO (CH 2) 3 Si (} CH 3) Cl 2, CH 2 = CHCOO (CH 2) 3 SiCl 3, CH 2 = C (CH 3) COO (CH 2) 2 Si (CH 3) (OCH 3) 2 , CH ₂ = C (CH ₃ ) CO
O (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CH ₂ ═C (CH ₃ ) COO (CH ₂ ) ₃ Si (CH ₃ ) (
_{OCH 3) 2, CH 2 =} C (CH 3) COO (CH 2) 3 Si (OCH 3) 3, CH 2 = C (CH 3) COO (CH 2) 2 Si (CH 3) Cl 2, CH 2 _{= C (CH 3) COO (} CH 2) 2 SiCl 3, CH 2 = C (CH 3) COO (CH 2) 3 Si (CH 3) Cl 2, CH 2 = C (CH 3) CO
O (CH ₂ ) ₃ SiCl ₃ ,

Can be mentioned. These can be used alone or in combination of two or more. Examples of other vinyl monomers copolymerized with the unsaturated silane compound include, for example, vinyl monomers having the functional group (α) exemplified in the method (I-1) and other vinyl monomers. A monomer etc. can be mentioned.

Other examples of the specific silyl group-containing polymer include specific silyl group-containing epoxy resins and specific silyl group-containing polyester resins. Examples of the specific silyl group-containing epoxy resin include epoxy groups in epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, aliphatic polyglycidyl ether, and aliphatic polyglycidyl ester. And aminosilanes having a specific silyl group, vinylsilanes, carboxysilanes, glycidylsilanes, and the like. The specific silyl group-containing polyester resin is
For example, it can be produced by reacting a carboxyl group or a hydroxyl group contained in a polyester resin with aminosilanes, carboxysilanes, glycidylsilanes having a specific silyl group.

The Mw of the specific silyl group-containing polymer is preferably 2,000 to 100,000, more preferably 4,000 to 50,000. The amount of the specific silyl group-containing polymer used is usually 2 to 900 parts by weight, preferably 10 to 400 parts by weight, more preferably 100 parts by weight of the complete hydrolysis condensate of the silane compound (c). 20 to 300 parts by weight. In this case, if the amount of the specific silyl group-containing polymer used is less than the above lower limit, the resulting coating film may be inferior in alkali resistance, whereas if it exceeds the above upper limit, the long-term weather resistance of the coating film decreases. Tend to. In addition, the said complete hydrolysis condensate is -OR < ⁴ > of the said silane compound (c).
The group is 100% hydrolyzed to become a SiOH group, and further completely condensed to a siloxane structure.

  Examples of the polymerization method for producing the specific silyl group-containing polymer include, for example, a method in which a monomer is added at once and polymerized, and after the polymerization of a part of the monomer, the remainder is continuously or Examples thereof include a method of intermittently adding or a method of continuously adding a monomer from the beginning of polymerization. Moreover, the polymerization method which combined these polymerization methods is also employable. A preferred polymerization method includes solution polymerization. As the solvent used for the solution polymerization, usual solvents can be used, and among them, ketones and alcohols are preferable. In this polymerization, known polymerization initiators, molecular weight regulators, chelating agents, and inorganic electrolytes can be used.

In the present invention, the specific silyl group-containing polymer can be used alone or in admixture of two or more obtained as described above.
The undercoat compositions (i) to (iv) are preferably co-condensed with the silane compound (c) and the specific silyl group-containing polymer in the presence of water and / or an organic solvent. In this case, the amount of water used is usually 0.2 mol or more, preferably about 0.3 to 2 mol, relative to 1 mol of -OR ⁴ in the silane compound (c). Here, the undercoat compositions (i) to (iv) are usually used in a form dissolved and dispersed in water and / or an organic solvent.

  The organic solvent is not particularly limited as long as each component can be mixed uniformly, and the organic solvents exemplified as the organic solvent (e2) can be used. Moreover, these organic solvents can be used individually or in mixture of 2 or more types.

The undercoating compositions (i) to (iv) may further comprise the catalyst (f), stability improver (g), inorganic compound powder and / or sol or Colloids can be blended. Examples of inorganic compounds that do not exhibit photocatalytic activity include AlGaAs, Al (OH) ₃ , Sb ₂ O ₅ , Si ₃ N ₄ , Sn—In ₂ O ₃ , Sb—In ₂ O ₃ , MgF,
CeF ₃ , CeO ₂ , 3Al ₂ O ₃ .2SiO ₂ , BeO, SiC, AlN, Fe, Co, C
_{o-FeOx, CrO 2, Fe} 4 N, BaTiO 3, BaO-Al 2 O 3 -SiO 2, Ba _{ferrite, SmCO 5, YCO 5, CeCO} 5, PrCO 5, Sm 2 CO 17, Nd 2 Fe 14 B, Al ₄ O ₃ , α-Si, SiN ₄ , CoO, Sb—SnO ₂ , Sb ₂ O ₅ , MnO ₂ , MnB, C
o ₃ O ₄ , Co ₃ B, LiTaO ₃ , MgO, MgAl ₂ O ₄ , BeAl ₂ O ₄ , ZrSiO ₄ ,
_{ZnSb, PbTe, GeSi, FeSi 2} , CrSi 2, CoSi 2, MnSi 1.73, M
g ₂ Si, β-B, BaC, BP, TiB ₂ , ZrB ₂ , HfB ₂ , Ru ₂ Si ₃ , TiO ₂ (
_{Rutile), TiO 3, PbTiO 3,} Al 2 TiO 5, Zn 2 SiO 4, Zr 2 SiO 4, 2MgO 2 -Al 2 O 3 -5SiO 2, Nb 2 O 5, Li 2 O-Al 2 O 3 - 4SiO _2, Mg ferrite, Ni ferrite, Ni-Zn ferrite, Li ferrite, and the like can be given Sr ferrite.

Further, the undercoating compositions (i) to (iv) may be blended with an ultraviolet absorber other than cerium oxide and zinc oxide, an ultraviolet stabilizer, and the like for the purpose of improving weather resistance and durability adhesion. Examples of the ultraviolet absorber include inorganic semiconductors such as TiO ₂ (not showing a photocatalytic function); organic ultraviolet absorbers such as salicylic acid, benzophenone, benzotriazole, cyanoacrylate, and triazine. Examples of the ultraviolet stabilizer include piperidine-based ultraviolet stabilizer.

  The undercoating compositions (i) to (iv) are blended with resins such as acrylic-urethane resins, epoxy resins, polyesters, acrylic resins, fluororesins, acrylic resin emulsions, epoxy resin emulsions, polyurethane emulsions, and polyester emulsions. May be.

  The total solid content concentration of the undercoat compositions (i) to (iv) is usually more than 0% by weight and 50% by weight or less, preferably 0.01% by weight or more and 40% by weight or less. It is adjusted as appropriate according to the coating method, coating film thickness, and the like.

[Laminate]
The laminate according to the present invention includes an organic base material, an intermediate layer formed on the organic base material, and a photocatalyst layer formed on the intermediate layer. The intermediate layer is formed using the undercoat composition, and the photocatalyst layer is formed using the visible light photocatalyst composition.

<Organic substrate>
As the organic substrate, phenol resin, epoxy resin, acrylic resin, polyester, polycarbonate (PC), polyethylene, polypropylene, acrylonitrile-butadiene-styrene resin (ABS resin), polymethyl methacrylate (PMMA), fluorine resin, thermoplastic Plastic molded products made of norbornene-based resins and the like and mixtures thereof;
Polyethylene, polypropylene, polyvinyl alcohol, polycarbonate (PC), polyethylene terephthalate (PET), polyurethane, polyimide, acrylic resin, polyvinyl chloride, polyvinyl fluoride, fluorine resin, thermoplastic norbornene resin, and mixtures thereof. , Plastic film and plastic sheet;
Examples include wood, paper, and non-woven fabric.

These substrates may be subjected to surface treatment in advance for the purpose of adjusting the foundation, improving adhesion, sealing the porous substrate, smoothing, patterning, and the like.
Surface treatments for plastic base materials include blast treatment, chemical treatment, degreasing, flame treatment, oxidation treatment, steam treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, ion treatment, etc .;
Polishing, sealing, insect repellent treatment, etc.
Examples of the surface treatment for the paper-based substrate include sealing and insect repellent treatment.

  Various primers may be applied in advance in order to ensure adhesion between the organic base material and the intermediate layer. The kind of primer is not specifically limited, What is necessary is just to have the effect | action which improves the adhesiveness of an organic base material and undercoat composition, and it selects according to the kind and intended purpose of an organic base material. The primer may be used alone or in admixture of two or more, and may be an enamel containing a coloring component such as a pigment or a clear containing no such coloring component.

As a primer, for example, alkyd resin, amino alkyd resin, epoxy resin,
Examples thereof include polyester, acrylic resin, urethane resin, fluororesin, acrylic silicon resin, acrylic resin emulsion, epoxy resin emulsion, polyurethane emulsion, and polyester emulsion. These primers can also be provided with various functional groups when adhesion between the organic base material and the coating film under severe conditions is required. Examples of such a functional group include a hydroxyl group, a carboxyl group, a carbonyl group, an amide group, an amine group, a glycidyl group, an alkoxysilyl group, an ether bond, and an ester bond. Further, the primer may contain an ultraviolet absorber, an ultraviolet stabilizer and the like.

<Method for producing laminate>
The laminate according to the present invention can be produced, for example, by the following method. First, the undercoat composition is formed on an organic substrate, and this coating film is dried to form an intermediate layer. Next, the visible light photocatalyst composition is formed on the intermediate layer, and the coating film is dried to form a photocatalyst layer.

  At this time, in order to accelerate the curing rate of the intermediate layer and the photocatalyst layer, a curing catalyst may be appropriately added to the undercoat composition and the visible light photocatalyst composition as necessary. In particular, when the coating film is dried at a low temperature of 100 ° C. or lower, it is preferable to use a curing catalyst. As the curing catalyst, the same compound as the catalyst (f) can be used. Further, in order to form an intermediate layer or a photocatalyst layer having a desired thickness, the undercoat composition and the visible light photocatalyst composition may be appropriately diluted with a solvent such as an organic solvent or water to form a film.

  As a method for forming a film for an undercoating composition or a visible light photocatalyst composition, for example, coating using a brush, roll coater, bar coater, flow coater, centrifugal coater, ultrasonic coater, (micro) gravure coater, etc .; Spray coating; spraying; screen process; electrodeposition; vapor deposition and the like.

  After forming the undercoat composition or visible light photocatalyst composition by these methods, the coating film is dried at room temperature or at a temperature of about 30 to 200 ° C., usually for 1 to 60 minutes. Alternatively, a photocatalytic layer can be formed.

  When the undercoat composition and the visible light photocatalyst composition used in the present invention are formed into a film, the dry film thickness is about 0.05 to 20 μm in the case of one application, and the dry film thickness is 0.1 in the case of two applications. A film of about ˜40 μm can be formed.

  The intermediate layer thus formed contains polysiloxane, and the photocatalyst layer contains the oxide semiconductor (a), polytitanoxane, and polysiloxane. The polysiloxane in the intermediate layer is considered to be derived from the silane compound (c) and the specific silyl group-containing polymer. The polytitanoxane of the photocatalyst layer is assumed to be derived from the titanium compound (b), and the polysiloxane is considered to be derived from the silane compound (c) and / or the organosiloxane oligomer (d).

The intermediate layer is located between the organic base material and the photocatalyst layer, and has an action of preventing the organic base material from being deteriorated by the photocatalytic action of the photocatalyst layer.
In the photocatalytic layer, it is desirable that the oxide semiconductor (a) is adjacent to the polytitanoxane and dispersed in the polysiloxane via the polytitanoxane. The oxide semiconductor (a) is considered to have an action of reducing the dispersed particle size of the oxide semiconductor (a) and an action of improving dispersibility by being bonded to the polysiloxane via the polytitanoxane. In addition, the polysiloxane has the effect of stabilizing the photocatalyst layer.

  The photocatalyst layer usually contains 1 to 100 parts by weight, preferably 2 to 90 parts by weight, more preferably 3 to 80 parts by weight of polytitanoxane with respect to 100 parts by weight of the solid content of the oxide semiconductor (a). It is desirable. When the content of polytitanoxane is less than the above lower limit, bond stability and dispersibility may be inferior, and when the upper limit is exceeded, the photocatalytic function with visible light may be impaired. Moreover, it is desirable that polysiloxane is contained in the coating film in an amount of usually 1 to 200 parts by weight, preferably 5 to 100 parts by weight, and more preferably 10 to 80 parts by weight. If the polysiloxane content is less than the above lower limit, sufficient dispersion stability may not be obtained, and if it exceeds the above upper limit, the photocatalytic function of the photocatalyst layer by visible light may deteriorate.

  The laminate according to the present invention is not particularly limited as long as the organic base material, the intermediate layer, and the photocatalyst layer are laminated in this order as described above. For example, the organic base material has a film thickness of 1000 μm or less. This film is useful as a visible light photocatalyst coating film. Such a visible light photocatalyst coating film can be used by being attached to the surface of various molded articles. Examples of the molded body include molded bodies made of organic materials such as lighting covers, joinery, wallpaper, and interior decorations, and molded bodies made of inorganic materials such as glass and mirrors.

  Moreover, the laminated body which concerns on this invention may laminate | stack the intermediate | middle layer and the photocatalyst layer in this order on the organic base material which consists of a molded object. As a molded object in this case, the molded object which consists of organic materials, such as a lighting cover, a fitting, a wallpaper, and an interior decoration, is mentioned.

[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by this Example. In the examples and comparative examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively, unless otherwise specified.

<Preparation of photocatalyst composition>
[Reference Example 1]
100 parts of sulfur-doped titanium dioxide having an absorbance at 400 nm of 0.15 measured by diffuse reflection spectrum measurement as an oxide semiconductor (a), and a tetramer of tetra-n-butoxytitanium as a titanium compound (b) (Japan) 56 parts of Soda Co., Ltd., trade name: B-10) and 700 parts of isopropyl alcohol as an organic solvent (e2) were put in a container, 600 parts of zirconia beads having a particle diameter of 0.3 mm were added, and 1 using a bead mill. Stirred and dispersed for hours.

  Next, after removing the beads, 96 parts of methyltrimethoxysilane as a silane compound (c) was added to the dispersion and stirred sufficiently, and then di-i-propoxy-ethyl acetoacetate aluminum 4 as a catalyst (f). And 12 parts of water (e1) were added and stirred while heating at 60 ° C. for 4 hours. Then, isopropyl alcohol was added to adjust the solid content concentration to about 10%, and the visible light photocatalyst composition (I-1 ) The transparency of this photocatalyst composition (I-1) was measured and evaluated by the following method. The results are shown in Table 1.

(Transparency evaluation)
The photocatalyst composition (I-1) was diluted with i-propyl alcohol to a solid content concentration of 5%. NO. 3 was applied on quartz glass so that the dry film thickness was 0.1 μm, and then dried at 150 ° C. for 30 minutes to prepare a photocatalyst layer. The haze of the photocatalyst layer was measured using a haze tester (haze-gard plus illuminant CIE-C) manufactured by Gardner, and the transparency of the photocatalyst layer was evaluated according to the following criteria.
AA: The haze is 1 or less.
A: The haze exceeds 1 and is 2 or less.
C: The haze exceeds 2.

[Reference Example 2]
100 parts of sulfur-doped titanium dioxide having an absorbance of 0.20 at 400 nm measured by diffuse reflectance spectrum measurement as an oxide semiconductor (a), tetramer of tetra-n-butoxytitanium as a titanium compound (b) (Japan) Soda Co., Ltd., trade name: B-10) 56 parts, organosiloxane oligomer (d) Mw of 10,000 organosiloxane oligomer (Nihon Unicar Co., Ltd., trade name: MAC-2101) 46 parts, 720 parts of isopropyl alcohol as an organic solvent (e2) was put in a container, 600 parts of zirconia beads having a particle diameter of 0.3 mm were added, and the mixture was stirred and dispersed for 1 hour using a bead mill.

  Next, after removing the beads, 96 parts of methyltrimethoxysilane as a silane compound (c) was added to the dispersion and stirred sufficiently, and then di-i-propoxy-ethyl acetoacetate aluminum 4 as a catalyst (f). And 12 parts of water (e1) were added and stirred while heating at 60 ° C. for 4 hours. Then, isopropyl alcohol was added to adjust the solid content concentration to about 10%, and the visible light photocatalyst composition (I-2 ) The transparency of this photocatalyst composition (I-2) was evaluated in the same manner as in Reference Example 1. The results are shown in Table 1.

[Reference Example 3]
Instead of using tetramer of tetra-n-butoxytitanium as a titanium compound (b) instead of tetramer of tetra-n-butoxytitanium (trade name: B-7, manufactured by Nippon Soda Co., Ltd.) Prepared a visible light photocatalyst composition (I-3) in the same manner as in Reference Example 2. The transparency of this photocatalyst composition (I-3) was evaluated in the same manner as in Reference Example 1. The results are shown in Table 1.

[Reference Example 4]
100 parts of sulfur-doped titanium dioxide having an absorbance of 0.20 at 400 nm measured by diffuse reflectance spectrum measurement as an oxide semiconductor (a), tetramer of tetra-n-butoxytitanium as a titanium compound (b) (Japan) Soda Co., Ltd., trade name: B-10) 56 parts, organosiloxane oligomer (d) Mw of 10,000 organosiloxane oligomer (Nihon Unicar Co., Ltd., trade name: MAC-2101) 46 parts, 720 parts of isopropyl alcohol as an organic solvent (e2) was put in a container, 600 parts of zirconia beads having a particle diameter of 0.3 mm were added, and the mixture was stirred and dispersed for 1 hour using a bead mill.

  Next, after removing the beads, isopropyl alcohol was added to adjust the solid content concentration to about 10% to obtain a visible light photocatalyst composition (I-4). The transparency of this photocatalyst composition (I-4) was evaluated in the same manner as in Reference Example 1. The results are shown in Table 1.

[Reference Examples 5 to 8]
Reference Example 1 except that 100 parts of oxygen-deficient titanium dioxide having an absorbance at 400 nm measured by diffuse reflection spectrum measurement of 0.20 was used instead of sulfur-doped titanium dioxide as the oxide semiconductor (a). Visible light photocatalyst compositions (I-5) to (I-8) were respectively prepared in the same manner as ˜4. The transparency of these photocatalyst compositions (I-5) to (I-8) was evaluated in the same manner as in Reference Example 1. The results are shown in Table 1.

[Reference Example 9]
100 parts of sulfur-doped titanium dioxide having an absorbance at 400 nm of 0.15 measured by diffuse reflection spectrum measurement as the oxide semiconductor (a), 96 parts of methyltrimethoxysilane as the silane compound (c), and an organic solvent (e2 ) 700 parts of isopropyl alcohol in a container, add 600 parts of zirconia beads having a particle diameter of 0.3 mm,
The mixture was stirred for 1 hour using a bead mill to obtain a visible light photocatalyst composition (Ia). However, when preparing the photocatalyst composition (Ia), an attempt was made to uniformly disperse the oxide semiconductor (a), but aggregation of the oxide semiconductor (a) occurred and a stable dispersion was obtained. I couldn't.

[Reference Example 10]
100 parts of sulfur-doped titanium dioxide having an absorbance at 400 nm of 0.20 as measured by diffuse reflection spectrum measurement as an oxide semiconductor (a), and an organosiloxane oligomer having an Mw of 10,000 as an organosiloxane oligomer (Japan) 46 parts by Unicar Co., Ltd., trade name: MAC-2101), 720 parts of isopropyl alcohol as an organic solvent (e2) are put in a container, 600 parts of zirconia beads having a particle diameter of 0.3 mm are added, and 1 hour using a bead mill. Stir and disperse.

  Next, after removing the beads, 96 parts of methyltrimethoxysilane as the silane compound (c), 4 parts of di-i-propoxyethylacetoacetate aluminum as the catalyst (f), and 12 parts of water (e1) are added to the dispersion. After adding and stirring while heating at 60 ° C. for 4 hours, isopropyl alcohol was added to adjust the solid content concentration to about 10% to obtain a visible light photocatalyst composition (Ib). This photocatalyst composition (Ib) was in a poorly dispersed state, and titanium dioxide was separated and settled.

[Reference Example 11]
Reference Example 9 except that 100 parts of oxygen defect type titanium dioxide having an absorbance at 0.20 nm measured by diffuse reflection spectrum measurement of 0.20 instead of sulfur-doped type titanium dioxide was used as the oxide semiconductor (a). In the same manner as above, a visible light photocatalyst composition (Ic) was prepared. However, this photocatalyst composition (Ic) also attempted to disperse the oxide semiconductor (a) uniformly, as in Reference Example 9, but the oxide semiconductor (a) aggregated, resulting in stable dispersion. No body was obtained.

[Reference Example 12]
Reference Example 10 except that 100 parts of oxygen defect type titanium dioxide having an absorbance at 0.20 nm measured by diffuse reflection spectrum measurement of 0.20 was used in place of sulfur-doped type titanium dioxide as the oxide semiconductor (a). In the same manner as above, a visible light photocatalyst composition (Id) was prepared. However, as in Reference Example 10, this photocatalyst composition (Id) was poorly dispersed, and titanium dioxide separated and settled.

[Reference Example 13]
Instead of sulfur-doped titanium dioxide having an absorbance at 400 nm of 0.20 measured by diffuse reflectance spectrum measurement as the oxide semiconductor (a), an anatase-type titanium oxide having an absorbance of less than 0.02 (Ishihara Sangyo ( A photocatalyst composition (Ie) was prepared in the same manner as in Reference Example 2 except that 100 parts by product (trade name: ST-01) were used. The transparency of this photocatalyst composition (Ie) was evaluated in the same manner as in Reference Example 1. The results are shown in Table 1.

<Preparation of coating composition for undercoat>
(Preparation of specific silyl group-containing polymer (A))
In a reactor equipped with a reflux condenser and a stirrer, 55 parts of methyl methacrylate, 5 parts of 2-ethylhexyl acrylate, 5 parts of cyclohexyl methacrylate, 10 parts of γ-methacryloxypropyltrimethoxysilane, 20 parts of glycidyl methacrylate, 4- (meth) 5 parts of acryloyloxy-2,2,6,6-tetramethylpiperidine, 75 parts of i-butyl alcohol, 50 parts of methyl ethyl ketone and 25 parts of methanol were added and mixed. Next, the mixture was heated to 80 ° C. with stirring, and a solution of 3 parts of azobisisovaleronitrile in 8 parts of xylene was added dropwise over 30 minutes, followed by reaction at 80 ° C. for 5 hours. Thereafter, 36 parts of methyl ethyl ketone was added and stirred to obtain a specific silyl group-containing polymer (A) (hereinafter referred to as “polymer (A)”) solution having a solid concentration of about 35% and Mw of 12,000.

(Preparation of specific silyl group-containing polymer (B))
The specific silyl group having a solid content concentration of about 35% and Mw of 13,000 is the same as the preparation of the specific silyl group-containing polymer (A) except that 20 parts of 2-hydroxyethyl methacrylate is used instead of glycidyl methacrylate. A solution containing polymer (B) (hereinafter referred to as “polymer (B)”) was obtained.

(Preparation of specific silyl group-containing polymer (C))
In a reactor equipped with a reflux condenser and a stirrer, 30 parts of methyl methacrylate, 10 parts of n-butyl acrylate, 10 parts of γ-methacryloxypropyltrimethoxysilane, 20 parts of glycidyl methacrylate, 4- (meth) acryloyloxy-2, 2,6,6-tetramethylpiperidine 10 parts, 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole 20 parts, i-butyl alcohol 75 parts, methyl ethyl ketone 50 parts and methanol 25 parts And mixed. Next, the mixture was heated to 80 ° C. with stirring, and a solution of 4 parts of azobisisovaleronitrile dissolved in 10 parts of xylene was added dropwise over 30 minutes, followed by reaction at 80 ° C. for 5 hours. Thereafter, 83 parts of methyl ethyl ketone was added and stirred to obtain a specific silyl group-containing polymer (C) (hereinafter referred to as “polymer (C)”) solution having a solid content concentration of 30% and Mw of 10,000.

[Preparation Example 1]
In a reactor equipped with a stirrer and a reflux condenser, 24 parts of methyltrimethoxysilane and 10 parts of dimethyldimethoxysilane as a silane compound, 118 parts of polymer (A) as a specific silyl group-containing polymer, and di-i- as a catalyst 2 parts of propoxy ethyl acetoacetate aluminum and 10 parts of i-propyl alcohol as an organic solvent were added and mixed. Next, this mixture was heated to 50 ° C. while stirring, and 6 parts of water was added dropwise over 30 minutes, followed by reaction at 60 ° C. for 4 hours. Thereafter, 2 parts of acetylacetone as a stability improver was added and stirred for 1 hour, and then cooled to room temperature. Further, 429 parts of methyl isobutyl ketone was added as a diluting solvent while stirring to obtain an undercoat coating composition (i-1) having a solid concentration of about 10%.

[Preparation Example 2]
After preparing a composition having a solid concentration of about 10% in the same manner as in Preparation Example 1, 100 parts of methyl isobutyl ketone-dispersed CeO ₂ (solid concentration: 10%) was added and stirred, and the solid concentration was about 10
% Undercoat coating composition (i-2) was obtained.

[Preparation Example 3]
After preparing a composition having a solid concentration of about 10% in the same manner as in Preparation Example 1, 300 parts of i-propyl alcohol dispersed colloidal silica (solid concentration: 10%) and methyl isobutyl ketone dispersed CeO ₂ (solid concentration) : 10%) 100 parts was added and stirred to obtain an undercoat coating composition (i-3) having a solid content concentration of about 10%.

[Preparation Example 4]
A composition having a solid content concentration of about 10% was prepared in the same manner as in Preparation Example 1 except that the silane compound, the specific silyl group-containing polymer, the organic solvent, water and the dilution solvent were changed to the compounds and amounts shown in Table 2. . To this composition, 300 parts of i-propyl alcohol-dispersed colloidal silica (solid content concentration: 10%) was added and stirred to obtain an undercoat coating composition (i-4) having a solid content concentration of about 10%.

[Preparation Example 5]
Undercoat coating composition for undercoating of about 10% solid content in the same manner as in Preparation Example 1 except that the silane compound, the specific silyl group-containing polymer, the organic solvent, water and the dilution solvent were changed to the compounds and amounts shown in Table 2. (I-5) was prepared.

[Preparation Example 6]
A composition having a solid content concentration of about 10% was prepared in the same manner as in Preparation Example 1 except that the silane compound, the specific silyl group-containing polymer, the organic solvent, water and the dilution solvent were changed to the compounds and amounts shown in Table 2. . To this composition, 300 parts of i-propyl alcohol-dispersed colloidal silica (solid content concentration: 10%) was added and stirred to obtain an undercoat coating composition (i-6) having a solid content concentration of about 10%.

[Examples 1 to 24]
Tables 3 to 4 show combinations of the organic base material, the undercoat coating composition, and the photocatalyst composition used in each example.

10 parts of i-propyl alcohol solution of dioctyltin dimaleate ester (solid content concentration of about 15%) is added as a curing catalyst to 100 parts of the coating composition for undercoat, and the well-stirred solution is dried on an organic substrate. The film was applied to a thickness of 1 μm and dried at 80 ° C. for 30 minutes to form an intermediate layer. When an acrylic resin film was used as the organic substrate, the intermediate layer was formed by drying at 50 ° C. for 60 minutes. In addition, when wood is used as the organic base material, a polyester emulsion is coated on the surface of the wood in advance to form a 5 μm coating film, and then an intermediate layer is formed on the coating film by the above method. .

  Next, 10 parts of i-propyl alcohol solution of dioctyltin dimaleate ester (solid content concentration of about 15%) as a curing catalyst was added to 100 parts of the photocatalyst composition, and the sufficiently stirred solution was added to the above intermediate layer. The film was applied to a dry film thickness of 1 μm and dried at 80 ° C. for 30 minutes to form a photocatalyst layer, thereby preparing a laminate comprising an organic substrate / intermediate layer / photocatalyst layer. In addition, when the acrylic resin film was used as an organic base material, it dried at 50 degreeC for 60 minutes, and formed the photocatalyst layer.

  The obtained laminate was evaluated for weather resistance according to the following method. Moreover, about the laminated body obtained in Examples 1-15, photocatalytic activity was also evaluated. The results are shown in Tables 3-4. In addition, it shows collectively about the transparency of the above-mentioned photocatalyst layer.

(1) Weather resistance:
The photocatalyst layer of the obtained laminate was irradiated with visible light from which ultraviolet rays of less than 400 nm were cut from a 400 W xenon lamp (USHIO INC.) Through a glass filter for 3000 hours. The layered product after irradiation with visible light was visually observed and evaluated according to the following criteria. Moreover, the tape peeling test was implemented using the cellophane tape (brand name: cello tape (R) No. 405) by Nichiban Co., Ltd., and the adhesion was evaluated according to the following criteria.
(Appearance) A: No change from before irradiation
C: Organic base material is whitened (adhesion) A: Photocatalyst layer and intermediate layer are not peeled off
B: Photocatalyst layer partially peeled
C: All photocatalyst layers are peeled off.
The obtained laminate was cut into 10 cm squares to produce test pieces. The test piece was placed in a 3 liter Tedlar bag, and the humidity in the Tedlar bag was adjusted to 60%. Next, 100 ppm of acetaldehyde was injected into the Tedlar bag to adjust the concentration of acetaldehyde after adsorption equilibrium to 100 ppm. Thereafter, the photocatalyst layer of this test piece was irradiated with visible light obtained by cutting UV light of less than 400 nm through a glass filter from a 400 W xenon lamp (manufactured by USHIO INC.) For 2 hours, and the residual amount of acetaldehyde after irradiation was measured by gas chromatography. Measured by graphy (FID detection) and evaluated according to the following criteria.
AA: 10 ppm or less A: More than 10 ppm, 50 ppm or less B: More than 50 ppm, 90 ppm or less C: More than 90 ppm [Comparative Examples 1 to 5]
Tables 3 to 4 show combinations of the organic base material, the undercoat coating composition and the photocatalyst composition used in each comparative example.

  In the same manner as in the above examples, an intermediate layer was formed on the surface of the organic substrate, and then a photocatalyst layer was formed on the intermediate layer. However, when not forming an intermediate | middle layer, according to the formation method of the said photocatalyst layer, the photocatalyst layer was formed directly on the surface of the organic base material.

  The thus-obtained laminate comprising an organic substrate / intermediate layer / photocatalyst layer, or a laminate comprising an organic substrate / photocatalyst layer was evaluated for weather resistance and photocatalytic activity in the same manner as in the above examples. . The results are shown in Tables 3-4.

  According to this invention, the laminated body which expresses a photocatalytic function on the surface can be obtained. If such a laminate is a film, various molded products such as lighting covers, joinery, wallpaper, interior decorations, glass, mirrors, etc. are applied to form molded products having a photocatalytic function. can do. Moreover, the said laminated body can be utilized as a molded object which has a photocatalytic function by using the molded object which consists of organic materials, for example, a lighting cover, a joinery, a wallpaper, the interior decoration etc. as a base material.

Claims (9)

A laminate comprising an organic substrate, an intermediate layer provided on the organic substrate, and a photocatalyst layer provided on the intermediate layer,
The photocatalytic layer is
(A) an oxide semiconductor having visible light photocatalytic activity,
(B) The following formula (1)
R ¹ _m Ti (OR ² ) _4-m (1)
(In the formula, R ¹ represents an organic group having 1 to 8 carbon atoms, and when two or more exist, they may be the same or different, and R ² represents an alkyl group having 1 to 6 carbon atoms, It represents an organic group selected from the group consisting of an acyl group having 1 to 6 carbon atoms and a phenyl group, and when there are a plurality of them, they may be the same or different, and R ¹ and R ² are the same Or m may be an integer of 0 to 3)
And at least one titanium compound selected from the group consisting of a titanium acylate represented by the above formula (1) and a derivative thereof, and (c) the following formula (2)
R ³ _n Si (OR ⁴ ) _4-n (2)
(In the formula, R ³ represents a monovalent organic group having 1 to 8 carbon atoms, and when a plurality of R ³ are present, they may be the same or different, and R ⁴ has 1 to 5 carbon atoms. Represents an alkyl group or an acyl group having 1 to 6 carbon atoms, and when there are a plurality of them, they may be the same or different, and R ³ and R ⁴ may be the same or different; n is an integer of 0 to 3)
A laminate formed of a visible light photocatalyst composition containing at least one silane compound selected from the group consisting of an organosilane represented by formula (1) and a derivative thereof. The visible light photocatalyst composition further has (d) a Si—O bond, a weight average molecular weight of 300 to 100,000, and a side chain and / or a terminal represented by the following formula (3):
_{^{- (R 5 O) p -}} (R 6 O) q -R 7 (3)
(Wherein R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 5 carbon atoms, R ⁷ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and p and q are p + q Is a number from 2 to 50)
The laminate according to claim 1, comprising an organosiloxane oligomer having a structure represented by: A laminate comprising an organic substrate, an intermediate layer provided on the organic substrate, and a photocatalyst layer provided on the intermediate layer,
The photocatalytic layer is
(A) an oxide semiconductor having visible light photocatalytic activity,
(B) The following formula (1)
R ¹ _m Ti (OR ² ) _4-m (1)
(In the formula, R ¹ represents an organic group having 1 to 8 carbon atoms, and when two or more exist, they may be the same or different, and R ² represents an alkyl group having 1 to 6 carbon atoms, It represents an organic group selected from the group consisting of an acyl group having 1 to 6 carbon atoms and a phenyl group, and when there are a plurality of them, they may be the same or different, and R ¹ and R ² are the same Or m may be an integer of 0 to 3)
And at least one titanium compound selected from the group consisting of a titanium alcoholate represented by the formula (1) and a titanium acylate represented by the formula (1) and a derivative thereof, and (d) a Si-O bond. Having a weight average molecular weight of 300 to 100,000, and having a side chain and / or a terminal represented by the following formula (3)
_{^{- (R 5 O) p -}} (R 6 O) q -R 7 (3)
(Wherein R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 5 carbon atoms, R ⁷ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and p and q are p + q Is a number from 2 to 50)
A laminate formed of a visible light photocatalyst composition containing an organosiloxane oligomer having a structure represented by:   The titanium compound (b) is at least one titanium selected from a titanium alcoholate condensate, a titanium alcoholate chelate condensate, a titanium acylate condensate and a titanium acylate chelate condensate. It is a compound, The laminated body in any one of Claims 1-3 characterized by the above-mentioned.   The laminate according to any one of claims 1 to 4, wherein the oxide semiconductor (a) is at least one oxide semiconductor selected from sulfur-doped titanium oxide and oxygen-deficient titanium oxide. The intermediate layer has the following formula (2)
R ³ _n Si (OR ⁴ ) _4-n (2)
(In the formula, R ³ represents a monovalent organic group having 1 to 8 carbon atoms, and when a plurality of R ³ are present, they may be the same or different, and R ⁴ has 1 to 5 carbon atoms. Represents an alkyl group or an acyl group having 1 to 6 carbon atoms, and when there are a plurality of them, they may be the same or different, and R ³ and R ⁴ may be the same or different; n is an integer of 0 to 3)
For at least one silane compound selected from the group consisting of organosilanes and derivatives thereof, and a silyl group-containing polymer having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group The laminate according to any one of claims 1 to 5, wherein the laminate is a layer formed from a coating composition.   It is a film which consists of a laminated body in any one of Claims 1-6, Comprising: The said organic base material is a film below 1000 micrometers in thickness, The visible light photocatalyst coating film characterized by the above-mentioned.   The molded object which has the visible light photocatalyst coating film of Claim 7 on the surface.   The molded object which consists of a laminated body in any one of Claims 1-6.