JP4771574B2 - Photocatalyst composition - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention shows the surface of a photocatalyst represented by titanium oxide, which is known to be applied to fields such as environmental purification, antifouling, and antifogging because it exhibits a substance decomposing action and a surface hydrophilizing action by light energy. Related to immobilization technology.
Specifically, the present invention relates to a photocatalyst composition that can easily immobilize a photocatalyst on the surface of a member. Further, the photocatalytic activity in which the photocatalyst is immobilized and / or controllability of water wettability (hydrophilicity, hydrophobicity) are provided. It is related with the member which has.
[0002]
[Prior art]
It is known that a photocatalyst represented by titanium oxide exhibits a substance decomposing action and a surface hydrophilizing action by light energy. When this photocatalyst is applied to fields such as environmental purification, antifouling, and antifogging, photocatalyst immobilization technology plays a very important role.
As a useful means of the photocatalyst immobilization technique, a coating of a photocatalyst on a substrate has attracted attention. Here, the following items are listed as the minimum conditions required for the photocatalyst immobilization technique by coating.
[0003]
(1) Firmly fixed without impairing photocatalytic activity.
(2) Stability so that the substrate and coating itself are not deteriorated by photocatalysis.
Furthermore, the following items are mentioned as preferable conditions for expanding the applicable range of the substrate to be immobilized.
(3) The immobilization conditions are mild (room temperature to about 100 ° C.).
(4) The coating film is excellent in transparency and forms a film with excellent durability, stain resistance, hardness, etc.
[0004]
By the way, various proposals have been made on the immobilization technique using a photocatalyst coating typified by titanium oxide.
For example, as a method for coating a substrate with a photocatalyst by a sputtering method or a sol-gel method, JP-A-60-044053 discloses a method for supporting a thin-film photocatalyst on a substrate by a sputtering method, JP-A-60-118236. The publication proposes a method of baking after applying an organic titanate. However, these methods have a drawback that they need to be fired at a high temperature for the production and crystallization of photocatalyst particles on the substrate, and it is difficult to fix a large area.
[0005]
As a method of using a photocatalyst sol that does not require photocatalyst particle generation and crystallization processes, for example, JP-A-6-278241 proposes a method of coating a base material with titanium oxide sol peptized in water. ing. Also in this method, since the titanium oxide sol does not have a film forming property under a mild condition, baking at a high temperature is necessary, and the formed film is brittle and easily broken to lose the catalytic effect.
[0006]
Furthermore, a method of mixing a photocatalyst in a resin paint and coating the resin paint on a substrate has been proposed. For example, in JP-A-9-59041, JP-A-9-188850, and JP-A-9-227831, a binder composed of a siloxane having a hydrolyzable silyl group such as an alkoxysilyl group is mixed with a photocatalyst, and coating is performed. A method for use as a composition has been proposed. However, when a siloxane having a hydrolyzable silyl group is used as a binder, the storage stability of the resulting photocatalyst coating composition is very poor, and in addition, the shrinkage strain when the binder forms a film by a condensation reaction is large. It was necessary to control the thickness very thinly, and there was a drawback that painting was very difficult.
[0007]
In other words, no technology has yet been developed that satisfies all of the conditions required for the above-mentioned fixing techniques (1) to (4) in the fixing technique using a photocatalyst coating.
[0008]
[Problems to be solved by the invention]
The subject of this invention is providing the photocatalyst composition which can form the coating film excellent in transparency, durability, hardness, etc. on mild conditions.
Another object of the present invention is to provide a photocatalyst composition capable of obtaining a member whose surface exhibits controllability of water wettability (hydrophilicity, hydrophobicity) and / or photocatalytic activity over a long period of time by light irradiation.
[0009]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the inventors have reached the present invention. That is, the present invention
1. A photocatalytic sol having a number average particle diameter of 400 nm or less and a silicone compound having two or more Si—H groups in one molecule (excluding a cyclic organosiloxane represented by the following general formula (1)) are mixed. And further comprising a polyfunctional vinyl compound and a platinum group compound. For coating film formation Photocatalyst composition.
[Chemical 3]
(However, n = 3-5 and R ₁ And R ₂ Is selected from the group consisting of hydrogen, alkyl groups, phenyl groups, alkoxyl groups, and vinyl groups. )
2. The photocatalyst composition as described in 1 above, wherein the silicone compound having two or more Si—H groups in the molecule includes a ladder structure represented by the general formula (1).
[Formula 4]
3. The photocatalyst composition as described in 1 above, wherein the silicone compound having two or more Si—H groups in the molecule is represented by the formula (2).
(R ² HSiO) a (R ² R ² SiO) b (R ² QSiO) c (R ² R ² R ² SiO _1/2 ) D
... (2)
(Wherein R ² Is a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, and an unsubstituted or alkyl group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms. Represents at least one hydrocarbon group selected from the group consisting of a C 6-20 aryl group substituted with a halogen atom, and Q is selected from the following groups (1) to (4): It is a group containing at least one functional group selected.
(1) Linear or branched alkyl group having 1 to 30 carbon atoms, cycloalkyl group having 5 to 20 carbon atoms, unsubstituted or alkyl group having 1 to 20 carbon atoms, 1 to 20 carbon atoms At least one selected from the group consisting of an aryl group having 6 to 20 carbon atoms substituted with at least one substituent selected from the group consisting of an alkoxy group and a halogen atom, and a fluoroalkyl group having 1 to 30 carbon atoms Hydrophobic group.
(2) At least one hydrophilic group selected from the group consisting of a carboxyl group and a salt thereof, a phosphoric acid group and a salt thereof, a sulfonic acid group and a salt thereof, and a polyoxyalkylene group.
(3) From epoxy group, acryloyl group, methacryloyl group, (cyclic) acid anhydride group, keto group, hydrazine residue, isocyanate group, isothiocyanate group, hydroxyl group, amino group, cyclic carbonate group, thiol group and ester group At least one reactive group selected from the group consisting of:
(4) At least one spectral sensitizing group.
a is an integer of 2 or more, and b and c are 0 or an integer of 1 or more. Further, (a + b + c) ≦ 10000. d is 0 or 2, and when d = 0, it represents a cyclic silicone compound, and when d = 2, it represents a chain silicone compound. The silicone compound may be a random copolymer or a block copolymer. )
4). 4. The photocatalyst composition as described in any one of 1 to 3 above, wherein the photocatalyst sol is a titanium oxide sol.
5. 5. The photocatalyst sol is a modified photocatalyst sol obtained by modifying a photocatalyst particle with a silicone compound having two or more Si—H groups in one molecule. Photocatalyst composition.
6). Polyamino compound, polyketo compound, polyisocyanate, polymethylol compound, polyalcohol, polysemicarbazide compound, polyhydrazide compound, polyepoxy compound, (meth) acrylic compound, polyvalent metal salt, polybasic acid 6. The photocatalyst composition as described in any one of 1 to 5 above, which contains a crosslinking agent.
7). 7. The photocatalyst composition as described in any one of 1 to 6 above, which contains a resin paint.
8). The member with which the photocatalyst composition in any one of said 1-7 was apply | coated.
It is.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
The photocatalyst sol that can be used in the photocatalyst composition of the present invention is a photocatalyst particle dispersed in water and / or an organic solvent at a solid content of 0.01 to 70% by weight, preferably 0.1 to 50% by weight. is there.
[0011]
The photocatalyst used as the photocatalyst sol is a valence electron when irradiated with light (excitation light) having energy (ie, short wavelength) larger than the energy gap between the conduction band and the valence band of the crystal. This refers to a substance capable of generating conduction electrons and holes by the excitation (photoexcitation) of electrons in the band, for example, TiO2, ZnO, SrTiO3, CdS, GaP, InP, GaAs, BaTiO3, BaTiO4, BaTi4O9, K2NbO3, Nb2O5. Fe2, O3, Ta2O5, K3Ta3Si2O3, WO3, SnO2, Bi2O3, BiVO4, NiO, Cu2O, SiC, MoS2, InPb, RuO2, CeO2 and the like, and at least one element selected from Ti, Nb, Ta, and V Layered oxide (Japanese Patent Laid-Open No. 62-74452, Japanese Patent Laid-Open No. -172535, JP-A-7-24329, JP-A-8-89799, JP-A-8-89800, JP-A-8-89804, JP-A-8-198061, JP-A-9-248465. And JP-A-10-99694 and JP-A-10-244165). Among these photocatalysts, those having an energy gap between the conduction band and the valence band of 0.5 to 5 eV, preferably 1 to 4 eV are suitably selected. In addition, a photocatalyst coated with a metal such as Pt, Rh, Ru, Nb, Cu, Sn, Ni, or Fe and / or a metal oxide added thereto or immobilized thereon, or a photocatalyst coated with porous calcium phosphate ( JP-A-11-267519) can also be used.
[0012]
The photocatalyst having a crystal particle diameter (primary particle diameter) of 1 to 200 nm, preferably 1 to 50 nm is suitably selected. Among these photocatalysts, TiO2 (titanium oxide) is preferable because it is harmless and has excellent chemical stability. Any of anatase, rutile, and brookite can be used as titanium oxide.
It is important that the photocatalyst used as the photocatalyst composition of the present invention is not a photocatalyst powder but a photocatalyst sol having a number average particle diameter of 400 nm or less.
[0013]
In general, powder composed of fine particles forms secondary particles in which single crystal particles (primary particles) are strongly agglomerated, so there are many surface properties to be wasted and dispersed into individual primary particles. Is very difficult. On the other hand, in the case of the photocatalyst sol, the photocatalyst particles are present in a form close to the primary particles without being dissolved, so that the surface characteristics can be used effectively. Therefore, in the photocatalyst composition of the present invention, the interaction between the photocatalyst particles present as the photocatalyst sol and the Si-H group-containing silicone compound used as the binder increases, and the coating film produced from the photocatalyst composition has transparency, hardness , Excellent durability and the like.
[0014]
As the photocatalyst sol that can be suitably used in the present invention, a mixture of primary particles and secondary particles having a number average particle diameter of 400 nm or less is desirable because the surface characteristics of the photocatalyst particles can be effectively utilized.
In addition, when a photocatalyst sol having a number average particle size of 200 nm or less is used, a transparent film can be obtained from the resulting modified photocatalyst sol, which is very preferable. More preferably, a photocatalyst sol having a thickness of 100 nm or less, 1 nm or more, and more preferably 20 nm or less, 3 nm or more is suitably selected.
[0015]
Conventionally, a numerical value simply displayed as a particle diameter in titanium dioxide or the like is mostly a primary particle diameter (crystal particle diameter), and is not a numerical value considering a secondary particle diameter due to aggregation.
[0016]
Taking a titanium oxide sol as an example of the photocatalyst sol, for example, a titanium oxide hydrosol in which water is substantially used as a dispersion medium and titanium oxide particles are peptized therein can be exemplified. (Here, substantially using water as a dispersion medium means that the dispersion medium contains about 80% or more of water.) The preparation of such a sol is well known and can be easily manufactured (specially JP-A-63-17221, JP-A-7-819, JP-A-9-165218, JP-A-11-43327, etc.). For example, metatitanic acid produced by heating and hydrolyzing an aqueous solution of titanium sulfate or titanium tetrachloride is neutralized with aqueous ammonia, and the precipitated hydrous titanium oxide is filtered, washed, and dehydrated to obtain aggregates of titanium oxide particles. It is done. Titanium oxide hydrosol can be obtained by peptizing the agglomerates under the action of nitric acid, hydrochloric acid, ammonia or the like and performing hydrothermal treatment. In addition, as titanium oxide hydrosols, titanium oxide particles are peptized under the action of acids and alkalis, and dispersion stabilizers are used as necessary without using acids or alkalis. A sol dispersed in water under water can also be used. Further, an anatase-type titanium oxide sol having excellent dispersion stability even in an aqueous solution having a pH near neutral and having a particle surface modified with a peroxo group can be easily obtained by the method proposed in JP-A-10-67516. it can.
[0017]
The titanium oxide hydrosol described above is commercially available as a titania sol. (For example, trade name “STS-02” / Ishihara Sangyo Co., Ltd./Japan, trade name “TO-240” / Tanaka Transcription Co., Ltd./Japan, etc.)
The solid content in the titanium oxide hydrosol is 50% by weight or less, preferably 30% by weight or less. More preferably, it is 30% by weight or less and 0.1% by weight or more. Such a hydrosol has a relatively low viscosity (20 ° C.) and may be, for example, in the range of about 2000 cps to 0.5 cps. Preferably it is 1000 cps-1 cps, More preferably, it is 500 cps-1 cps.
[0018]
Further, for example, a cerium oxide sol (JP-A-8-59235) or a layered oxide sol having at least one element selected from Ti, Nb, Ta, and V (JP-A-9-25123, JP-A-9-9). -67124, JP-A-9-227122, JP-A-9-227123, JP-A-10-259023, etc.) are also disclosed in the same manner as titanium oxide sol. .
[0019]
In addition, a titanium oxide organosol in which an organic solvent is substantially used as a dispersion medium and titanium oxide particles are dispersed therein is also commercially available. (For example, trade name “TKS-251” / Taika Co., Ltd.) Here, substantially using an organic solvent as a dispersion medium means that the dispersion medium contains about 80% or more of the organic solvent.
The photocatalyst composition of the present invention comprises the photocatalyst sol described above and a silicone compound having two or more Si—H groups in one molecule. In this case, when the photocatalyst and the Si—H group have some interaction such as a chemical bond, the coating film formed from the photocatalyst composition has high hardness and excellent durability.
[0020]
Examples of the silicone compound having two or more Si-H groups in one molecule that can be used in the photocatalyst composition of the present invention include two or more Si-H groups in the molecule and the general formulas (1) and (3 ), (4) and a silicone compound containing at least one structure of a silicone bond represented by (5).
[0021]
[Chemical 2]
[0022]
[Chemical 3]
[0023]
[Formula 4]
[0024]
[Chemical formula 5]
[0025]
(Wherein R ¹ Are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms. Or a hydrocarbon group composed of one or more selected from an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms substituted with a halogen atom, or the following (1) to (4) It is a group containing at least one functional group selected from the group consisting of.
[0026]
(1) Linear or branched alkyl group having 1 to 30 carbon atoms, cycloalkyl group having 5 to 20 carbon atoms, unsubstituted alkyl group having 1 to 20 carbon atoms, or 1 carbon atom An at least one hydrophobic group selected from the group consisting of an alkoxy group having -20 carbon atoms, an aryl group having 6-20 carbon atoms substituted with a halogen atom, and a fluoroalkyl group having 1-30 carbon atoms.
(2) At least one hydrophilic group selected from the group consisting of a carboxyl group or a salt thereof, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof, and a polyoxyalkylene group.
[0027]
(3) From epoxy group, acryloyl group, methacryloyl group, (cyclic) acid anhydride group, keto group, carboxyl group, hydrazine residue, isocyanate group, isothiocyanate group, hydroxyl group, amino group, cyclic carbonate group, ester group At least one reactive group selected from the group consisting of:
(4) At least one spectral sensitizing group. )
Among these, when a silicone compound having a ladder structure represented by the above general formula (1) is selected as a silicone compound having two or more Si-H groups in one molecule, it is formed from the photocatalyst composition of the present invention. The coating film is preferable because it is extremely excellent in terms of hardness, heat resistance, weather resistance, stain resistance, chemical resistance, and the like.
[0028]
The silicone compound containing the ladder structure and having two or more Si-H groups in one molecule is prepared by using trichlorosilane and / or organotrichlorosilane (and further dialkyldichlorosilane, if necessary) and water in a solvent such as dioxane. Is reacted at a low concentration of 0.1 to 40% by weight, preferably about 1 to 30% by weight, followed by hydrolysis and condensation polymerization, and then reacted with a silylating agent represented by the formula (6) as a terminal terminator Thereafter, it is obtained by introducing a functional group by a hydrosilylation reaction, which will be described later, if necessary.
[0029]
Z-SiR ^Three R ^Four R ^Five (6)
(R ^Three , R ^Four , R ^Five May be the same or different and may be a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or unsubstituted or A hydrocarbon group selected from an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms substituted with a halogen atom. Z represents a halogen atom or a hydroxyl group. )
[0030]
Here, it is also possible to use an alcohol in combination with the silylating agent represented by the above formula (6) as an end terminator or alternatively, but the alkoxysilyl group produced in this case is reactive with water. The storage stability of the resulting photocatalyst composition is extremely poor, which is not preferable.
[0031]
In addition to the ladder structure represented by the above formula (1), the dialkyl represented by the formula (3) is used as a silicone compound having two or more Si—H groups in one molecule used in the photocatalyst composition of the present invention. When a film having a silicone structure of 50% by weight or less, preferably 30% by weight or less is selected, the coating film formed from the photocatalyst composition of the present invention has hardness, heat resistance, weather resistance, stain resistance, It is preferable because it is excellent not only in chemical resistance and the like, but also in terms of film forming property, substrate adhesion, and the like. The silicone compound can be obtained by synthesizing a silicone compound having a ladder structure and having two or more Si—H groups in one molecule in the presence of the silicone compound represented by the following formula (19). The molecular structure can be obtained as follows.
[0032]
Y- (R ² R ² SiO) f- (R ² R ² Si) -Y (19)
(Wherein R ² Is a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, and an unsubstituted or alkyl group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms. Or at least one hydrocarbon group selected from the group consisting of an aryl group having 6 to 20 carbon atoms substituted with a halogen atom, Y is a hydroxyl group or an alkoxy group having 1 to 20 carbon atoms, It represents at least one hydrolyzable group selected from the group consisting of a hydroxyimino group, an enoxy group, an amino group, an amide group, an acyloxy group, an aminoxy group, and a halogen atom.
f represents an integer of 1 or more and 10,000 or less. )
[0033]
Another example of the silicone compound having two or more Si—H groups in one molecule that can be used in the photocatalyst composition of the present invention is a silicone compound represented by the formula (2).
(R ² HSiO) a (R ² R ² SiO) b (R ² QSiO) c (R ² R ² R ² SiO _1/2 ) D
... (2)
(Wherein R ² Is a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, and an unsubstituted or alkyl group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms. And at least one hydrocarbon group selected from the group consisting of C6-C20 aryl groups substituted with a halogen atom, and Q is selected from the group consisting of (1) to (4) below. It is a group containing at least one functional group selected.
[0034]
(1) Linear or branched alkyl group having 1 to 30 carbon atoms, cycloalkyl group having 5 to 20 carbon atoms, unsubstituted or alkyl group having 1 to 20 carbon atoms, 1 to 20 carbon atoms At least one selected from the group consisting of an aryl group having 6 to 20 carbon atoms substituted with at least one substituent selected from the group consisting of an alkoxy group and a halogen atom, and a fluoroalkyl group having 1 to 30 carbon atoms Hydrophobic group.
[0035]
(2) At least one hydrophilic group selected from the group consisting of carboxyl groups and salts thereof, phosphoric acid groups and salts thereof, sulfonic acid groups and salts thereof, and polyoxyalkylene groups.
(3) From epoxy group, acryloyl group, methacryloyl group, (cyclic) acid anhydride group, keto group, hydrazine residue, isocyanate group, isothiocyanate group, hydroxyl group, amino group, cyclic carbonate group, thiol group and ester group At least one reactive group selected from the group consisting of:
[0036]
(4) At least one spectral sensitizing group.
a is an integer of 2 or more, and b and c are 0 or an integer of 1 or more.
Further, (a + b + c) ≦ 10000.
d is 0 or 2, and when d = 0, it represents a cyclic silicone compound, and when d = 2, it represents a chain silicone compound. The silicone compound may be a random copolymer or a block copolymer. )
[0037]
Here, the silicone compound which has 2 or more of Si-H groups in 1 molecule which can be used for the photocatalyst composition of this invention mentioned above is represented by the following average composition formula (7) for convenience.
H _p R _q Q _r X _s SiO _{(4-pqrs) / 2} (7)
(In the formula, R is a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, and an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; It represents at least one hydrocarbon group selected from the group consisting of an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms substituted with a halogen atom.
Q represents a group containing at least one functionality-imparting group selected from the group consisting of the following (1) to (4).
[0038]
(1) Linear or branched alkyl group having 1 to 30 carbon atoms, cycloalkyl group having 5 to 20 carbon atoms, unsubstituted alkyl group having 1 to 20 carbon atoms, or 1 carbon atom An at least one hydrophobic group selected from the group consisting of an alkoxy group having -20 carbon atoms, an aryl group having 6-20 carbon atoms substituted with a halogen atom, and a fluoroalkyl group having 1-30 carbon atoms.
(2) At least one hydrophilic group selected from the group consisting of a carboxyl group or a salt thereof, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof, and a polyoxyalkylene group.
[0039]
(3) Epoxy group, acryloyl group, methacryloyl group, (cyclic) acid anhydride group, keto group, carboxyl group, hydrazine residue, isocyanate group, isothiocyanate group, hydroxyl group, amino group, cyclic carbonate group, thiol group, At least one reactive group selected from the group consisting of ester groups;
(4) At least one spectral sensitizing group.
X represents at least one hydrolyzable group selected from the group consisting of an alkoxy group having 1 to 20 carbon atoms, a hydroxyimino group, an enoxy group, an amino group, an amide group, an acyloxy group, an aminoxy group, and a halogen atom.
p is a value satisfying that there are two or more Si-H groups in one molecule;
0 ≦ q <4, 0 ≦ r <4, 0 ≦ s <4, and (p + q + r + s) <4. )
[0040]
When a silicone compound having two or more Si—H groups in one molecule used in the photocatalyst composition of the present invention is represented by the above average composition formula (7) for convenience, the functional group in the average composition formula (7) X (hydrolyzable group) deteriorates the storage stability of the photocatalyst composition of the present invention. Therefore, in the silicone compound having two or more Si—H groups in one molecule represented by the average composition formula (7) for convenience, it is preferable that the content of the functional group X is small. A more preferable form of the average composition formula (7) is a system that does not substantially contain the functional group X.
[0041]
Moreover, when what has a functional provision group containing group (Q) is selected as a silicone compound which has two or more Si-H groups in 1 molecule represented by the said average compositional formula (7), it is obtained by this invention. This is preferable because various functions can be imparted to the photocatalytic composition.
For example, as the functional group-containing group (Q), at least one hydrophilic group selected from the group consisting of a carboxyl group or a salt thereof, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof, or a polyoxyalkylene group When a compound having (2 in formula (7)) is selected, a silicone compound having two or more Si-H groups in one molecule has very good solubility or dispersion stability in water. Therefore, the photocatalyst composition obtained in the present invention can be used as an aqueous coating agent.
[0042]
Here, as preferable specific examples of the hydrophilic group, for example, a monovalent group including a polyoxyethylene group represented by the formula (8), a sulfonic acid group represented by the formula (9) or a salt thereof, Examples thereof include a monovalent group including a carboxyl group represented by the formula (10) and the formula (11) or a salt thereof.
-CH ₂ CH ₂ CH ₂ O (CH ₂ CH ₂ O) mR ⁷ (8)
(In the formula, m represents an integer of 1 to 1000. R ⁷ Represents a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms. )
[0043]
[Chemical 6]
[0044]
(In the formula, n represents an integer of 1 to 100. R ⁸ Represents a linear or branched alkyl group having 1 to 30 carbon atoms.
B represents a hydrogen atom, an alkali metal, ammonium, or a substituted ammonium represented by the formula (12).
HNR ⁹ R ^Ten R ¹¹ (12)
(R ⁹ , R ^Ten , R ¹¹ Each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with a hydroxyl group. ))
[0045]
[Chemical 7]
[0046]
(In the formula, B is the same as defined in formula (12).)
[0047]
[Chemical 8]
[0048]
(In the formula, B is the same as defined in formula (7).)
Further, for example, when a functional group-containing group (Q) having a monovalent hydrophobic group (1 in formula (7)) containing a fluoroalkyl group having 1 to 30 carbon atoms is selected, it can be obtained. It is possible to obtain a coating film with extremely high hydrophobicity from the photocatalyst composition obtained.
[0049]
Further, for example, as the functional group-containing group (Q), a monovalent group containing an epoxy group, a monovalent group containing an acryloyl group, a monovalent group containing a methacryloyl group, or a (cyclic) acid anhydride group Monovalent group, monovalent group containing keto group, monovalent group containing carboxyl group, monovalent group containing hydrazine residue, monovalent group containing isocyanate group, monovalent group containing thioisocyanate group A monovalent group containing a hydroxyl group, a monovalent group containing an amino group, a monovalent group containing a thiol group, a monovalent group containing a cyclic carbonate group, and a monovalent group containing an ester group. When a compound having at least one reactive group selected from the group ((3) in formula (7)) is selected, the photocatalyst composition of the present invention can be cross-linked by a cross-linking agent, and has excellent durability and the like. It is preferable because a coated film can be formed. Here, as the crosslinking agent, polyamino compounds, polyketo compounds, polyisocyanates, polymethylol compounds, polyalcohols, polysemicarbazide compounds, polyhydrazide compounds, polyepoxy compounds, (meth) acrylic compounds, polyvalent metal salts, polybasic acids And the combination thereof.
[0050]
In addition, for example, the functional group-containing group (Q) has a functional group ((4) in the formula (7)) composed of one or more monovalent organic groups including a spectral sensitizing dye. When selected, the coating film formed from the photocatalyst composition of the present invention exhibits a catalytic activity and a photoelectric conversion function not only by irradiation of light in the ultraviolet region but also in the visible region and / or infrared region. And can cause a superhydrophilic phenomenon.
[0051]
Here, the spectral sensitizing dye refers to various metal complexes and organic dyes having absorption in the visible light region and / or the infrared light region. Examples of such spectral sensitizing dyes include xanthene dyes, oxonol dyes, cyanine dyes, merocyanine dyes, rhodocyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes, phthalocyanine dyes (metal complexes). ), Porphyrin dyes (including metal complexes), triphenylmethane dyes, perylene dyes, coronene dyes, azo dyes, nitrophenol dyes, as well as JP-A 1-220380 and patent application publications Examples of the complex of ruthenium, osmium, iron, and zinc described in JP-A-5-504023 and metal complexes such as ruthenium red can be given.
[0052]
Among these spectral sensitizing dyes, those having absorption in a wavelength region of 400 nm or more and having the lowest empty orbit energy level (excited state redox potential) higher than the energy level of the photocatalyst conduction band are preferable. Selected. Such spectral sensitizing dyes are selected by measuring the absorption spectrum of light in the infrared, visible, and ultraviolet regions, and measuring the redox potential by an electrochemical method (T. Tani, Photogr. Sci. Eng., 14, 72 (1970); RWBerriman, etal., Ibid., 17.235 (1973); PBGilman Jr., ibid., 18,475 (1974), etc.), calculation of energy level using molecular orbital method (T. Tani, etal. , Photogr. Sci. Eng., 11, 129 (1967); DMSturmer, etal., Ibid., 17.146 (1973); ibid., 18, 49 (1974); RGSelby, etal., J. Opt. Soc. Am., 33, 1 (1970), etc.), and the presence or efficiency of electromotive force due to light irradiation of a Gratzel-type wet solar cell prepared with a photocatalyst and a spectral sensitizing dye, and the like.
[0053]
Examples of preferable spectral sensitizing dyes from such a viewpoint include a compound having a 9-phenylxanthene skeleton, a ruthenium complex containing a 2,2-bipyridine derivative as a ligand, a compound having a perylene skeleton, and a phthalocyanine metal. A complex, a porphyrin type metal complex, etc. can be mentioned.
The functional group-containing group (Q) can be used by selecting at least one kind from those described above.
[0054]
In the present invention, a silicone compound having two or more Si—H groups in one molecule represented by the above average composition formula (7) and having a functional group-containing group (Q) is, for example, the following average: The Si—H group-containing silicone compound represented by the composition formula (13) and the functional group-containing carbon-carbon unsaturated bond compound can be obtained by a hydrosilylation reaction.
H _{(p + r)} R _q X _s SiO _{(4-pqrs) / 2} (13)
(In the formula, R is a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms. Alternatively, it represents a hydrocarbon group composed of one or more selected from an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms substituted with a halogen atom.
[0055]
X represents at least one hydrolyzable group selected from the group consisting of an alkoxy group having 1 to 20 carbon atoms, a hydroxyimino group, an enoxy group, an amino group, an amide group, an acyloxy group, an aminoxy group, and a halogen atom.
0 <p <4, 0 ≦ q <4, 0 <r <4, 0 ≦ s <4, and (p + q + r + s) ≦ 4. )
[0056]
The carbon-carbon unsaturated bond compound used for introducing a hydrophilic group as a functional group to the Si—H group-containing silicone compound represented by the above formula (13) includes a carboxyl group or a salt thereof, and a phosphate group. Or olefins, allyl ethers, vinyl ethers, vinyl esters having at least one hydrophilic group selected from the group consisting of salts thereof, sulfonic acid groups or salts thereof, polyoxyalkylene groups, cyclic acid anhydrides, ( And (meth) acrylic acid esters and styrene derivatives.
[0057]
Preferred specific examples of the carbon-carbon unsaturated bond compound having a hydrophilic group include, for example, a polyoxyethylene group-containing allyl ether represented by the formula (14), a sulfonic acid group represented by the formula (15), or a salt thereof. An allyl ether having a monovalent group containing, 5-norbornene-2,3-dicarboxylic acid anhydride, allyl succinic acid anhydride and the like.
Here, when using a carbon-carbon unsaturated bond compound having an anhydride of carboxylic acid, the Si-H group-containing silicone compound of the formula (13) is hydrosilylated and then introduced into the silicone compound. By hydrolyzing the acid anhydride group in the presence or absence of a base, a silicone compound having two or more Si-H groups in one molecule having a carboxyl group or a salt thereof can be obtained.
CH ₂ = CHCH ₂ O (CH ₂ CH ₂ O) mR ⁷ (14)
(Where m and R ⁷ Is the same as defined in equation (8). )
[0058]
[Chemical 9]
[0059]
(Where n, R ⁸ , B are the same as defined in equation (9). )
Further, the Si—H group-containing silicone compound represented by the above formula (13) is added to a linear or branched alkyl group having 1 to 30 carbon atoms as a functional group and a cyclohexane having 5 to 20 carbon atoms. Hydrophobicity selected from an alkyl group, an unsubstituted or alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms substituted with a halogen atom Examples of the carbon-carbon unsaturated bond compound used for introducing a group include propylene, 1-butene, 1-hexene, 1-octene, isobutene, 2-methyl-1-butene, 2-hexene, cyclohexene, and 5-norbornene. Allyl esters such as allyl acetate, allyl acetate, allyl propionate, allyl 2-ethylhexanoate, allyl benzoate, and allyl methyl ether , Allyl ethers such as allyl ethyl ether, allyl-n-hexyl ether, allyl cyclohexyl ether, allyl-2-ethyl hexyl ether, allyl phenyl ether, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acryl (Meth) acrylates such as butyl acid, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl stearate, Carboxylic acid vinyl esters such as vinyl benzoate, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, styrene, (meth) acrylonitrile, Carbon atoms such as Tonsan esters - like carbon unsaturated bond compounds. Of these, terminal olefins, 5-norbornenes, allyl esters, and allyl ethers are preferred in terms of reactivity.
[0060]
Moreover, as a carbon-carbon unsaturated bond compound used when introduce | transducing a C1-C30 fluoroalkyl group into a Si-H group containing silicone compound represented by the said Formula (13) as a functional provision group, For example, olefins having a perfluoroalkyl group represented by the formula (16), allyl ethers, allyl esters, vinyl ethers, (meth) acrylic acid esters, and the like can be used.
-(CF ₂ ) _g CF _Three (16)
(In the formula, g represents an integer of 0 to 29.)
[0061]
Moreover, as a carbon-carbon unsaturated bond compound used for introducing a reactive group as a functional group to the Si—H group-containing silicone compound represented by the above formula (13), an epoxy group, (meth) acryloyl At least one reaction selected from the group consisting of a group, a (cyclic) acid anhydride group, a keto group, a carboxyl group, a hydrazine residue, an isocyanate group, an isothiocyanate group, a hydroxyl group, an amino group, a cyclic carbonate group, and an ester group Examples include olefins having a functional group, allyl ethers, allyl esters, vinyl ethers, vinyl esters, (meth) acrylic acid esters, styrene derivatives, and the like.
[0062]
Preferable specific examples of the carbon-carbon unsaturated bond compound having the reactive group include, for example, allyl glycidyl ether, glycidyl (meth) acrylate, allyl (meth) acrylate, diallyl ether, diallyl phthalate, vinyl (meth) acrylate. , Vinyl crotonic acid, ethylene glycol di (meth) acrylate, maleic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, 5-hexen-2-one, allyl isocyanate, allyl alcohol, ethylene glycol monoallyl Examples include ether, allylamine, allyl isothiocyanate, allyl semicarbazide, (meth) acrylic acid hydrazide, 4-allyloxymethyl-2-oxo-1,3-dioxolane, and the like.
[0063]
Moreover, as a carbon-carbon unsaturated bond compound used for introducing a spectral sensitizing dye into the Si—H group-containing silicone compound represented by the above formula (13), olefins having the aforementioned spectral sensitizing dye, Examples include allyl ethers, allyl esters, vinyl ethers, vinyl esters, (meth) acrylic acid esters, styrene derivatives and the like. These can be easily obtained, for example, by reacting the above-described carbon-carbon unsaturated bond compound having a reactive group with a spectral sensitizing dye having reactivity with the reactive group.
[0064]
For example, the reactive group of a carbon-carbon unsaturated bond compound having a reactive group is an epoxy group, (cyclic) acid anhydride, isocyanate group, thioisocyanate group, cyclic carbonate group, ester group, keto group, (meth) acryloyl. In the case of a group, it is a spectral sensitizing dye having at least one functional group selected from the group consisting of an amino group, a carboxyl group, a hydroxyl group, a hydrazine residue, and a (meth) acryloyl group. When the reactive group of the carbon-carbon unsaturated bond compound has an amino group, carboxyl group, hydroxyl group, hydrazine residue, or (meth) acryloyl group, an epoxy group, (cyclic) acid anhydride, isocyanate group, thioisocyanate At least selected from the group consisting of a group, a cyclic carbonate group, an ester group, a keto group, and a (meth) acryloyl group Spectral sensitizing dye having a single functional group.
[0065]
The reaction between the carbon-carbon unsaturated bond compound having the reactive group and the spectral sensitizing dye having reactivity thereto is performed by changing reaction conditions such as reaction temperature, reaction pressure, and solvent according to the type of each reactive group. Can be selected and implemented. At that time, from the viewpoint of the stability of the spectral sensitizing dye, the reaction temperature is preferably 300 ° C. or lower, more preferably 150 ° C. or lower and 0 ° C. or higher.
The hydrosilylation reaction of the functional group-containing carbon-carbon unsaturated bond compound and the Si—H group-containing silicone compound represented by the above average composition formula (13) is preferably performed in the presence of a catalyst and in the presence of an organic solvent. Or it can carry out by making a carbon-carbon unsaturated bond compound and the Si-H group containing silicone compound represented by an average composition formula (13) contact at 0-200 degreeC in absence.
[0066]
As the catalyst for the hydrosilylation reaction, a platinum group catalyst, that is, a ruthenium, rhodium, palladium, osmium, iridium, or platinum compound is suitable, and a platinum compound and a palladium compound are particularly suitable. Examples of platinum compounds include platinum chloride (II), tetrachloroplatinic acid (II), platinum chloride (IV), hexachloroplatinic acid (IV), hexachloroplatinum (IV) ammonium, hexachloroplatinum (IV) potassium, hydroxide Platinum (II), platinum dioxide (IV), dichloro-dicyclopentadienyl-platinum (II), platinum-vinylsiloxane complex, platinum-phosphine complex, platinum-olefin complex, platinum simple substance, alumina, silica and activated carbon The thing which carry | supported solid platinum is mentioned. Examples of the palladium compound include palladium (II) chloride, ammonium tetraamminepalladium (II) chloride, palladium (II) oxide and the like. The activity of these platinum group catalysts can be controlled by adding an activity inhibitor such as various organic nitrogen compounds, organic phosphorus compounds, and acetylene compounds as necessary after the hydrosilylation reaction.
[0067]
Examples of the organic solvent that can be used in the hydrosilylation reaction include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, cyclohexane, and heptane, esters such as ethyl acetate and n-butyl acetate, Ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethers such as tetrahydrofuran and dioxane, amides such as dimethylacetamide and dimethylformamide, halogen compounds such as chloroform, methylene chloride and carbon tetrachloride, dimethyl sulfoxide, nitrobenzene and the like A mixture of two or more of these may be mentioned.
[0068]
In the photocatalyst composition of the present invention, the solid content weight ratio of the photocatalyst sol (A) and the silicone compound (B) having two or more Si—H groups in one molecule is (A) / (B) = 0.1. /99.9 to 90/10, but preferably (A) / (B) = 1/99 to 80/20. When it is smaller than (A) / (B) = 0.1 / 99.9, the photocatalytic activity of the coating film formed from the photocatalyst composition becomes very small. From (A) / (B) = 90/10 When it becomes large, a coating film having good physical properties such as durability cannot be obtained from the photocatalyst composition.
[0069]
In the photocatalyst composition of the present invention, when a modified photocatalyst sol modified with a silicone compound having two or more Si—H groups in one molecule is used as the photocatalyst sol, Si— A photocatalytic composition composed of a silicone compound having two or more H groups is preferable because it enables a coating film having very excellent transparency to be formed.
As a method for obtaining the modified photocatalyst sol, the photocatalyst sol (A) described above and the silicone compound (B) having two or more Si—H groups in the same molecule as described above are used in a solid content weight ratio (A). / (B) = 20/80 to 99/1, preferably (A) / (B) = 50/50 to 95/5, and heated at 0 to 200 ° C., preferably 10 to 80 ° C. Can be obtained.
[0070]
For example, when a titanium oxide sol is used as the photocatalyst sol, the reduction of Ti—OH groups is caused by 3630 to 3640 cm in the IR spectrum by the above modification operation. ^-1 Observed as a decrease in absorption.
For the purpose of further improving the strength of the coating film formed from the photocatalyst composition of the present invention, it is preferable to use a photocatalyst composition to which a polyfunctional vinyl compound and a platinum group compound are added as a crosslinking agent. In this case, a crosslinked structure is formed by an addition reaction between the Si—H group and the polyfunctional vinyl compound present in the photocatalyst composition using a white metal compound as a catalyst. Moreover, the coating film formed from this photocatalyst composition in order to accelerate | stimulate this crosslinking reaction is normally 20-200 degreeC, Preferably it heats at 30-120 degreeC.
[0071]
Here, examples of the white metal compound include a white metal catalyst used as a catalyst for the hydrosilylation reaction described above.
The polyfunctional vinyl compound is a compound having two or more vinyl groups in one molecule. For example, vinyl silicones, olefins, allyl ethers, allyl esters, vinyl ethers, vinyl esters, (meta ) Acrylic acid esters, styrene derivatives
Etc. Among these, vinyl silicones represented by the following formulas (17) and (18) are preferable from the viewpoint of compatibility with the photocatalyst composition of the present invention.
[0072]
CH ₂ = CH- (R ² R ² SiO) e- (R ² R ² Si) -CH = CH ₂ (17)
(Wherein R ² Is the same as defined in equation (2). e represents an integer of 1 or more and 10,000 or less. )
(R ² R ² SiO) i (R ² YSiO) j (R ² R ² R ² SiO _1/2 ) K (18)
(Wherein R ² Is the same as defined in equation (2). Y represents a vinyl group.
j is an integer of 2 or more, and i is 0 or an integer of 1 or more.
Further, (i + j) ≦ 10000.
k is 0 or 2, and when k = 0, it represents a cyclic vinyl silicone compound, and when k = 2, it represents a chain vinyl silicone compound. The vinyl silicone compound may be a random copolymer or a block copolymer. )
[0073]
In the photocatalyst composition of the present invention, the resin coating is used in accordance with the purpose. The solid content weight ratio of the photocatalyst sol (A) to the resin coating (C) (A) / (C) = 5/95 to 95/5, preferably (A ) / (C) = 20/80 to 90/10.
[0074]
The resin coating is not particularly limited. For example, oil-based coatings, lacquers, solvent-based synthetic resin coatings (acrylic resins, epoxy resins, urethane resins, fluororesins, silicon-acrylic resins, alkyd resins, aminoalkyds, etc. Resin-based, vinyl resin-based, unsaturated polyester resin-based, chlorinated rubber-based), water-based synthetic resin coatings (emulsion-based, water-based resin-based, etc.), solvent-free synthetic resin coatings (powder coatings, etc.), inorganic coatings, electrical insulation A paint etc. can be illustrated.
[0075]
Among these resin coatings, silicon resins and fluorine resins that are hardly decomposable with respect to the photocatalyst, and a combined system of silicon resin and fluorine resin are preferably used.
Examples of such silicon-based resins include alkoxysilanes and / or organoalkoxysilanes and their hydrolysis products (polysiloxanes) and / or colloidal silica, and acrylic-silicon resins having a silicon content of 1 to 80% by weight. , Epoxy-silicone resin, urethane-silicone resin, alkoxysilane and / or organoalkoxysilane, a hydrolysis product thereof (polysiloxane) and / or a resin containing 1 to 80% by weight of colloidal silica. These silicon resins may be any of a solvent-soluble type, a dispersion type, and a powder type, and may contain additives such as a crosslinking agent and a catalyst.
[0076]
Examples of the fluorine-based resin include PTFE, polyvinylidene fluoride, and acrylic-fluorine resin, epoxy-fluorine resin, urethane-fluorine resin, fluoroolefin, and carbon-carbon unsaturated carbon having a fluorine content of 1 to 80% by weight. Examples thereof include copolymers with compounds (vinyl ethers, vinyl esters, allyl compounds, (meth) acrylic acid esters, etc.). These fluorine-based resins may be any of a solvent-soluble type, a dispersion type, and a powder type, and may contain additives such as a crosslinking agent and a catalyst.
[0077]
In addition, a silicone compound having two or more Si-H groups in one molecule used in the present invention is an epoxy group, an acryloyl group, a methacryloyl group, a (cyclic) acid anhydride group, a keto group, a carboxyl group, or a hydrazine residue. , Isocyanate group, thioisocyanate group, hydroxyl group, amino group, cyclic carbonate group, thiol group, and at least one reactive group selected from the group consisting of ester groups, It is preferable to use for the photocatalyst composition a resin paint containing a reactive group and a reactive functional group of a silicone compound having two or more -H groups.
[0078]
In addition, the photocatalyst composition of the present invention contains components that are usually added to and blended with paints as necessary, for example, pigments, fillers, dispersants, light stabilizers, wetting agents, thickeners, rheology control agents, antifoaming agents. Plasticizers, film-forming aids, rust inhibitors, dyes, preservatives, and the like can be selected, combined, and blended according to their respective purposes.
In the present invention, as a method for obtaining a member from the photocatalyst composition, the photocatalyst composition is applied to a substrate, dried, and then subjected to heat treatment or the like as necessary, so that it becomes hydrophobic or hydrophilic by irradiation with light and / or. A member having photocatalytic activity and further a photoelectric conversion function can be obtained. Examples of the coating method include spray spraying, flow coating, roll coating, brush coating, dip coating, spin coating, screen printing, casting, gravure printing, flexographic printing, and the like.
[0079]
A member such as a substrate having a coating film formed from the photocatalyst composition of the present invention is light having an energy higher than the band gap energy of the photocatalyst contained therein (when the photocatalyst composition has a spectral sensitizing dye, Irradiation with light (including light absorbed by the spectral sensitizing dye) exhibits hydrophobicity or hydrophilicity and / or photocatalytic activity, and further a photoelectric conversion function.
In the present invention, as a light source including light having energy higher than the band gap energy of the photocatalyst and absorption light of the spectral sensitizing dye, in addition to light obtained in a general residential environment such as sunlight and indoor lighting, Light such as black light, xenon lamp and mercury lamp can be used.
[0080]
The member provided by the present invention, which has photocatalytic activity such as organic matter decomposition, exhibits various functions such as antibacterial, antifouling, deodorant, NOx decomposition, and the like, such as environmental purification of air, water, etc. Can be used for applications.
The above-mentioned member provided by the present invention, wherein a hydrophilic member (hydrophilic structural material or hydrophilic property) having a contact angle with water at 20 ° C. of 60 ° or less (preferably 10 ° or less) by light irradiation. The film and the substrate coated with the hydrophilic film) can be applied to anti-fogging technology for preventing fogging of mirrors and glass, and further to antifouling technology and antistatic technology for building exteriors, etc. , Window glass, mirrors, lenses, goggles, covers, insulators, building materials, building exteriors, building interiors, structural members, exterior and painting of vehicles, exteriors of machinery and articles, various display devices, lighting devices, housing equipment, tableware, It can be used for kitchen appliances, household electrical appliances, magnetic optical recording media, optical recording media and the like.
[0081]
A hydrophobic member (hydrophobic structural material or hydrophobic member) according to the present invention, wherein the contact angle with water at 20 ° C. is 70 ° or more (preferably 90 ° or more) by light irradiation. Membranes and base materials coated with the hydrophobic membranes) to provide drip-proofing and drainage properties, antifouling technology using water-based soil adhesion prevention and running water washability, and further to ice and snow prevention technology, etc. Window glass, windshield glass, mirrors, lenses, goggles, covers, insulators, building materials, building exteriors, building interiors, structural members, vehicle exteriors and coatings, machinery and article exteriors, various display devices It can be used for applications such as lighting equipment, housing equipment, tableware, kitchenware, household electrical appliances, roofing materials, antennas, power transmission lines, ice and snow slides.
[0082]
The member provided by the present invention and having a photoelectric conversion function can express functions such as power conversion of solar energy, and is used for an optical semiconductor electrode used in a (wet) solar cell or the like. Can be used for
In addition, the member provided by the present invention whose wettability with water is changed (change from hydrophobic to hydrophilic, or from hydrophilic to hydrophobic) by light irradiation is applied to an offset printing original plate or the like. Very useful for application.
[0083]
DETAILED DESCRIPTION OF THE INVENTION
The measuring methods of various physical properties used in the examples are as follows.
(1) Number average particle size
The number average particle diameter was measured using a wet particle size analyzer (Microtrack UPA-9230 manufactured by Nikkiso Co., Ltd.).
In addition, the number average particle size of titanium oxide organosol (trade name: TKS-251, manufactured by Teika Co., Ltd.) using toluene as a dispersion medium is 5 weights with water after solvent replacement of toluene of the dispersion medium with butyl cellosolve. % And measured by the above method.
[0084]
(2) Molecular weight
It calculated | required from the dimethyl silicone sample calibration curve using the gel permeation chromatography.
(3) Infrared absorption spectrum
The infrared absorption spectrum was measured with JASCO FT / IR-410.
[0085]
▲ 4 ▼ Coating hardness
The hardness of the coating film was determined as pencil hardness (scratch of the coating film) according to JIS-K5400.
The coating film hardness after UV irradiation was measured by measuring the UV intensity of the coating film with a UV intensity meter (UVR-2 (light receiving part: UD-36 (310-400 nm) manufactured by Topcon Corporation)) of 1 mW / cm. ² It was carried out by irradiating with a light of black light (FL20S BLB manufactured by Toshiba Lighting & Technology Co., Ltd.) adjusted for 3 days and then measuring by the above method.
[0086]
▲ 5 ▼ Water contact angle of parts
The contact angle of water of the member is measured by using a contact angle meter (CA-X150, manufactured by Kyowa Interface Science Co., Ltd.) and measuring the contact angle one minute after dropping a drop of deionized water in a 20 ° C environment. did.
The change in contact angle of the member with water due to ultraviolet irradiation was measured by measuring the member with an ultraviolet intensity meter (UVR-2 manufactured by Topcon Corporation (light receiving part: UD-36 (310 to 400 nm)) having an ultraviolet intensity of 1 mW / cm. ² After irradiating with light of a black light (FL20S BLB manufactured by Toshiba Lighting & Technology Co., Ltd.) adjusted for 3 days, the contact angle of water of each member was measured by the above method. The one where the contact angle of water is smaller is hydrophilic.
[0087]
(6) Photocatalytic activity of members
The photocatalytic activity of the member was measured with an ultraviolet intensity meter (UVR-2 (light receiving part: UD-36 (310 to 400 nm) manufactured by Topcon Co., Ltd.)) after applying a 5 wt% ethanol solution of methylene blue to the member. UV intensity is 1mW / cm ² After irradiating with light of a black light (FL20S BLB manufactured by Toshiba Lighting & Technology Co., Ltd.) adjusted for 5 days, the degree of decomposition of methylene blue was evaluated.
A: Methylene blue is completely decomposed.
Δ: Slightly methylene blue blue remains.
X: Methylene blue was hardly decomposed.
[0088]
[Reference Example 1]
Synthesis of silicone compound (1) having two or more Si-H groups in one molecule.
After adding 26.0 g of methyltrichlorosilane to 235 g of dioxane in a reactor having a reflux condenser, a thermometer and a stirring device, the mixture was stirred at room temperature for about 10 minutes. A mixed solution consisting of 4.7 g of water and 18.8 g of dioxane was added dropwise thereto over about 30 minutes while maintaining the reaction solution at 10 to 15 ° C., followed by further stirring at 10 to 15 ° C. for about 30 minutes, The reaction solution was heated to 60 ° C. and stirred for 3 hours. The resulting reaction solution was cooled to 25-30 ° C., 235 g of toluene was added dropwise over about 30 minutes, and then the reaction solution was heated again to 60 ° C. and stirred for 2 hours.
[0089]
The obtained reaction solution was cooled to 10 to 15 ° C., 25.1 g of dimethylchlorosilane was added, and a mixture of 1.56 g of water and 6.24 g of dioxane was added while maintaining the temperature at 10 to 15 ° C. Added over minutes. Thereafter, stirring was further continued at 25-30 ° C. for about 2 hours, and then the reaction solution was heated to 60 ° C. and stirred for 2 hours. A silicone compound (1) having a ladder skeleton having a weight average molecular weight of 5300 and having two or more Si—H groups in one molecule is obtained by distilling off the solvent from the obtained reaction solution at 60 ° C. under reduced pressure. Obtained. (The obtained compound (1) has an absorption (1118 cm) derived from stretching vibration of the ladder skeleton in the IR spectrum. ^-1 And 1048 cm ^-1 ) Was observed. )
[0090]
After dissolving 0.21 g of the obtained compound (1) in 8 g of butyl cellosolve, 12.0 ml of hydrogen gas was generated at 22 ° C. when 8 ml of 1N sodium hydroxide aqueous solution was added. The amount of Si—H groups in the compound (1) determined from the amount of hydrogen produced was 2.4 mmol / g.
[0091]
[Reference Example 2]
Synthesis of silicone compound (2) having two or more Si-H groups in one molecule.
94 g of dioxane in a reactor equipped with a reflux condenser, a thermometer and a stirrer, 26.0 g of methyltrichlorosilane, 8.7 g of phenyltrichlorosilane and a terminal silanol dimethylsiloxane copolymer (trade name: DMS-S15, Chisso Corporation) (Production, weight average molecular weight 2000) 2.0 g was added, followed by stirring at room temperature for about 10 minutes. A liquid mixture consisting of 5.8 g of water and 23.2 g of dioxane was added dropwise thereto over about 30 minutes while maintaining the reaction liquid at 10 to 15 ° C., followed by further stirring at 10 to 15 ° C. for about 30 minutes, The reaction solution was heated to 60 ° C. and stirred for 3 hours. The resulting reaction solution was cooled to 25-30 ° C., 376 g of toluene was added dropwise over about 30 minutes, and then the reaction solution was again heated to 60 ° C. and stirred for 2 hours.
[0092]
The obtained reaction solution was cooled to 10 to 15 ° C., 25.3 g of dimethylchlorosilane was added, and then a mixture of 1.9 g of water and 7.7 g of dioxane was added for about 30 minutes while maintaining the temperature at 10 to 15 ° C. Added over time. Thereafter, stirring was further continued at 25-30 ° C. for about 2 hours, and then the reaction solution was heated to 60 ° C. and stirred for 2 hours. By distilling off the solvent from the obtained reaction solution under reduced pressure at 60 ° C., the weight average molecular weight is 10800, the ladder skeleton and the dimethyl silicone skeleton are included, and two or more Si—H groups are contained in one molecule. A silicone compound (2) was obtained. (The obtained compound (2) has an absorption (1118 cm) derived from stretching vibration of the ladder skeleton in the IR spectrum. ^-1 And 1053 cm ^-1 ) And absorption derived from the stretching vibration of the dimethylsiloxane skeleton (1090 cm) ^-1 ) Was observed. )
[0093]
After 0.30 g of the obtained compound (2) was dissolved in 8 g of butyl cellosolve, 15.0 ml of hydrogen gas was generated at 27 ° C. when 8 ml of 1N sodium hydroxide aqueous solution was added. The amount of Si—H groups in the compound (2) determined from the amount of hydrogen produced was 2.0 mmol / g.
[0094]
[Reference Example 3]
Synthesis of silicone compound (3) having two or more Si-H groups in one molecule.
After adding 51.6 g of methyltrichlorosilane and 25.9 g of trichlorosilane to 1500 g of dioxane in a reactor having a reflux condenser, a thermometer and a stirring device, the mixture was stirred at room temperature for about 10 minutes. A mixture of 14.5 g of water and 58.0 g of dioxane was added dropwise thereto over about 30 minutes while maintaining the reaction solution at 10 to 15 ° C., followed by further stirring at 10 to 15 ° C. for about 30 minutes, The temperature of the reaction solution was raised to 60 ° C. and stirred for 3 hours.
[0095]
The obtained reaction solution was cooled to 10 to 15 ° C., 65.5 g of trimethylchlorosilane was added, and a mixture of 5.4 g of water and 21.7 g of dioxane was added for about 30 minutes while maintaining the temperature at 10 to 15 ° C. Added over time. Subsequently, stirring was continued at 25 to 30 ° C. for about 2 hours, and then the temperature of the reaction solution was further raised to 60 ° C. and stirred for 3 hours. Silicone compound (3) having a ladder skeleton with a weight average molecular weight of 3800 and having two or more Si-H groups in one molecule by distilling off the solvent from the resulting reaction solution at about 60 ° C. under reduced pressure. Got. (The obtained compound (3) has absorption (1128 cm) derived from stretching vibration of the ladder skeleton in the IR spectrum. ^-1 And 1053 cm ^-1 ) Was observed. )
[0096]
After 0.16 g of the obtained compound (3) was dissolved in 8 g of butyl cellosolve, 2 ml of hydrogen gas was generated at 28 ° C. when 8 ml of 1N aqueous sodium hydroxide solution was added. The amount of Si—H groups in the compound (3) determined from the amount of hydrogen produced was 4.9 mmol / g.
[0097]
[Reference Example 4]
Synthesis of a silicone compound (4) having two or more Si-H groups in one water-dispersible molecule.
10 g of the compound (3) synthesized in Reference Example 3 and 20 g of tetrahydrofuran were added to a reactor having a reflux condenser, a thermometer, and a stirring device, and kept at 30 ° C. with stirring. After adding 0.2 g of a 2.2 wt% xylene solution of a platinum-divinyltetramethyldisiloxane complex to this, a compound represented by the following formula (20) (trade name: Adeka Soap SE-10N, Asahi Denka ( Co., Ltd.) 1.5 g of tetrahydrofuran and 14.5 g of tetrahydrofuran was added at 30 ° C. over about 2 hours, and stirring was further continued at 30 ° C. for 3 hours. A tetrahydrofuran solution of the silicone compound (4) having two or more H groups was obtained.
[0098]
After 1.75 parts of the resulting tetrahydrofuran solution of the compound (4) was dissolved in 8 parts of butyl cellosolve, 8 ml of 1N aqueous sodium hydroxide solution was added to generate 43.4 ml of hydrogen gas at 22 ° C. The amount of Si—H groups in the tetrahydrofuran solution of the Si—H group-containing compound (3) having a ladder skeleton determined from the hydrogen generation amount was 0.96 mmol / g (Si—H converted per solid content of the compound (4)). The base amount was about 4.4 mmol / g).
[0099]
[Chemical Formula 10]
[0100]
[Reference Example 5]
Synthesis of silicone compound (5) containing no Si-H group.
After adding 26.0 g of methyltrichlorosilane to 235 g of dioxane in a reactor having a reflux condenser, a thermometer and a stirring device, the mixture was stirred at room temperature for about 10 minutes. A mixed solution consisting of 4.7 g of water and 18.8 g of dioxane was added dropwise thereto over about 30 minutes while maintaining the reaction solution at 10 to 15 ° C., followed by further stirring at 10 to 15 ° C. for about 30 minutes, The reaction solution was heated to 60 ° C. and stirred for 3 hours. The resulting reaction solution was cooled to 25-30 ° C., 235 g of toluene was added dropwise over about 30 minutes, and then the reaction solution was heated again to 60 ° C. and stirred for 2 hours.
[0101]
The obtained reaction solution was cooled to 10 to 15 ° C., 21.6 g of trimethylchlorosilane was added, and then a mixed solution composed of 1.56 g of water and 6.24 g of dioxane was maintained while maintaining the temperature at 10 to 15 ° C. Added over minutes. Thereafter, stirring was further continued at 25-30 ° C. for about 2 hours, and then the reaction solution was heated to 60 ° C. and stirred for 2 hours. The solvent was distilled off from the resulting reaction solution at 60 ° C. under reduced pressure to obtain a silicone compound (5) having a ladder skeleton having a weight average molecular weight of 7100 and containing no Si—H group. (The obtained compound (5) has an absorption (1120 cm) derived from stretching vibration of the ladder skeleton in the IR spectrum. ^-1 And 1040 cm ^-1 ) Was observed. )
[0102]
[Reference Example 6]
Synthesis of modified titanium oxide organosol (6).
Titanium oxide organosol (trade name: TKS-251, manufactured by Teika Co., Ltd., dispersion medium: toluene, TiO2 concentration 20% by weight, number average particle diameter 80 nm) in a reactor having a reflux condenser, a thermometer and a stirrer 8 g of a 20 wt% toluene solution of the compound (1) synthesized in Reference Example 1 was added to 32 g of an average crystallite diameter of 6 nm (catalog value) at 50 ° C. over about 30 minutes, and further stirred for 6 hours. By continuing, a modified titanium oxide organosol (6) having very good dispersibility was obtained. At this time, the amount of hydrogen gas produced by the reaction of the compound (1) was 53 ml at 23 ° C. Further, when the obtained modified titanium oxide organosol was coated on a KBr plate and the IR spectrum was measured, absorption of Ti—OH group (3630-3640 cm). ^-1 ) Was observed.
[0103]
In addition, 10 g of the obtained modified titanium oxide organosol (6) 8 g of butyl cellosolve was added, and after removing toluene under reduced pressure at 50 ° C., the solid content was diluted to 5 wt% with water, and the particle size distribution was measured. The number average particle size was 100 nm.
[0104]
[ reference Example 1
Titanium oxide organosol (trade name: TKS-251, manufactured by Teika Co., Ltd., dispersion medium: toluene, TiO) was added to 10 g of a 20 wt% toluene solution of the compound (1) synthesized in Reference Example 1. ₂ A photocatalyst composition (1) was obtained by adding 10 g at a concentration of 20% by weight, a number average particle diameter of 80 nm and an average crystallite diameter of 6 nm (catalog value) at room temperature under stirring. The obtained photocatalyst composition (1) was stable without gelation even after 3 months at 30 ° C.
[0105]
The obtained photocatalyst composition (1) was spray-coated on a glass plate so as to have a film thickness of 1 μm, and then dried at room temperature for 1 week to obtain a glass plate having a transparent and smooth coating film.
The resulting glass plate having the coating film had a pencil hardness of HB and a contact angle with water of 84 °.
Further, the glass plate having the coating film obtained had a pencil hardness of 5H or more after irradiation with ultraviolet light (black light), and a water contact angle of 0 °. Furthermore, the photocatalytic activity evaluation result was also very good (良好).
[0106]
[ reference Example 2
Titanium oxide organosol (trade name: TKS-251, manufactured by Teika Co., Ltd., dispersion medium: toluene, TiO) was added to 10 g of a 20 wt% toluene solution of the compound (1) synthesized in Reference Example 1. ₂ 20 g of a concentration of 20% by weight, a number average particle size of 80 nm, an average crystallite size of 6 nm (catalog value)) was added with stirring at room temperature to obtain a photocatalyst composition (2). The obtained photocatalyst composition (2) was stable without gelation even after 3 months at 30 ° C.
[0107]
The obtained photocatalyst composition (2) was spray-coated on a glass plate so as to have a film thickness of 1 μm, and then dried at room temperature for 1 week to obtain a glass plate having a transparent and smooth coating film.
The glass plate having the coating film thus obtained had a pencil hardness of HB and a contact angle with water of 60 °.
Further, the glass plate having the coating film obtained had a pencil hardness of 5H or more after irradiation with ultraviolet light (black light), and a water contact angle of 0 °. Furthermore, the photocatalytic activity evaluation result was also very good (良好).
[0108]
[ reference Example 3
10 g of the modified titanium oxide organosol (6) synthesized in Reference Example 6 was added to 10 g of a 20 wt% toluene solution of the compound (2) synthesized in Reference Example 2 at room temperature with stirring to obtain a photocatalyst composition (3). . The obtained photocatalyst composition (3) was stable without gelation even after 3 months at 30 ° C. The obtained photocatalyst composition (3) was spray-coated on a glass plate so as to have a film thickness of 5 μm, and then dried at room temperature for 1 week to obtain a glass plate having a transparent and smooth coating film.
[0109]
The glass plate having the obtained coating film had a pencil hardness of HB and a contact angle with water of 97 °.
Moreover, the pencil hardness after the ultraviolet ray (black light) irradiation of the obtained glass plate having the coating film was 4H, and the contact angle of water was 30 °. Furthermore, the photocatalytic activity evaluation result was also very good (良好).
[0110]
【Example 1 ]
reference 10 g of the photocatalyst composition (1) prepared in Example 1 was added with 0.2 g of terminal vinyl polydimethylsiloxane (trade name: DMS-V00, manufactured by Chisso Corporation) as a crosslinking agent and dichloro-dicyclopentadienyl-platinum ( A photocatalyst composition (4) was obtained by adding 0.4 g of a 0.25% dioxane solution of II) at room temperature with stirring.
[0111]
The resulting photocatalyst composition (4) is spray-coated on a glass plate to a film thickness of 1 μm, dried at room temperature for 1 day, and then heated at 80 ° C. for 1 hour to form a transparent and smooth coating film A glass plate having
The glass plate having the coating film thus obtained had a pencil hardness of F and a contact angle with water of 92 °.
Further, the glass plate having the coating film obtained had a pencil hardness of 5H or more after irradiation with ultraviolet light (black light), and a water contact angle of 0 °. Furthermore, the photocatalytic activity evaluation result was also very good (良好).
[0112]
[ reference Example 4 ]
Titanium oxide hydrosol (trade name: Tynoch A-6, manufactured by Taki Chemical Co., Ltd., ammonia peptizer, TiO ₂ 8 g of a 25 wt% tetrahydrofuran solution of the compound (4) synthesized in Reference Example 4 was added to 50 g with a concentration of 6 wt%, a number average particle diameter of 10 nm and an average crystallite diameter of 10 nm (catalog value) at room temperature with stirring. An aqueous photocatalyst composition (5) was obtained.
[0113]
The obtained photocatalyst composition (5) was spray-coated on a glass plate so as to have a film thickness of 1 μm, and then dried at room temperature for 1 week to obtain a glass plate having a transparent and smooth coating film.
The glass plate having the coating film thus obtained had a pencil hardness of HB and a contact angle with water of 86 °.
Further, the glass plate having the coating film obtained had a pencil hardness of 5H or more after irradiation with ultraviolet light (black light), and a water contact angle of 0 °. Furthermore, the photocatalytic activity evaluation result was also very good (良好).
[0114]
[Comparative Example 1]
To 10 g of a 20 wt% toluene solution of the compound (5) containing no Si—H group synthesized in Reference Example 5, titanium oxide organosol (trade name: TKS-251, manufactured by Teika Co., Ltd., dispersion medium: toluene, TiO 2 concentration 10 g of 20% by weight, number average particle size 80 nm, average crystallite size 6 nm (catalog value) was added at room temperature under stirring to obtain a photocatalyst composition (6).
The obtained photocatalyst composition (6) was spray-coated on a glass plate so as to have a film thickness of 1 μm, and then dried at room temperature for 1 week, but the cloudy pencil hardness was less than 6B and the coating was very tacky. Since only a film was obtained, physical properties could not be evaluated.
[0115]
[Comparative Example 2]
2 g of titanium oxide powder (product name: ST-01, manufactured by Ishihara Sangyo Co., Ltd., average crystallite diameter of 7 nm (catalog value)) in 10 g of a 20 wt% toluene solution of the compound (1) synthesized in Reference Example 1 And 8 g of toluene were added with stirring at room temperature to obtain a photocatalyst composition (7).
The obtained photocatalyst composition (7) was spray-coated on a glass plate so as to have a film thickness of 1 μm, and then dried at room temperature for 1 week, but only a cracked white turbid coating film was obtained. It was possible.
[0116]
【The invention's effect】
The photocatalyst composition of the present invention has good storage stability, is excellent in transparency, durability, hardness, etc., and can form a coating film having photocatalytic activity under mild conditions.

Claims (8)

A photocatalytic sol having a number average particle diameter of 400 nm or less and a silicone compound having two or more Si—H groups in one molecule (excluding a cyclic organosiloxane represented by the following general formula (1)) are mixed. A photocatalytic composition for forming a coating film , further comprising a polyfunctional vinyl compound and a platinum group compound.
(However, n = 3-5, and R ₁ and R ₂ are selected from the group consisting of hydrogen, alkyl groups, phenyl groups, alkoxyl groups, and vinyl groups.) The photocatalyst composition according to claim 1, wherein the silicone compound having two or more Si-H groups in one molecule includes a ladder structure represented by the general formula (1).
(In the formula, each R ¹ is independently a hydrogen atom, a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or an unsubstituted or substituted carbon group. A hydrocarbon group consisting of one or more selected from an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms substituted with a halogen atom, or It is a group containing at least one functionality-imparting group selected from the group consisting of (1) to (4).
(1) A linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an unsubstituted or alkyl group having 1 to 20 carbon atoms, or 1 carbon atom An at least one hydrophobic group selected from the group consisting of an alkoxy group having -20 carbon atoms, an aryl group having 6-20 carbon atoms substituted with a halogen atom, and a fluoroalkyl group having 1-30 carbon atoms.
(2) At least one hydrophilic group selected from the group consisting of a carboxyl group or a salt thereof, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof, and a polyoxyalkylene group.
(3) Epoxy group, acryloyl group, methacryloyl group, (cyclic) acid anhydride group, keto group, carboxyl group, hydrazine residue, isocyanate group, isothiocyanate group, hydroxyl group, amino group, cyclic carbonate group, thiol group, At least one reactive group selected from the group consisting of ester groups;
(4) At least one spectral sensitizing group. ) The photocatalyst composition according to claim 1, wherein the silicone compound having two or more Si-H groups in one molecule is represented by the formula (2).
^{(R 2 HSiO) a (R} 2 R 2 SiO) b (R 2 QSiO) c (R 2 R 2 R 2 SiO 1/2) d
... (2)
(In the formula, R ² is a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, and an unsubstituted or alkyl group having 1 to 20 carbon atoms. Represents at least one hydrocarbon group selected from the group consisting of an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms substituted with a halogen atom, and Q is the following (1) to ( It is a group containing at least one functional group selected from the group consisting of 4).
(1) Linear or branched alkyl group having 1 to 30 carbon atoms, cycloalkyl group having 5 to 20 carbon atoms, unsubstituted or alkyl group having 1 to 20 carbon atoms, 1 to 20 carbon atoms At least one selected from the group consisting of an aryl group having 6 to 20 carbon atoms substituted with at least one substituent selected from the group consisting of an alkoxy group and a halogen atom, and a fluoroalkyl group having 1 to 30 carbon atoms Hydrophobic group.
(2) At least one hydrophilic group selected from the group consisting of a carboxyl group and a salt thereof, a phosphoric acid group and a salt thereof, a sulfonic acid group and a salt thereof, and a polyoxyalkylene group.
(3) From epoxy group, acryloyl group, methacryloyl group, (cyclic) acid anhydride group, keto group, hydrazine residue, isocyanate group, isothiocyanate group, hydroxyl group, amino group, cyclic carbonate group, thiol group and ester group At least one reactive group selected from the group consisting of:
(4) At least one spectral sensitizing group.
a is an integer of 2 or more, and b and c are 0 or an integer of 1 or more. Further, (a + b + c) ≦ 10000. d is 0 or 2, and when d = 0, it represents a cyclic silicone compound, and when d = 2, it represents a chain silicone compound. The silicone compound may be a random copolymer or a block copolymer. )   The photocatalyst composition according to any one of claims 1 to 3, wherein the photocatalyst sol is a titanium oxide sol.   The photocatalyst sol is a modified photocatalyst sol obtained by modifying a photocatalyst particle with a silicone compound having two or more Si-H groups in one molecule. Photocatalyst composition.   Polyamino compound, polyketo compound, polyisocyanate, polymethylol compound, polyalcohol, polysemicarbazide compound, polyhydrazide compound, polyepoxy compound, (meth) acrylic compound, polyvalent metal salt, polybasic acid The photocatalyst composition according to any one of claims 1 to 5, comprising a crosslinking agent.   The photocatalyst composition according to claim 1, further comprising a resin paint.   The member with which the photocatalyst composition in any one of Claims 1-7 was apply | coated.