JP2004262941A - Deodorizing, antibacterial and antifungal coating composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a deodorizing, antibacterial and antifungal coating composition utilizing a photocatalyst, having good fixation to a material, having good deodorization and sterilization functions, capable of exhibiting a function of decomposing a hazardous material, and capable of exhibiting an excellent stain-resistant function for a long period, even when applied to an organic matrial. <P>SOLUTION: This deodorizing, antibacterial and fungicidal coating composition contains the modified photocatalyst (A) which is obtained by modifying and treating a photocatalyst (a) with at least one kind of modifier compound (b) selected from the group consisting of compounds having at least one kind of structural unit selected from the group consisting a triorganosilane unit, a monooxydiorganosilane unit, a dioxyorganosilane unit, and a fluorinated methylene (CF<SB>2</SB>) unit. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

  The present invention uses a modified photocatalyst to deodorize refrigerators, decompose toilet odors, and remove bad odors such as tobacco odors attached to curtains, blinds or carpets in offices and homes, public buildings, transportation, and the like. Decomposition, removal of roasted meat odor and the like attached to various fixtures installed in restaurants and home rooms, or trace organic odors such as formaldehyde and toluene gradually released from new construction materials that have recently been regarded as a problem. Deodorizing and deodorizing applications, such as response to the `` syndrome, '' preventing the growth of bacteria and mold on the walls and ceiling of baths, preventing slimming of kitchen and bath supplies, hospitals, food, pharmaceutical factories, public facilities, and mass transportation The present invention relates to a deodorant, antibacterial, and antifungal coating composition that can be widely used for purifying the environment of living spaces, such as antibacterial and antifungal applications for sanitary management in means and the like.

In recent years, the demand for securing a comfortable living space has been increasing along with the improvement of the standard of living of the people, and products and technologies that have been subjected to deodorant, antibacterial, and mold-proof treatments have been put into practical use in various fields of clothing, food and shelter (for example, JP-A-6-205977, JP-A-63-63465, and JP-A-1-119394.
Normally, in deodorant, antibacterial and antifungal processing, antibacterial agents or water repellents are used as deodorants to suppress the growth of various bacteria and mold that cause malodor, or organic substances that cause malodor by water repellent. Prevents adhesion. As the deodorizing process using these chemicals, for example, the chemicals are mixed into raw materials at the stage of manufacturing a product, and processing is performed in each process such as dyeing, painting, and finishing. However, these methods require a large-scale apparatus and a high level of skill in order to perform the deodorizing process on the entire product, and lack the simplicity, and are limited in the design and processing of the product.

  On the other hand, deodorant / antibacterial / mildew-proof treatment using a slurry or spray in which a deodorant / antibacterial / antifungal agent is dissolved and dispersed can be easily processed, and can be directly applied to the product. Cause no problems. As such a treatment method, for example, Japanese Patent Application Laid-Open No. 60-90564 describes a method of treating with an aqueous solution in which a bactericide is dispersed with a surfactant. Also, as novel antibacterial agents, amino acid saccharide antibacterial agents are disclosed in JP-A-3-130470, organosilicon quaternary ammonium salts are disclosed in JP-A-3-69670, and JP-A-6-212256 is disclosed. Antimicrobial agents containing metal ions are described.

  However, such conventional organic antibacterial agents have a problem in safety, and in order to adhere to products, they need to be spread with various resins, which changes the texture and texture of the material. There is a problem of doing. In addition, since the organic antibacterial agent and the resin for adhesion thereof decompose or lose their performance at a high temperature, for example, when this is used for clothing, it is deodorized by ironing (maximum temperature about 200 ° C.). Antibacterial and antifungal effects disappear. Furthermore, conventional organic antibacterial agents are expensive, and thus have a problem in practical use, for example, their use is restricted depending on the product. In addition, conventional inorganic antibacterial agents have insufficient effects, and coloring of products due to ions is also a problem. The conventional antibacterial agent has an effect on malodors derived from bacteria, but has no effect on living odors such as tobacco odor and grilled meat odor.

In order to solve these problems, attention has been paid to dispersing or thin-filming a photocatalyst on a predetermined member, and imparting the deodorant, antibacterial, and antifungal functions to the predetermined member. This means that the photocatalytic substance such as titanium oxide is activated by the irradiation of light of a specific wavelength, and rapidly decomposes organic substances (microorganisms, odors, harmful chemical substances, etc.) that cause odor. It can be used for purification in various situations of the living environment.
For example, JP-A-9-316435, JP-A-8-325467, and JP-A-2001-81409 disclose deodorization using a composition containing a photocatalyst having such excellent deodorant, antibacterial, and antifungal functions.・ An antibacterial / antifungal treatment method is proposed. However, this method has a problem that the photocatalyst does not sufficiently adhere to the member and easily falls off, so that the antifouling function cannot be maintained for a long time. Further, when the member to be coated is an organic material, this method has a disadvantage that the member itself is decomposed by photocatalysis.

  To cope with such a problem, for example, Japanese Patent Application Laid-Open No. Hei 8-165215 discloses a photocatalytic titanium oxide-containing germicidal and fungicide containing a surface treatment agent such as a titanate coupling agent for the purpose of improving the adhesion to members. , Anti-fouling and soil dissolving spray. In this method, the photocatalytic titanium oxide and the organic member are bonded with the surface treatment agent so as to firmly adhere to the surface of the organic member. According to this method, since the titanium oxide is in a state of being bonded to the surface of the organic member, the decomposition speed of the organic member is slower than directly supporting the member, and even if the titanium oxide falls off, there is no change in appearance at all. There are features. However, in this method, although the effect of slightly delaying the decomposition of the organic member by the photocatalysis can be expected, the decomposition of the organic member cannot be completely prevented, so that the above-described problem is not fundamentally solved. .

With respect to the above problem, for example, in JP-A-11-207871, JP-A-2000-85354, etc., in order to protect an organic member, a base coat using a compound that is hardly decomposable against the oxidative decomposition action of a photocatalyst is applied. A method has been proposed in which a protective layer is formed and then a coating agent in which a photocatalyst is dispersed is applied. However, since the operation of applying a base coat becomes complicated, a composition for deodorant, antibacterial, and antifungal coating which does not require a base coat has long been desired.
That is, a composition for deodorant / antibacterial / antifungal coating utilizing a photocatalyst which has good fixability to a member and can exhibit an excellent antifouling function for a long period of time even when applied to an organic member has not been completed yet.

JP-A-6-205977 JP-A-63-63465 JP-A-1-119394 JP-A-60-90564 JP-A-3-130470 JP-A-3-69670 JP-A-6-21256 JP-A-9-316435 JP-A-8-325467 JP 2001-81409 A JP-A-8-165215 JP-A-11-207871 JP-A-2000-85354

  An object of the present invention is to provide a good fixing property to a member, exhibit a good decomposing function of harmful substances such as deodorization and sterilization, and also have an excellent deodorant / antibacterial / antifungal function even when applied to an organic member. To provide a deodorant, antibacterial, and antifungal coating composition using a photocatalyst capable of exhibiting a long term.

  The present inventors have conducted intensive studies and found that a deodorant, antibacterial, and antifungal coating composition containing a modified photocatalyst modified with a specific modifier compound has a good odor-decomposition function such as deodorization and sterilization. The present invention has been found to be able to provide a member that can exhibit excellent deodorizing, antibacterial, and antifungal functions over a long period of time, while achieving the present invention. That is, the present invention is as follows.

A first aspect of the present invention is to use a photocatalyst (a) as a triorganosilane unit represented by the formula (1), a monooxydiorganosilane unit represented by the formula (2), and a dioxyorganosilane represented by the formula (3). Denaturation treatment using at least one modifier compound (b) selected from the group consisting of a compound having at least one structural unit selected from the group consisting of a unit and a methylene fluoride (—CF ₂ —) unit. It is a composition for deodorant / antibacterial / antifungal coating, characterized by containing the modified photocatalyst (A).
R ₃ Si- (1)
(Wherein, R is each independently a straight-chain or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a straight-chain or branched A fluoroalkyl group, a linear or branched alkenyl group having 2 to 30 carbon atoms, a phenyl group, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group)
— (R ₂ SiO) — (2)
(In the formula, R is as defined in the formula (1).)

(In the formula, R is as defined in the formula (1).)
A second aspect of the present invention is the first deodorant / antibacterial / antifungal coating composition according to the first aspect, wherein the modified photocatalyst (A) has a wax property.
A third aspect of the invention is the first or second aspect of the invention, wherein the modified photocatalyst (A) increases the BET surface area by irradiating light having an energy higher than its band gap energy. -It is a fungicidal coating composition.
A fourth aspect of the present invention is that the modified photocatalyst (A) irradiates light having an energy higher than its band gap energy, whereby the contact angle with water at 20 ° C. is increased by 10 ° or more than before the light irradiation, and The composition for deodorant, antibacterial, and mold-proof coating according to any one of the first to third aspects of the invention, wherein the light irradiation reduces the contact angle with water at 20 ° C. by 10 ° or more than before the light irradiation. Things.

A fifth aspect of the present invention is the first deodorant, antibacterial, and antibacterial compound of the invention, wherein the modifier compound (b) is a Si—H group-containing silicon compound (b1) represented by the general formula (4). It is a composition for fungicide coating.
_{H x R y Q z SiO (} 4-x-y-z) / 2 (4)
(Wherein, R is each independently a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a linear or branched carbon group having 1 to 30 carbon atoms) It represents a group consisting of at least 30 fluoroalkyl groups, alkenyl groups having 2 to 30 carbon atoms, phenyl groups, alkoxy groups having 1 to 20 carbon atoms, and hydroxyl groups.

In the formula, Q is a group containing at least one functional group that is selected from the group consisting of (A) to (U) below.
(A) 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, an amino group or a salt thereof, and a polyoxyalkylene group.
(I) 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.
(U) at least one spectral sensitizing group;
Also, 0 <x <4, 0 <y <4, 0 ≦ z <4, and (x + y + z) ≦ 4. )

A sixth aspect of the present invention is a Si-H group-containing silicon compound, wherein the modifier compound (b) has a functional group-containing group (Q) represented by the formula (6) and / or the formula (8). The composition for deodorizing, antibacterial, and antifungal coating according to any one of the first to fifth aspects of the present invention.
_{H- (R 2 SiO) m -SiR} 2 -Q (6)
(Wherein, R is each independently a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a linear or branched carbon group having 1 to 30 carbon atoms) It represents a group consisting of at least 30 fluoroalkyl groups, alkenyl groups having 2 to 30 carbon atoms, phenyl groups, alkoxy groups having 1 to 20 carbon atoms, and hydroxyl groups.

In the formula, Q is a group containing at least one functional group that is selected from the group consisting of (A) to (U) below.
(A) 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, an amino group or a salt thereof, and a polyoxyalkylene group.
(I) 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.
(U) at least one spectral sensitizing group; m is an integer and 0 ≦ m ≦ 1000. )
(RHSiO) _p (R ₂ SiO) _q (RQSiO) _r (R ₃ SiO _1/2 ) _s (8)
(Wherein, R and Q are as defined in formula (6).
p is an integer of 1 or more, q and r are 0 or an integer of 1 or more, (p + q + r) ≦ 10000, and s is 0 or 2. However, when (p + q + r) is an integer of 2 or more and s = 0, the H silicone compound is a cyclic silicone compound, and when s = 2, the H silicone compound is a chain silicone compound. )

A seventh aspect of the present invention is the composition according to any one of the first to sixth aspects, wherein the modifier compound (b) has a polyoxyalkylene group.
Eighth invention is characterized in that the modifier compound (b) is a fluororesin (b2) having a structure represented by the formula (13): -It is a composition for fungicide coating.

(In the formula, A ^{1 to} A ⁵ may be the same or different and are each selected from a fluorine atom, a hydrogen atom, a chlorine atom, an alkyl group having 1 to 6 carbon atoms, and a halo-substituted alkyl group having 1 to 6 carbon atoms. Y represents a w-valent organic group having a molecular weight of 14 to 50000. V represents an epoxy group, a hydroxyl group, an acetoacetyl group, a thiol group, a cyclic acid anhydride group, a carboxyl group, a sulfonic acid group, Represents at least one functional group selected from the group consisting of an oxyalkylene group and a hydrolyzable silyl group, k is an integer of 0 to 1,000,000, l is an integer of 1 to 100,000, and w is 1 to 1. It is an integer of 20.)

A ninth aspect of the present invention is the composition according to any one of the first to eighth aspects, wherein the modified photocatalyst (A) is a visible light responsive photocatalyst.
In a tenth aspect of the present invention, the photocatalyst (a) is a metal-modified apatite in which a metal oxide having a photocatalytic action is formed by ion exchange in an apatite crystal structure. Any one of the compositions for deodorant / antibacterial / antifungal coating.
An eleventh aspect of the present invention is a modified photocatalyst of an adsorption-type deodorant-photocatalyst composite type, wherein the modified photocatalyst (A) is subjected to a modification treatment of the photocatalyst (a) with a denaturant compound (b) in the presence of an adsorption-type deodorant. (A ′) The composition according to any one of the first to ninth aspects of the invention, which is (A ′).
A twelfth aspect of the present invention is the composition for deodorizing, antibacterial, and antifungal coating according to any one of the first to eleventh aspects of the present invention, further comprising an adsorption-type deodorant.

A thirteenth aspect of the present invention is the composition according to any one of the first to twelfth aspects, further comprising an antibacterial metal.
A fourteenth aspect of the present invention is the composition according to any one of the first to thirteenth aspects, further comprising a resin having a surface energy larger than that of the modified photocatalyst (A). is there.
A fifteenth aspect of the present invention is the composition according to any one of the first to fourteenth aspects, further comprising ethanol.
According to a sixteenth aspect of the present invention, there is provided the composition according to any one of the first to fifteenth aspects, further comprising a propellant.
A seventeenth aspect of the present invention is a deodorant / antibacterial / mildew-resistant member treated with any one of the first to sixteenth aspects of the present invention.

  From the composition for deodorant / antibacterial / mildew-proof coating of the present invention, harmful substances are decomposed by light irradiation and deodorant / antibacterial / mildew-proof which can exhibit excellent odor-proof / antibacterial / mildew-proof performance for a long time. Sex members can be provided.

Hereinafter, the present invention will be described in detail.
The composition for deodorant / antibacterial / mold-proof coating of the present invention contains a modified photocatalyst (A). The member treated with the deodorant / antibacterial / mold-proof coating composition of the present invention is capable of decomposing harmful substances by light irradiation and exhibiting excellent deodorant / antibacterial / mildew-proof performance over a long period of time.
The modified photocatalyst (A) of the present invention can be obtained by modifying the photocatalyst (a) with at least one type of modifier compound (b) described below.
In the present invention, "modification" means immobilizing at least one modifier compound (b) described below on the surface of the photocatalyst (a). The immobilization of the modifier compound on the surface of the photocatalyst particles is based on van der Waals force (physical adsorption), Coulomb force or chemical bonding. it is conceivable that. In particular, modification using a chemical bond is preferable because the interaction between the modifier compound and the photocatalyst is strong, and the modifier compound is firmly fixed to the surface of the photocatalyst particles.

  In the present invention, the photocatalyst (a) refers to a substance that causes an oxidation or reduction reaction by light irradiation. That is, when light (excitation light) having an energy (that is, a shorter wavelength) larger than the energy gap between the conduction band and the valence band is irradiated, excitation of electrons in the valence band (photoexcitation) occurs, and A substance that can generate electrons and holes. At this time, various chemical reactions are performed using the reducing power of the electrons generated in the conduction band and / or the oxidizing power of the holes generated in the valence band. Can be. For example, oxidative decomposition reactions of various organic substances can be mentioned.

The photocatalyst (a), for _{example, TiO 2, ZnO, SrTiO 3} , CdS, GaP, InP, GaAs, BaTiO 3, BaTiO 4, BaTi 4 O 9, K 2 NbO 3, Nb 2 O 5, Fe 2 O 3 _{, Ta 2 O 5, K 3} Ta 3 Si 2 O 3, WO 3, SnO 2, Bi 2 O 3, BiVO 4, NiO, Cu 2 O, SiC, MoS 2, InPb, RuO 2, CeO 2, Ta 3 N _5, etc., further Ti, Nb, Ta, layered oxide containing at least one element selected from V (for example, JP 62-74452, JP-a No. 2-172535, JP-a No. 7- JP-A-24329, JP-A-8-89799, JP-A-8-89800, JP-A-8-89804, JP-A-8-198061, -248465, JP-A No. 10-99694 and JP-reference Publication No. Hei 10-244165) can be mentioned.

Among these photocatalysts (a), TiO ₂ (titanium oxide) is preferable because it is harmless and has excellent chemical stability. As titanium oxide, any of anatase, rutile and brookite can be used.
When a visible light responsive photocatalyst capable of exhibiting photocatalytic activity and / or hydrophilicity by irradiation with visible light (for example, a wavelength of about 400 to 800 nm) is selected as the photocatalyst (a) used in the present invention, The deodorant / antibacterial / mildew-resistant member treated with the inventive deodorant / antimicrobial / mildew-proof coating composition sufficiently exhibits the deodorant / antimicrobial / mildew-proof effect even in places such as indoors where ultraviolet rays are not sufficiently irradiated. It is preferable because it can be performed.

Any of the above visible light responsive photocatalysts can be used as long as they exhibit photocatalytic activity and / or hydrophilicity with visible light. For example, TaON, LaTiO ₂ N, CaNbO ₂ N, LaTaON ₂ , and CaTaO ₂ N Oxynitride compounds (for example, see JP-A-2002-66333), oxysulfide compounds such as Sm ₂ Ti ₂ S ₂ O ₇ (for example, see JP-A-2002-233770), and nitriding such as Ta ₃ N _5. Compounds, oxides containing metal ions in the d10 electronic state such as CaIn ₂ O ₄ , SrIn ₂ O ₄ , ZnGa ₂ O ₄ , and Na ₂ Sb ₂ O ₆ (see, for example, JP-A-2002-59008), ammonia and urea In the presence of nitrogen-containing compounds such as titanium oxide precursors (titanium oxysulfate, titanium chloride, alkoxy titan Etc.) and nitrogen-doped titanium oxide obtained by firing high surface titanium oxide (for example, JP-A-2002-29750, JP-A-2002-87818, JP-A-2002-154823, JP-A-2001-207082) Sulfur-doped titanium oxide and titanium oxide obtained by calcining titanium oxide precursors (titanium oxysulfate, titanium chloride, alkoxytitanium, etc.) in the presence of sulfur compounds such as thiourea, etc. Oxygen-deficient titanium oxide (for example, see JP-A-2001-98219) obtained by heat-treating the photocatalyst particles with a halogenated platinum compound (for example, JP-A-2002-239353). Treatment) and treatment with a tungsten alkoxide (see JP-A-2001-286755). A surface-treated photocatalyst or the like obtained by the above method can be suitably used.

Among the above visible light responsive photocatalysts, oxynitride compounds and oxysulfide compounds have high photocatalytic activity by visible light and can be used particularly preferably.
The oxynitride compound that can be particularly preferably used in the present invention is an oxynitride containing a transition metal, and as having high photocatalytic activity, the transition metal is preferably selected from the group consisting of Ta, Nb, Ti, Zr, and W. Oxynitride, characterized by further comprising at least one element selected from the group consisting of alkali, alkaline earth and Group IIIB metals. Oxynitride, and more preferably oxynitride, further comprising at least one metal element selected from the group consisting of Ca, Sr, Ba, Rb, La, and Nd.

Examples of oxynitride containing the transition _{metal, LaTiO 2 N, La v Ca} w TiO 2 N (v + w = 3), La v Ca w TaO 2 N (v + w = 3), LaTaON 2, CaTaO 2 N, General formula AMO _x N _y such as SrTaO ₂ N, BaTaO ₂ N, CaNbO ₂ N, CaWO ₂ N, and SrWO ₂ N (A = alkali metal, alkaline earth metal, group IIIB metal; M = Ta, Nb, Ti, Zr, W; compound represented by x + y = 3), TaON, NbON, WON, Li ₂ LaTa ₂ O ₆ N, and the like. Among _{these, LaTiO 2 N, La v Ca} w TiO 2 N (v + w = 3), La v Ca w TaO 2 N (v + w = 3), TaON are preferable for photocatalytic activity is very large in the visible light.

The oxysulfide compound that can be particularly preferably used in the present invention is an oxysulfide containing a transition metal, and as having high photocatalytic activity, the transition metal is preferably selected from the group consisting of Ta, Nb, Ti, Zr, and W. An oxysulfide characterized by at least one, more preferably an oxysulfide further comprising at least one element selected from the group consisting of alkali, alkaline earth and Group IIIB metals And more preferably an oxysulfide further containing a rare earth element.
Examples of the oxysulfide containing the transition metal include Sm ₂ Ti ₂ S ₂ O ₅ , Nd ₂ Ti ₂ S ₂ O ₅ , La ₆ Ti ₂ S ₈ O ₅ , Pr ₂ Ti ₂ S ₂ O ₅ , and Sm _3. NbS ₃ O _{4 and the} like can be mentioned. Among them, Sm ₂ Ti ₂ S ₂ O ₅ and Nd ₂ Ti ₂ S ₂ O ₅ are very preferable because of their extremely high photocatalytic activity in visible light.

Further, as the photocatalyst (a) in the present invention, a metal-modified apatite in which a metal oxide having a photocatalytic action is formed in an apatite crystal structure by ion exchange, for example, a part of calcium ion in calcium hydroxyapatite crystal is converted to titanium ion Titanium-modified calcium hydroxyapatite (see JP-A-2000-327315), which is ion-exchanged, can be used very preferably because of its excellent adsorption property against bacteria, viruses, dirt, and the like.
Further, the above-mentioned photocatalyst (a) is preferably added or fixed with a metal such as Pt, Rh, Ru, Nb, Cu, Sn, Ni, Fe and / or an oxide thereof, or coated with porous calcium phosphate or the like. It can also be used as a photocatalyst (for example, see JP-A-10-244166).

As the form of the photocatalyst particles (a) used in the present invention, any of powder, dispersion, and sol can be used. In the modification treatment with the modifier compound (b) in the present invention, it is preferable to use a photocatalyst sol or a photocatalyst dispersion liquid for reasons such as efficiency and uniformity. Here, the photocatalyst sol and the photocatalyst dispersion used in the present invention are such that the photocatalyst particles are preferably 0.01 to 80% by mass in water and / or an organic solvent, more preferably 0.01 to 70% by mass, and still more preferably. Is 0.1 to 50% by mass dispersed as primary particles and / or secondary particles.
Here, as the organic solvent used in the photocatalyst sol or photocatalyst dispersion, for example, ethylene glycol, butyl cellosolve, n-propanol, isopropanol, n-butanol, ethanol, alcohols such as methanol, toluene and xylene and the like Aromatic hydrocarbons, 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; dimethylsulfoxide and nitrobenzene; and mixtures of two or more of these.

  Taking 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 deflocculated therein can be exemplified. (Here, "substantially using water as a dispersion medium" means that about 80% or more of water is contained in the dispersion medium.) The preparation of such a sol is known and can be easily produced (for example, 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 an aggregate of titanium oxide particles. Can be The aggregates are peptized under the action of nitric acid, hydrochloric acid, ammonia, or the like, and subjected to hydrothermal treatment or the like to obtain a titanium oxide hydrosol. In addition, as the titanium oxide hydrosol, one obtained by peptizing titanium oxide particles under the action of an acid or an alkali, or a dispersion stabilizer such as sodium polyacrylate as necessary without using an acid or an alkali, is used. Sols that are used and dispersed in water under strong shear can also be used. Furthermore, an anatase-type titanium oxide sol whose particle surface is modified with a peroxo group, which has excellent dispersion stability even in an aqueous solution having a pH around neutrality, can be easily obtained by the method proposed in, for example, JP-A-10-67516. Can be.

The titanium oxide hydrosol described above is also commercially available as a titania sol. (For example, "STS-02" manufactured by Ishihara Sangyo Co., Ltd., "TO-240" manufactured by Tanaka Transcription Co., Ltd.)
The solid content in the titanium oxide hydrosol is preferably 50% by mass or less, more preferably 30% by mass or less. More preferably, the content is 30% by mass or less and 0.1% by mass or more.
Further, a cerium oxide sol (see, for example, JP-A-8-59235) and a layered oxide sol containing at least one element selected from the group consisting of Ti, Nb, Ta, and V (for example, see JP-A-9-25123) JP-A-9-67124, JP-A-9-227122, JP-A-9-227123, JP-A-10-259023, etc.) and the like. Also known.

Further, a visible light responsive photocatalyst sol that can be suitably used in the present invention is also commercially available. (For example, "NTB-200" manufactured by Showa Denko KK, "TSS-4110" manufactured by Sumitomo Chemical Co., Ltd.)
Further, a visible light responsive photocatalyst aqueous dispersion of metal-modified apatite that can be suitably used in the present invention is also commercially available. (For example, "PHTOHAP PDAP-L20" manufactured by Taihei Chemical Industry Co., Ltd.)
Further, a photocatalyst organosol in which an organic solvent is substantially used as a dispersion medium and photocatalyst particles are dispersed therein is, for example, a compound having a phase transfer activity such as polyethylene glycol (eg, a different first phase and a second phase). A third phase is formed at the interface with the phase, and the first phase, the second phase, and the third phase are treated with a compound that dissolves and / or solubilizes each other and diluted with an organic solvent (for example, JP-A-10-167727), a method of preparing a sol by dispersing and transferring in an organic solvent insoluble in water with an anionic surfactant such as sodium dodecylbenzenesulfonate (for example, JP-A-58-29863). After adding an alcohol having a boiling point higher than that of water such as butylcellosolve or water to the photocatalyst hydrosol, the water can be removed by distillation (reduced pressure) or the like.

Further, a titanium oxide organosol in which titanium oxide particles are substantially dispersed in an organic solvent as a dispersion medium is commercially available (for example, “TKS-251” manufactured by Teica Corporation). Here, “substantially using an organic solvent as a dispersion medium” means that the organic solvent is contained in the dispersion medium in an amount of about 20% by mass or more.
In the present invention, the properties of the photocatalyst particles (a) to be used are important factors for the dispersion stability, film formability, and expression of various functions of the modified photocatalyst (A). As the photocatalyst particles (a) used in the present invention, a photocatalyst particle having a number average dispersed particle diameter of a mixture of primary particles and secondary particles (only primary particles or secondary particles may be used) of 400 nm or less is used. Is desirable because the surface characteristics of the photocatalyst after modification can be used effectively. In particular, when photocatalyst particles having a number average dispersed particle diameter of 100 nm or less are used, a film excellent in transparency can be obtained from the resulting composition for deodorant / antibacterial / antifungal coating comprising the modified photocatalyst (A). Very preferred. More preferably, a photocatalyst particle having a size of 80 nm or less and 3 nm or more, further preferably 50 nm or less and 3 nm or more is suitably selected. Conventionally, most of the numerical values simply indicated as particle diameters in titanium dioxide or the like are the diameters of primary particles (crystal particle diameters), not numerical values in consideration of the secondary particle diameter due to aggregation.

In the composition for deodorant / antibacterial / mold-proof coating of the present invention, the photocatalyst (a) may be a triorganosilane unit represented by the formula (1), a monooxydiorganosilane unit represented by the formula (2), At least one compound selected from the group consisting of compounds having at least one structural unit selected from the group consisting of dioxyorganosilane units represented by (3) and methylene fluoride (—CF ₂ —) units The modified photocatalyst (A) modified with the modifier compound (b) is used.
R ₃ Si- (1)
(Wherein, R is each independently a straight-chain or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a straight-chain or branched A fluoroalkyl group, a linear or branched alkenyl group having 2 to 30 carbon atoms, a phenyl group, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group)
— (R ₂ SiO) — (2)
(In the formula, R is as defined in the formula (1).)

(In the formula, R is as defined in the formula (1).)
In the present invention, the modification treatment of the photocatalyst (a) with the modifier compound (b) is preferably performed in the presence or absence of water and / or an organic solvent, by using the photocatalyst (a) and the modifier compound (b) described above. Is the mass ratio (a) / (b) = 1/99 to 99.99 / 0.01, more preferably (a) / (b) = 1/99 to 99.99 / 0.1, and still more preferably ( a) / (b) = 10/90 to 99.9 / 0.1, and mixed at a rate of preferably 0 to 200 ° C., more preferably 10 to 80 ° C., or distillation (reduced pressure) or the like. It can be obtained by performing an operation such as changing the solvent composition of the mixture.

  Examples of the organic solvent that can be used in the above modification 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; and ethylene glycol. Alcohols such as butyl cellosolve, isopropanol, n-butanol, ethanol and methanol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ethers such as tetrahydrofuran and dioxane; amides such as dimethylacetamide and dimethylformamide; chloroform; Examples thereof include halogen compounds such as methylene and carbon tetrachloride, dimethyl sulfoxide, nitrobenzene, and the like, and a mixture of two or more thereof.

Examples of the modifier compound (b) used to obtain the modified photocatalyst (A) of the present invention include a Si-H group, a hydrolyzable silyl group (alkoxysilyl group, hydroxysilyl group, halogenated silyl group, (Acetoxysilyl group, aminoxysilyl group, etc.), epoxy group, acetoacetyl group, thiol group, acid anhydride group, etc., reactive with photocatalyst particles (a), silicon compound, fluoroalkyl compound, fluoroolefin polymer, etc. Can be mentioned.
Other examples of the modifier compound (b) include, for example, a structure that interacts with the photocatalyst particles (a) by van der Waals force, Coulomb force, and the like, such as a polyoxyalkylene group, a sulfonic acid group, Examples thereof include a silicon compound, a fluoroalkyl compound, and a fluoroolefin polymer having a group.

When the Si—H group-containing silicon compound (b1) represented by the general formula (4) is used as the modifier compound (b) used in the present invention, the particle surface of the photocatalyst (a) can be very efficiently used. It is preferable because it can be modified and various functional groups can be effectively introduced into the photocatalyst (a).
_{H x R y Q z SiO (} 4-x-y-z) / 2 (4)
(Wherein, R is each independently a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a linear or branched carbon group having 1 to 30 carbon atoms) It represents a group consisting of at least 30 fluoroalkyl groups, alkenyl groups having 2 to 30 carbon atoms, phenyl groups, alkoxy groups having 1 to 20 carbon atoms, and hydroxyl groups.

In the formula, Q is a group containing at least one functional group that is selected from the group consisting of (A) to (U) below.
(A) 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, an amino group or a salt thereof, and a polyoxyalkylene group.
(I) 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.
(U) at least one spectral sensitizing group;
Also, 0 <x <4, 0 <y <4, 0 ≦ z <4, and (x + y + z) ≦ 4. )
In the present invention, the modification of the photocatalyst (a) with the Si—H group-containing silicon compound represented by the general formula (4) is carried out in the presence or absence of water and / or an organic solvent. The Si-H group-containing silicon compound (b1) preferably has a mass ratio of (a) / (b1) = 1/99 to 99.9 / 0.1, more preferably (a) / (b1) = 10/90. It can be carried out by mixing at a ratio of preferably 99 to 1 at 0 to 200C.

Hydrogen gas is generated from the mixed solution by this denaturation operation, and when a photocatalyst sol is used as the photocatalyst (a), an increase in the average particle diameter is observed.
When titanium oxide is used as the photocatalyst (a), a decrease in the Ti-OH group is observed as a decrease or disappearance of the absorption at 3630 to 3640 cm ^{-1 in} the IR spectrum due to the modification operation.
From these facts, when the Si—H group-containing silicon compound (b1) represented by the general formula (4) is selected as the modifier compound (b), the modified photocatalyst (A) is a Si—H group-containing silicon compound. It is not a mere mixture of (b1) and the photocatalyst (a), but it can be predicted that some interaction between the two occurs due to a chemical reaction.

In fact, the modified photocatalyst (A) obtained in this way has extremely excellent dispersion stability in a solvent, chemical stability, durability and the like.
In the present invention, in the Si—H group-containing silicon compound (b1) represented by the composition formula (4), the Si—H group is an essential functional group for modifying the photocatalyst under mild conditions with good selectivity. . On the other hand, an alkoxy group or a hydroxyl group bonded to a silicon atom can be similarly used for denaturation of a photocatalyst, but contains many side reactions and deteriorates the stability of the resulting modified photocatalyst (A). A smaller amount is preferred.
Examples of the Si—H group-containing silicon compound (b1) represented by the general formula (4) that can be suitably used in the present invention include, for example, a mono-Si—H group-containing silicon compound represented by the formula (5) or (6). At least one Si-H group-containing silicon compound selected from the group consisting of a compound, a compound having Si-H groups at both ends represented by the formula (7), and an H silicone compound represented by the formula (8). Can be.

(Wherein, R is each independently a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a linear or branched carbon group having 1 to 30 carbon atoms. It is composed of at least one selected from 30 fluoroalkyl groups, alkenyl groups having 2 to 30 carbon atoms, phenyl groups, alkoxy groups having 1 to 20 carbon atoms, hydroxyl groups, or siloxy groups represented by the formula (9). Represents a group.
—O— (R ₂ SiO) _n —SiR ₃ (9)
(In the formula, R is independently selected from a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, and a phenyl group. And n is an integer, and 0 ≦ n ≦ 1000.))
_{H- (R 2 SiO) m -SiR} 2 -Q (6)
(Wherein, R is as defined in formula (5).

In the formula, Q is a group containing at least one functional group that is selected from the group consisting of (A) to (U) below.
(A) 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, an amino group or a salt thereof, and a polyoxyalkylene group.
(I) 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.
(U) at least one spectral sensitizing group;
m is an integer and 0 ≦ m ≦ 1000. )
_{H- (R 2 SiO) m -SiR} 2 -H (7)
(In the formula, R is as defined in the formula (5). M is an integer and 0 ≦ m ≦ 1000.)
(RHSiO) _p (R ₂ SiO) _q (RQSiO) _r (R ₃ SiO _1/2 ) _s
(8)
(Wherein, R is as defined in equation (5) and Q is as defined in equation (6).
p is an integer of 1 or more, q and r are 0 or an integer of 1 or more, (p + q + r) ≦ 10000, and s is 0 or 2. However, when (p + q + r) is an integer of 2 or more and s = 0, the H silicone compound is a cyclic silicone compound, and when s = 2, the H silicone compound is a chain silicone compound. )

  Specific examples of the mono-Si-H group-containing compound represented by the above formula (5) include, for example, bis (trimethylsiloxy) methylsilane, bis (trimethylsiloxy) ethylsilane, bis (trimethylsiloxy) n-propylsilane, bis (trimethyl) (Siloxy) i-propylsilane, bis (trimethylsiloxy) n-butylsilane, bis (trimethylsiloxy) n-hexylsilane, bis (trimethylsiloxy) cyclohexylsilane, bis (trimethylsiloxy) phenylsilane, bis (triethylsiloxy) methylsilane, bis (Triethylsiloxy) ethylsilane, tris (trimethylsiloxy) silane, tris (triethylsiloxy) silane, pentamethyldisiloxane, 1,1,1,3,3,5,5-heptamethyltrisiloxane, 1,1,1 3,3,5,5,6,6-nonamethyltetrasiloxane, trimethylsilane, ethyldimethylsilane, methyldiethylsilane, triethylsilane, phenyldimethylsilane, diphenylmethylsilane, cyclohexyldimethylsilane, t-butyldimethylsilane, -T-butylmethylsilane, n-octadecyldimethylsilane, tri-n-propylsilane, tri-i-propylsilane, tri-i-butylsilane, tri-n-hexylsilane, triphenylsilane, allyldimethylsilane, 1- Allyl-1,1,3,3-tetramethyldisiloxane, chloromethyldimethylsilane, 7-octenyldimethylsilane and the like can be mentioned.

  Specific examples of the compound having a Si—H group at both ends represented by the above formula (7) include, for example, 1,1,3,3-tetramethyldisiloxane, 1,1,3,3,5,5-hexa. H-terminal polydimethylsiloxanes having a number average molecular weight of 50,000 or less, preferably 50 or more, such as methyltrisiloxane, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane, and 1,1,3 Number average molecular weight 50,000 such as 1,3-tetraethyldisiloxane, 1,1,3,3,5,5-hexaethyltrisiloxane, 1,1,3,3,5,5,7,7-octaethyltetrasiloxane And preferably 50 or more H-terminal polydiethylsiloxanes, 1,1,3,3-tetraphenyldisiloxane, 1,1,3,3,5,5-hexaphenyltrisiloxane, 1,1,3 , 3, H-terminal polydiphenylsiloxanes having a number average molecular weight of 50,000 or less, preferably 50 or more, such as 1,5,7,7-octaphenyltetrasiloxane, 1,3-diphenyl-1,3-dimethyl-disiloxane, 1,3 , 5-trimethyl-1,3,5-triphenyl-trisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetraphenyl-tetrasiloxane, etc., preferably having a number average molecular weight of 50,000 or less Are 50 or more H-terminal polyphenylmethylsiloxanes, dimethylsilane, ethylmethylsilane, diethylsilane, phenylmethylsilane, diphenylsilane, cyclohexylmethylsilane, t-butylmethylsilane, di-t-butylsilane, n-octadecylmethyl Examples thereof include silane and allylmethylsilane.

The H silicone compound represented by the formula (8) has a number average molecular weight of preferably 100,000 or less from the viewpoint of dispersion stability (prevention of aggregation of the photocatalyst (a) particles) during the modification treatment of the photocatalyst (a). Preferably, an H silicone compound of 200 or more, more preferably 50,000 or less and 500 or more, even more preferably 20,000 or less and preferably 1,000 or more can be suitably used.
Further, as the Si—H group-containing silicon compound (b1) represented by the general formula (4), those having a functional group-providing group-containing group (Q) (formulas (6) and (8), where r is (One or more positive numbers) is preferred because various functions can be imparted to the modified photocatalyst (A) obtained in the present invention.

Here, the functional group-providing group-containing group (Q) is preferably a group represented by the following formula (10).
−Z− (W) _t (10)
(Wherein, Z represents a t-valent organic group having a molecular weight of 14 to 50,000 (a group having a t-valence other than bonding to the silicon atom of the organic group Z), and W represents the functionality in the formula (4). (It is at least one selected from the group consisting of imparting groups (A) to (U), and t is an integer of 1 to 20.)
For example, as the functional group-containing group (Q), a monovalent group containing a carboxyl group or a salt thereof, a monovalent group containing a phosphate group or a salt thereof, a monovalent group containing a sulfonic acid group or a salt thereof, When a compound having at least one hydrophilic group [(a) in the formula (4)] selected from the group consisting of a monovalent group containing an amino group or a salt thereof and a polyoxyalkylene group is selected, the modified compound is obtained. The dispersion stability of the photocatalyst (A) in water becomes very good.

Examples of the functional group-containing group (Q) include an epoxy group, an acryloyl group, a methacryloyl group, a (cyclic) acid anhydride group, a keto group, a carboxyl group, a hydrazine residue, an isocyanate group, an isothiocyanate group, and a hydroxyl group. When a group containing at least one reactive group [(i) in the formula (4)] selected from the group consisting of an amino group, a cyclic carbonate group, a thiol group and an ester group is selected, the modified photocatalyst of the present invention ( A) is preferable because it has a crosslinking property and can be firmly fixed to the surface.
Further, for example, when a group having a spectral sensitizing group is selected as the functional group-containing group (Q), the modified photocatalyst (A) of the present invention can be used not only in the ultraviolet region but also in the visible light region and / or the infrared light region. The catalytic activity and the photoelectric conversion function can also be exhibited by irradiating the region with light.

Here, the spectral sensitizing group means a group derived from various metal complexes or organic dyes (that is, sensitizing dyes) having absorption in a visible light region and / or an infrared light region.
Examples of the sensitizing dye include xanthene dyes, oxonol dyes, cyanine dyes, merocyanine dyes, rhodocyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes, phthalocyanine dyes (including metal complexes), Porphyrin-based dyes (including metal complexes), triphenylmethane-based dyes, perylene-based dyes, coronene-based dyes, azo-based dyes, and nitrophenol-based dyes, as well as JP-A-1-220380 and Patent Application Publication No. 5-504023 And ruthenium, osmium, iron and zinc complexes, and other metal complexes such as ruthenium red.

  Among these sensitizing dyes, it has absorption in the wavelength region of 400 nm or more, and the energy level of the lowest unoccupied orbital (redox potential in the excited state) is higher than the energy level of the conduction band of the photocatalyst (a). Those having features are preferred. Characteristics of such a sensitizing dye include measurement of absorption spectra of light in the infrared, visible, and ultraviolet regions, measurement of oxidation-reduction potential by an electrochemical method (for example, T. Tani, Photogr. Sci. Eng., 14, 72 (1970); RWBerriman et al., Ibid., 17.235 (1973); PBGilman Jr., ibid., 18, 475 (1974), etc.), energy level calculation using molecular orbital method ( For example, T. Tani et al., Photogr. Sci. Eng., 11, 129 (1967); DMSturmer et al., Ibid., 17.146 (1973); ibid., 18, 49 (1974); RGSelby et al., J. Opt. Soc. Am., 33, 1 (1970), etc.) and the presence or absence of electromotive force due to light irradiation of a Gratzel-type wet solar cell made with a photocatalyst (a) and a spectral sensitizing dye. It can be confirmed by efficiency or the like.

Examples of the sensitizing dye having the above characteristics 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, a phthalocyanine-based metal complex, and a porphyrin-based Metal complexes and the like can be mentioned.
In the present invention, as a method for obtaining the Si—H group-containing silicon compound having the above-described functional group-providing group-containing group (Q),
(Q-1)-As a method, a Si-H group-containing compound represented by the following general formula (11), and a carbon-carbon having a functionality-imparting group [(A) to (U) in formula (4)] A method in which an unsaturated bond compound is subjected to a hydrosilylation reaction.
(Q-2) —As a method, a Si—H group-containing silicon compound represented by the following general formula (11) and a carbon-carbon unsaturated bond compound having a reactive group [(i) in the formula (4)] Is subjected to a hydrosilylation reaction to obtain a Si-H group-containing silicon compound having a reactive group, and then the reactive group is reacted with a functional group-containing compound having reactivity.
_{H (x + z) R y} SiO (4-x-y-z) / 2 (11)
(Wherein, R is each independently a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a linear or branched carbon group having 1 to 30 carbon atoms) It represents a group consisting of at least 30 fluoroalkyl groups, alkenyl groups having 2 to 30 carbon atoms, phenyl groups, alkoxy groups having 1 to 20 carbon atoms, and hydroxyl groups.

Also, 0 <(x + z) <4, 0 <y <4, and (x + y + z) ≦ 4. )
First, as a method for obtaining a Si-H group-containing silicon compound having a functionality imparting group (Q), the above-mentioned method (Q-1) [hereinafter, (Q-1) -method] will be described.
In the (Q-1) -method, the carbon-carbon unsaturated bond compound used for introducing a hydrophilic group as a functional group into the Si-H group-containing silicon compound represented by the formula (11) includes: 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, an amino group or a salt thereof, a polyoxyalkylene group, and a cyclic acid anhydride. Olefins, allyl ethers, vinyl ethers, vinyl esters, (meth) acrylates, styrene derivatives, and the like.

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 (12), and 5-norbornene-2,3-dicarboxylic anhydride. And allyl succinic anhydride.
CH ₂ ＣＨCHCH ₂ O (CH ₂ CH ₂ O) _t R ⁴ (12)
(In the formula, t represents an integer of 1 to 1000. R ⁴ represents a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms.)
Examples of the carbon-carbon unsaturated bond compound used to introduce a reactive group into the Si—H group-containing silicon compound represented by the formula (11) include an epoxy group, a (meth) acryloyl group, and a (cyclic) group. Olefin having at least one reactive group selected from the group consisting of acid anhydride groups, keto groups, carboxyl groups, hydrazine residues, isocyanate groups, isothiocyanate groups, hydroxyl groups, amino groups, cyclic carbonate groups, and ester groups , Allyl ethers, allyl esters, vinyl ethers, vinyl esters, (meth) acrylates, styrene derivatives and the like.

  Preferred 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 crotonate, ethylene glycol di (meth) acrylate, maleic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, 5-hexen-2-one, allyl isocyanate, allyl alcohol, ethylene glycol monoallyl Ether, allylamine, allyl isothiocyanate, allyl semicarbazide, (meth) acrylic acid hydrazide, 4-allyloxymethyl-2-oxo-1,3-dioxolane and the like can be mentioned.

  Examples of the carbon-carbon unsaturated bond compound used to introduce the spectral sensitizing group into the Si—H group-containing silicon compound represented by the formula (11) include olefins having the spectral sensitizing dye described above, Examples include allyl ethers, allyl esters, vinyl ethers, vinyl esters, (meth) acrylates, and styrene derivatives. 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.

  For example, the reactive group of the carbon-carbon unsaturated bond compound having a reactive group may be an epoxy group, (cyclic) acid anhydride, isocyanate group, isothiocyanate 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 is an amino group, a carboxyl group, a hydroxyl group, a hydrazine residue, a (meth) acryloyl group, an epoxy group, a (cyclic) acid anhydride, an isocyanate group, an isothiocyanate group, At least one functional group selected from the group consisting of a cyclic carbonate group, an ester group, a keto group, and a (meth) acryloyl group; Spectral sensitizing dye and the like.

The reaction between the carbon-carbon unsaturated bond compound having the reactive group and the spectral sensitizing dye having reactivity with the compound is performed under the reaction conditions such as a reaction temperature, a reaction pressure, and a 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.
In the (Q-1) -method, the hydrosilylation reaction between the carbon-carbon unsaturated bond compound and the Si—H group-containing silicon compound represented by the formula (11) is preferably carried out in the presence of a catalyst using an organic solvent. The carbon-carbon unsaturated bond compound (E) and the Si—H group-containing silicon compound (b1 ′) represented by the formula (11) at 0 to 200 ° C. in the presence or absence of E) / (b1 ′) = 0.01 or more, more preferably (E) / (b1 ′) = 0.01 to 2, more preferably (E) / (b1 ′) = 0.01 to 1 Can be performed.

  As the catalyst for the hydrosilylation reaction, a platinum group catalyst, that is, a compound of ruthenium, rhodium, palladium, osmium, iridium, and platinum is suitable, and a compound of platinum and a compound of palladium are particularly preferable. Examples of the platinum compound include platinum (II) chloride, tetrachloroplatinic acid (II), platinum chloride (IV), hexachloroplatinic acid (IV), ammonium hexachloroplatinum (IV), potassium hexachloroplatinum (IV), and hydroxide. Platinum (II), platinum dioxide (IV), dichloro-dicyclopentadienyl-platinum (II), platinum-vinylsiloxane complex, platinum-phosphine complex, platinum-olefin complex and platinum alone, alumina, silica and activated carbon What carried solid platinum is mentioned. Examples of the palladium compound include palladium (II) chloride, ammonium tetraammonium palladium (II) chloride, palladium (II) oxide and the like.

  Examples of the organic solvent that can be used for the hydrosilylation reaction include, for example, aromatic hydrocarbons such as toluene and xylene, hexane, cyclohexane, aliphatic hydrocarbons such as heptane, ethyl acetate, esters such as 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.

Next, as a method for obtaining a Si-H group-containing silicon compound having a functional group, a method (Q-2) described above (hereinafter, (Q-2) -method) will be described.
As the carbon-carbon unsaturated bond compound having a reactive group used in the (Q-2) -method, those described in the (Q-1) -method can be exemplified. The hydrosilylation reaction between the Si-H group-containing silicon compound represented by the above formula (11) and the carbon-carbon unsaturated bond compound having the reactive group was described in the (Q-1) -method. It can be carried out under the same conditions as the hydrosilylation reaction.
According to the (Q-2) -method, a Si-H group-containing silicon compound having a reactive group can be obtained by the hydrosilylation reaction. The reaction between the Si-H group-containing silicon compound having a reactive group and the functional group-providing group-containing compound having reactivity with the compound is performed by a reaction such as a reaction temperature, a reaction pressure, or a solvent depending on the type of each reactive group. It can be implemented by selecting conditions. At that time, from the viewpoint of the stability of the Si—H group, the reaction temperature is preferably 300 ° C. or lower, more preferably 150 ° C. or lower and 0 ° C. or higher.

  When a fluororesin (b2) having a structure represented by the general formula (13) is used as the modifier compound (b) used in the present invention, the modified photocatalyst (A) modified with the fluororesin is used. ) Is preferable because it is excellent in both the antifouling property and the protection property of the organic base material.

(In the formula, A ^{1 to} A ⁵ may be the same or different and are each selected from a fluorine atom, a hydrogen atom, a chlorine atom, an alkyl group having 1 to 6 carbon atoms, and a halo-substituted alkyl group having 1 to 6 carbon atoms. Y is a w-valent organic group having a molecular weight of 14 to 50,000 (a group having a w-valence other than bonding to the main chain of the organic group Y, preferably a group having a methylene fluoride unit, more preferably V represents a group having an epoxy group, a hydroxyl group, an acetoacetyl group, a thiol group, a cyclic acid anhydride group, a carboxyl group, a sulfonic acid group, a polyoxyalkylene group, or a hydrolyzable silyl group. Represents at least one functional group selected from the group consisting of: k is an integer of 0 or more and 1,000,000 or less, and l is an integer of 1 or more and 100000 or less, provided that k = 0. The at least one fluorine atom in ^A 3 to A ^5, more preferably an integer of .w 1 to 20 representing the ^A 3, ^{A 4} are both fluorine atoms.)

  In the present invention, the modification of the photocatalyst (a) with the fluororesin (b2) having a structure represented by the formula (13) is carried out in the presence or absence of water and / or an organic solvent. And the fluororesin (b2) are preferably in a mass ratio of (a) / (b2) = 1/99 to 99.99 / 0.01, more preferably (a) / (b2) = 10/90 to 99. It can be obtained by mixing at a ratio of 9 / 0.1, preferably at 0 to 200 ° C., and preferably changing the solvent composition of the mixture by distillation (reduced pressure) or the like.

  Preferred examples of the fluorine-based resin (b2) include, for example, a perfluorocarbonsulfonic acid polymer (b2 ') having a structure represented by the formula (14). The perfluorocarbon sulfonic acid polymer (b2 ′) dissolves in a mixed solvent of ethanol and water but hardly dissolves in water alone. For example, the perfluorocarbon sulfonic acid polymer (b2 ′) is dissolved in a mixed solvent of photocatalyst (a), ethanol and water. The perfluorocarbon sulfonic acid polymer (b2 ′) is preferably prepared by mass ratio (a) / (b2 ′) = 1/99 to 99.9 / 0.1, more preferably (a) / (b2 ′) = 10 / After mixing at a ratio of 90 to 99/1, preferably at 0 to 200 ° C., the photocatalyst (a) can be efficiently modified by removing ethanol from the mixture by (reduced pressure) distillation or the like.

(In the formula, x is an integer of 1 to 1,000,000, y represents an integer of 1 to 100,000, and m is an integer of 0 to 20, and n represents an integer of 0 to 20.)
In a preferred embodiment of the modified photocatalyst (A) of the present invention, the number average dispersed particle diameter of a mixture of primary particles and secondary particles of the modified photocatalyst (only primary particles or secondary particles may be 400 nm or less) And more preferably 1 nm or more and 100 nm or less, particularly preferably 5 nm or more and 80 nm or less. It is preferably in the form of a sol or an aqueous dispersion. The smaller the number average dispersed particle size, the more preferable because it can cover a large area with a small amount and is less noticeable when attached to the surface.

The modified photocatalyst (A) used in the present invention, which has a wax property, is very preferable since the composition containing the composition for deodorization, antibacterial and antifungal coating has good coating performance on members.
Here, the wax property in the present invention means one that passes the evaluation of the ease of spreading and wiping in the JIS K 2236 test.
Further, the modified photocatalyst having a wax property in the present invention preferably has a spreadability measured by the following method of 10 cm or more, more preferably has a spreadability of 50 cm or more, and has a spreadability of 200 cm or more. Very preferred.

(Spreadability test)
1) About 0.03 g (1 drop with a dropper) of a dispersion of the modified photocatalyst dispersed in a solvent (a solvent having a boiling point of 150 ° C. or lower, preferably water) so as to be 5% by mass is dropped on a glass plate.
2) The glass plate on which the sample has been dropped is dried at 105 ° C. for 30 minutes.
3) Cool for 30 minutes at 23 ° C. and 55% humidity.
4) The dried modified photocatalyst is stretched with a spatula made of plastic, the length until the modified photocatalyst film to be formed starts to be interrupted is measured, and the elongation (cm) per 0.01 g of the modified photocatalyst mass is calculated. Make it spreadable.

The modified photocatalyst (A) used in the present invention includes light having an energy higher than the band gap energy of the modified photocatalyst (A) (when the modified photocatalyst (A) has a spectral sensitizing dye, When a material that increases the BET surface area by irradiation with light containing light absorbed by a dye) is preferably 10 m ² / g or more, more preferably 20 m ² / g or more, and still more preferably 50 m ² / g or more, denaturation is performed. While the photocatalyst (A) is firmly fixed to the member (when the member is an organic substrate, in a state having substrate protection), the photocatalyst (A) has excellent deodorant, antibacterial, antifungal properties and decomposition of harmful substances. It is preferable to exhibit performance.
Here, as a light source of light having an energy higher than the band gap energy of the modified photocatalyst (A) (or light containing absorption light of the spectral sensitizing dye when the modified photocatalyst (A) has a spectral sensitizing dye) For example, in addition to light obtained in a general residential environment such as sunlight or indoor lighting, light such as a black light, a xenon lamp, a mercury lamp, and an LED can be used.

Further, the modified photocatalyst (A) used in the present invention is irradiated with light having an energy higher than the band gap energy of the modified photocatalyst (A) so that the contact angle with water at 20 ° C. is higher than before the light irradiation. Those which increase by 10 ° or more and further reduce the contact angle with water at 20 ° C. by 10 ° or more by performing the light irradiation as compared with before the light irradiation preferably have a large ability to increase the BET surface area by the light irradiation described above.
The above-mentioned modified photocatalyst (A) in which the BET surface area is increased by the wax property and / or light irradiation is, for example, a photocatalyst (a) obtained by converting the photocatalyst (a) into a functional group-containing group represented by the formula (6) and / or (8) ( It can be suitably obtained by performing a modification treatment using a Si-H group-containing silicon compound having Q) as a modifier compound (b).
_{H- (R 2 SiO) m -SiR} 2 -Q (6)
(Wherein, R is each independently a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a linear or branched carbon group having 1 to 30 carbon atoms) It represents a group consisting of at least 30 fluoroalkyl groups, alkenyl groups having 2 to 30 carbon atoms, phenyl groups, alkoxy groups having 1 to 20 carbon atoms, and hydroxyl groups.

In the formula, Q is a group containing at least one functional group that is selected from the group consisting of (A) to (U) below.
(A) 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, an amino group or a salt thereof, and a polyoxyalkylene group.
(I) 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.
(U) at least one spectral sensitizing group; m is an integer and 0 ≦ m ≦ 1000. )
(RHSiO) _p (R ₂ SiO) _q (RQSiO) _r (R ₃ SiO _1/2 ) _s (8)
(Wherein, R and Q are as defined in formula (6).
p is an integer of 1 or more, q and r are 0 or an integer of 1 or more, (p + q + r) ≦ 10000, and s is 0 or 2. However, when (p + q + r) is an integer of 2 or more and s = 0, the H silicone compound is a cyclic silicone compound, and when s = 2, the H silicone compound is a chain silicone compound. )

Further, for example, the photocatalyst (a) is converted to a modifier compound (b) having a polyoxyalkylene group, for example, a polyoxyalkylene group as a functional group-containing group (Q), preferably a polyoxyalkylene group represented by the following formula (17). The modified photocatalyst (A) obtained by the modification treatment with the Si—H group-containing silicon compound represented by the above formula (6) and / or formula (8) having an oxyethylene group easily exhibits the above-mentioned wax properties. It is also preferable because it also has the ability to increase the BET surface area by the light irradiation described above.
_{-CHCH 2 O (CH 2 CH 2} O) t R 4 (17)
(In the formula, t represents an integer of 1 to 1000. R ⁴ represents a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms.)
Here, the content of the polyoxyalkylene group in the Si—H group-containing silicon compound represented by the formula (6) and / or the formula (8) is preferably 1 to 99% by mass, more preferably 5 to 99% by mass. ９０90% by mass.

The deodorant / antibacterial / mold-proof coating composition of the present invention preferably has the modified photocatalyst (A) dispersed in a solvent. At this time, the content of the modified photocatalyst (A) in the deodorant / antibacterial / mold-proof coating composition is preferably 0.001 to 30% by mass, more preferably 0.01 to 30% by mass. When the content of the modified photocatalyst (A) in the composition for deodorant / antibacterial / mold-proof coating is less than 0.001% by mass, a sufficient effect cannot be obtained unless a large amount is sprayed on the member. If it exceeds, the modified photocatalyst (A) adheres to the member in layers more than necessary, which is not efficient.
Examples of the solvent used in the composition for deodorant / antibacterial / mold-proof coating of the present invention include water and / or an organic solvent.
Examples of the organic solvent include hydrocarbon solvents having 8 to 20 carbon atoms, alcohol solvents such as alcohols and polyhydric alcohols, and ether solvents. Specific examples of the hydrocarbon solvent include decane, undecane, dodecane, paraffin and isoparaffin, and specific examples of the alcohol solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, Examples thereof include 2-butanol, denatured ethanol (8-acetylsucrose denatured alcohol), ethylene glycol and glycerin. Specific examples of the ether solvent include monoalkyl monoglyceryl ether having an alkyl chain having 1 to 12 carbon atoms, diethylene glycol. Monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monobutyl ether, Jipu b propylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monobutyl ether or di or tetraethylene glycol monophenyl ether.

  As the solvent suitably used for the deodorant / antibacterial / antifungal coating composition of the present invention, water and / or a water-soluble organic solvent are preferable. As the water-soluble organic solvent, among the above specific examples, particularly, ethanol, Denatured ethanol, glycerin, monoalkyl monoglyceryl ether having 3 to 8 carbon atoms in the alkyl chain, propylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monoethyl ether, dipropylene Glycol monobutyl ether or di- or tetraethylene glycol monophenyl ether is preferred.

The most preferable example of the solvent suitably used in the composition for deodorant, antibacterial, and antifungal coating of the present invention is that drying is quick due to safety and sterilization ability, influence on a coated surface, and spraying on a wall surface. Thus, it is a mixture of water and ethanol in a mass ratio of 10/90 to 99.9 / 0.1.
In the composition for deodorant, antibacterial and fungicide coating of the present invention, when a composition containing an adsorption-type deodorant is selected, the deodorizing effect of the member treated with the composition for deodorant, antibacterial and fungicide coating has a rapid effect. It is preferable because it is provided and the deodorizing function can be more efficiently expressed. That is, the adsorption type deodorant has a quick effect and quickly adsorbs and deodorizes a high concentration of malodorous substances, but its deodorizing ability is limited and has no sustainability. Therefore, if the modified photocatalyst (A) and the adsorption-type deodorant are used in combination as described above, the modified photocatalyst (A) has a capability of eliminating and odorizing malodorous substances over a long period of time. The adsorbed malodorous substance is also decomposed, and as a result, the deodorizing ability of the adsorptive deodorant is restored, so that it has both long-term rapidity and long-term stability.

  As the adsorption deodorant used in the present invention, for example, a physical adsorbent, a chemical adsorbent, a physicochemical adsorbent, etc., refers to those that adsorb malodorous substances and exhibit a deodorizing effect, and are colorless or white. Non-toxic ones are preferred. Examples of such an adsorption type deodorant include zeolite (hydrophilic / hydrophobic), activated clay, acid clay, hydrotalcite, sepiolite, silica-alumina, silica-magnesia, a composition of silica and zinc oxide, activated carbon, and the like. Absorbents (trade name, manufactured by Union Showa Co., Ltd.) and the like as physical adsorbents, and shoe cleans (trade name, manufactured by Lhasa Industry Co., Ltd.) and Kyoward (Kyowa Chemical Industry Co., Ltd.) as chemical adsorbents. Are commercially available. These can be used alone or in combination of two or more.

In the composition for deodorant / antibacterial / antifungal coating of the present invention, an adsorbent-based deodorant-photocatalyst modified by the modifier (b) in the presence of the photocatalyst (a) and the adsorbent-based deodorant. The use of the composite modified photocatalyst (A ′) is very preferable because the synergistic effect of the above-mentioned adsorption deodorant and the photocatalyst can be efficiently exhibited.
When a composition containing an antibacterial metal is selected in the deodorant / antibacterial / mildew-proof coating composition of the present invention, the antibacterial / mildew-proof effect of the member treated with the deodorant / antibacterial / mildew-proof coating composition is quickly effected. This is preferred because the property is imparted and the antibacterial and antifungal functions can be more efficiently expressed. That is, an antibacterial metal is known to have a strong ability to bind to an active center in a cell such as a bacterium or a mold from the beginning, and to have an antibacterial property. When used in combination with the modified photocatalyst (A) of the present invention, the antibacterial and antifungal effect of the modified photocatalyst at the time of light irradiation and the antibacterial and antifungal effect of the antibacterial metal in a dark place can be combined. Preferred.

Examples of the antibacterial metal that can be used in the present invention include metals such as silver, copper, platinum, gold, palladium, nickel, cobalt, rhodium, niobium, tin and / or oxides and mixtures thereof. Can be. Among these, it is preferable to use silver or copper.
The antibacterial metal can be used by simply adding it to the modified photocatalyst (A) or by immobilizing it. Examples of a method of immobilizing the antibacterial metal on the modified photocatalyst (A) include a method of physically adsorbing the antibacterial metal on the modified photocatalyst (A), a method of immobilizing the modified anticatalyst by a photoreduction method, or a heat treatment. Alternatively, the antibacterial metal can be immobilized on the photocatalyst (a) by physical adsorption, photoreduction, heat treatment, or the like, and then subjected to the modification treatment using the modifier compound (b) as described above.

When the composition for deodorant, antibacterial, and antifungal coating of the present invention is used as an aerosol composition containing a propellant, the modified photocatalyst (A) of the present invention spreads on the member simply by spraying on the member, and can be easily prepared. This is preferable because a member exhibiting an antifouling effect can be obtained.
The propellant may be any propellant used in ordinary aerosols, for example, nitrogen gas, nitrous oxide gas, carbon dioxide, alternative chlorofluorocarbon gas, liquefied petroleum gas (LPG), dimethyl ether or the like alone or Can be used in combination. The amount of the propellant is preferably from 30 to 98% by mass, more preferably from 80 to 98% by mass, based on the total amount of the deodorant / antibacterial / antifungal coating composition.

Since the modified photocatalyst (A) contained in the composition for deodorant / antibacterial / mold-proof coating of the present invention has a film-forming property on itself, it forms a film with good adhesion to the member, and has excellent deodorant / antibacterial properties. -Can exhibit antifungal performance.
The composition for deodorant / antibacterial / mildew-proof coating of the present invention is prepared by adding the resin (F) to the modified photocatalyst (A) of the present invention in a mass ratio (A) for the purpose of assisting adhesiveness to members. ) / (F) = 0.1 / 99.9 to 99/1, preferably those containing (A) / (F) = 1/99 to 90/10 can also be used.
As the resin (F) that can be used in the composition for deodorant / antibacterial / mold-proof coating of the present invention, all synthetic resins and natural resins can be used.

  As the synthetic resin, a thermoplastic resin and a curable resin (a thermosetting resin, a photocurable resin, a moisture-curable resin, and the like) can be used. For example, an acrylic resin, a methacrylic resin, a fluororesin, an alkyd resin, Amino alkyd resin, vinyl resin, polyester resin, styrene-butadiene resin, polyolefin resin, polystyrene resin, polyketone resin, polyamide resin, polycarbonate resin, polyacetal resin, polyetheretherketone resin, polyphenylene oxide resin, polysulfone resin, polyphenylene sulfone resin Polyether resin, polyvinyl chloride resin, polyvinylidene chloride resin, urea resin, phenol resin, melamine resin, epoxy resin, urethane resin, silicone-acrylic resin, silicone resin, water glass and zirconia Beam compounds include inorganic compounds such as titanium peroxide.

Examples of the natural polymer include cellulose resins such as nitrocellulose, isoprene resins such as natural rubber, protein resins such as casein, and starch.
The resin (F) having a higher surface energy than the modified photocatalyst (A) used in the present invention (the surface energy difference is preferably 2 mN / m or more, more preferably 5 mN / m or more, and still more preferably 10 mN / m or more). Is preferred, the composition for deodorant / antibacterial / mildew-proof coating of the present invention can have a large self-gradient in the distribution of the modified photocatalyst (A).

Here, the term “self-gradient” means that when a film is formed from the deodorant / antibacterial / mold-proof coating composition containing the modified photocatalyst (A) and the resin (F), the modified photocatalyst (A) forms the film during the formation process. Means autonomously forming a structure having a concentration gradient of the modified photocatalyst (A) in accordance with the properties of the interface (especially hydrophilic / hydrophobic) with which the photocatalyst is in contact. The modified photocatalyst (A) modified with the modifier compound (b) has a large amount on the surface of the film in contact with air.
In this specification, the expression “film” is used, but it is not necessarily a continuous film, and may be a discontinuous film, an island-shaped dispersion film, or the like.

In the present invention, the surface energy and the relative difference between the surface energies can be preferably determined by referring to, for example, a Polymer Handbook (published by A Wiley-interscience publication in the United States) or by the following method.
For example, a substrate having a resin (F) film is prepared, deionized water is dropped, a contact angle (θ) at 20 ° C. is measured, and the surface energy is calculated by the following Sell and Neumann empirical formula. Can also.

[In the formula, γs represents the surface energy (mN / m) of the surface layer measured for the contact angle of deionized water, and γ1 represents the surface energy of water {72.8 mN / m (20 ° C.)}. ]
As the resin (F) having a relatively large surface energy which can be suitably used for the composition for deodorant / antibacterial / antifungal coating of the present invention, for example, a phenyl group-containing silicone (BP) represented by the following formula (15) ).
^{_{R 1 p R 2 q X r}} SiO (4-p-q-r) / 2 (15)
(Wherein each R ¹ represents a phenyl group, and each R ² is independently a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a linear or branched X represents a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, an aminooxy group, a carbon atom having 1 to 30 carbon atoms, each independently representing a branched alkenyl group having 2 to 30 carbon atoms. Represents an oxime group of ２０20, a halogen atom, and p, q and r are 0 <p <4, 0 ≦ q <4, 0 ≦ r <4, and 0 <(p + q + r) <4; .05 ≦ p / (p + q) ≦ 1.)

Further, as the phenyl group-containing silicone (BP), a phenyl group-containing silicone (BP1) containing no alkyl group represented by the following formula (16) has a higher surface energy, and thus is preferable.
R ¹ _{s Xt} SiO _(4- ^st _{) / 2} (16)
(Wherein, R ¹ represents a phenyl group, X is each independently a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, an aminoxy group, an oxime having 1 to 20 carbon atoms. Represents a group and a halogen atom, and s and t are 0 <s <4, 0 ≦ t <4, and 0 <(s + t) <4.)
Further, at least one selected from the group consisting of a hydroxyl group and / or an alkoxy group having 1 to 20 carbon atoms, an enoxy group, an acyloxy group having 1 to 20 carbon atoms, an aminoxy group, an oxime group having 1 to 20 carbon atoms, and a halogen atom. The acrylic polymer having a silyl group having a silicon atom bonded to a hydrolyzable group at the terminal and / or side chain of the polymer molecular chain also has a relatively high surface energy and is excellent in weather resistance. Can be preferably used.

  Further, the composition for deodorant, antibacterial, and antifungal coating of the present invention contains a surfactant for the purpose of improving wettability to members and dirt components, and improving adhesion, coating properties, and spreadability. It is preferably added. Surfactants that can be added include, for example, salts of higher fatty acids, resin acids, acidic fatty alcohols, sulfates, higher alkyl sulfonic acids, alkyl allyl sulfonates, sulfonated castor oil, sulfosuccinates, and alkenyl succinic acids. Surfactants, or nonionic surfactants typified by known reaction products of ethylene oxide with long-chain fatty alcohols or phenols and phosphoric acids, and cationic interfaces containing quaternary ammonium salts and the like Activators, (partially saponified) polymer dispersion stabilizers such as polyvinyl alcohol, and those in which an ethylene glycol chain or a propylene glycol chain is bonded to a silicone polymer chain in a block polymer type, side chain-modified type, or terminal-modified type. Silicone surfactant, perfour B polyoxyethylene ethanols, perfluoroalkyl alkoxylates, include fluorine-based surfactants and their combination, such as fluorinated alkyl esters.

  In the composition for deodorant / antibacterial / antifungal coating of the present invention, as a leveling agent, for example, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, 4-hydroxy-4-methyl-2-pentanone, Propylene glycol, tripropylene glycol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, propylene glycol monomethyl ether, 1-propoxy-2-propanol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, Tripropylene glycol monoethyl ether, acetylene alcohol, liquid paraffin, isopropyl myristate, octyl myristate, dodecyl myristate, isopropyl palmitate, diiso adipate Ropyl, diisobutyl adipate, decamethylcyclopentasiloxane, silicone oil, avocado oil, jojoba oil, lanolin, cetyl 2-ethylhexanoate, butyl stearate, hexadecyl alcohol, isostearic acid, triethyl citrate, acetyl tributyl citrate, Butyl phthalate, cetyl octoate, diisoadipate adipate and the like can also be added.

In addition, as long as the effects of the present invention are not impaired, defoamers, waxes, fragrances, bactericides, fungicides, chelating agents, antioxidants, pH adjusters, ultraviolet absorbers, pigments, dyes, An inorganic filler or the like can be blended.
In the modified photocatalyst (A) of the present invention, the surface of the photocatalyst (a) is modified with the modifier compound (b) whose skeletal structure does not change due to photocatalytic activity. Difficult to contact resin (F) and the like. Therefore, even when the composition for deodorant, antibacterial, and antifungal coating of the present invention is used for treating an organic member, a base coat for protecting the organic member is not required, and the bandgap energy of the modified photocatalyst (A) can be reduced. Irradiation with high-energy light (when the modified photocatalyst (A) has a spectral sensitizing dye, light containing the absorption light of the spectral sensitizing dye) exhibits excellent stain decomposition performance and deodorization. -Antibacterial and antifungal performance can be exhibited over a long period of time.

Here, as a light source of light having an energy higher than the band gap energy of the modified photocatalyst (A) (or light containing absorption light of the spectral sensitizing dye when the modified photocatalyst (A) has a spectral sensitizing dye) For example, in addition to light obtained in a general residential environment such as sunlight or indoor lighting, light such as a black light, a xenon lamp, a mercury lamp, and an LED can be used.
When fixing the deodorant / antibacterial / mold-proof coating composition of the present invention to a member, the amount thereof is determined by the amount of the modified photocatalyst (A) attached to the member, and the amount of the modified photocatalyst (A) attached is , to the area in contact with the hazardous substances and the like, preferably ^{0.0001g / m 2 ~100g / m 2} , more preferably ^{0.001g / m 2 ~10g / m 2} .

At this time, the state of adhesion of the modified photocatalyst (A) may be a continuous film, a discontinuous film, an island-shaped dispersion film, or the like.
As a method of adhering the modified photocatalyst (A) to the member in the present invention, for example, the above-mentioned composition for deodorant / antibacterial / antifungal coating is applied to the member and dried, and then preferably 20 ° C to 500 ° C, if desired. Preferably, a method of performing a heat treatment at 40 ° C. to 250 ° C., ultraviolet irradiation, or the like can be used. Examples of the application method include a spraying method, a flow coating method, a roll coating method, a brush coating method, a dip coating method, a spin coating method, a screen printing method, a casting method, a gravure printing method, and a flexographic printing method.

In addition, the commercial form of the composition for coating the deodorant / antibacterial / antifungal of the present invention can be arbitrarily selected from various forms such as a spray type, a glue type, a wet wiper type and a squeegee type.
Further, when the modified photocatalyst (A) used in the deodorant / antibacterial / antifungal coating composition of the present invention has the above-mentioned waxy property, it may be applied to a member while spreading it, or may be applied to a member after excessively applying to the member. Thus, the modified photocatalyst (A) can be suitably adhered by a method of wiping the surplus.
The substrate of the member to which the modified photocatalyst (A) is attached using the deodorant / antibacterial / mold-proof coating composition of the present invention is not particularly limited, and can be applied to a wide variety of substrates. Examples of such base materials include organic base materials such as synthetic resins and natural resins, and inorganic base materials such as metals, ceramics, glass, stone, cement, and concrete, and combinations and composites thereof. Painted or metal-plated surfaces can be mentioned.

The composition for deodorant, antibacterial, and fungicide coating of the present invention is applied to a member contaminated with microorganisms, slime by microorganisms, molds, fungi, harmful chemical substances, etc., and performs the above-described light irradiation to deodorize, It has a bactericidal action and has a function to clean and clean the members.
At this time, since the modified photocatalyst (A) used in the composition for deodorant / antibacterial / antifungal coating of the present invention can have an affinity for harmful substances, harmful substances can be decomposed efficiently.
Further, even if the member treated with the deodorant / antibacterial / mold-proof coating composition of the present invention is contaminated with a harmful substance, the harmful substance is decomposed by light irradiation by the action of the modified photocatalyst (A) attached to the member. In addition, the members can be kept clean and neat. At this time, even when an organic base material that decomposes with a photocatalyst is used as the member, the durability is extremely excellent. That is, the deodorant / antibacterial / mold-proof coating composition of the present invention is a deodorant / antibacterial / mold-resistant member having excellent durability even on an organic substrate which could not be used conventionally due to a problem of durability. Can be provided.

  For example, when treating fibers and textiles with the deodorant / antibacterial / antifungal coating composition of the present invention, the type of fiber, weave, and use of the fiber cloth are not limited. For example, sportswear, swimwear, wets -Sports clothing such as shoes, leotards, sportswear, bedding sheets, futon covers, futon side lining, pillow covers, bedding, work clothes, nursing clothes, white coats, student clothes, drivers -Uniforms such as clothes, kimono such as undergarments, robes, half-collars, yukata, clothes, women's clothes, children's clothes, men's clothes, ties, bags, clothing covers, eyeglass wipes, celite, industrial wiping cloths, Windproof waterproof clothing such as household wiping cloths, cotton case products, futons, pillows, cushions, jackets, coats, blousons, skiwear, snowboards, and trekking wear, air conditioner covers, air Cover for purifier, fan Bars, belly bands, swimwear, underwear, towels, socks, pantyhose, innerwear, cartens, tablecloths, slippers, hats, mattresses, carpets, shoes, insoles, non-woven fabrics, tents, sails, It can be applied to hoods, ropes, wallpapers, etc.

Further, the composition for deodorant / antibacterial / mildew-proof coating of the present invention can be applied to furniture, electric appliances, walls, and the like, without being limited by the type, material, and application thereof. Furniture such as ZET, cupboards, tables, chairs, sofas, etc., appliances such as refrigerators, air conditioner filters, vacuum cleaner outlets, interior and exterior walls of houses, blinds, bathrooms, toilets, kitchen surroundings, automobiles, railways It can be applied to the interior of vehicles, airplanes, ships, and the like.
The composition for deodorant / antibacterial / mold-proof coating of the present invention can be widely used for members in hospitals as a method for preventing hospital-acquired infection. The members in the hospital include, for example, floors, carpets, walls, windows, ceilings, handrails, doors, and the like in places where an unspecified number of things come into contact, such as hospital rooms, examination rooms, corridors, stairs, elevators, waiting rooms, and washrooms. Examples include a door handle, a bed, a water tap, various medical devices, and the like. Further, antibacterial properties and antifungal properties can be effectively imparted not only to hospitals but also to various members in places requiring hygiene, such as ambulances, food storage rooms, food preparation rooms, and the like.

Further, the composition for deodorant / antibacterial / mildew-proof coating of the present invention is not limited to members in hospitals, various members of ambulances, food / pharmaceutical factories, public facilities such as schools / gymnasiums / stations, taxi / train / For sanitary control in mass transportation such as aircraft, public baths, public toilets, inns, hotels, homes, condominiums, etc. It can also be used on surfaces such as.
And the composition for deodorant / antibacterial / mold-proof coating of the present invention, besides directly spraying on the member of the object, for example, used to protect the target member for odor-proof / antibacterial / mold-proof treatment, fiber, paper, resin Alternatively, the modified photocatalyst (A) or the like may be sprayed onto a substrate such as wood or glass to remove harmful microorganisms such as external bacteria and mold, or odors.

  Furthermore, by spraying the deodorant / antibacterial / mold-proof coating composition of the present invention and installing the deodorant / antibacterial / mold-proof treated member in a living space, bacteria, harmful microorganisms such as mold and the like, and odors can be removed. Is also possible.

The present invention will be specifically described with reference to the following examples, reference examples, and comparative examples, but these do not limit the scope of the present invention. In Examples, Reference Examples and Comparative Examples, various physical properties were measured by the following methods.
1. Particle size distribution and number average particle size The solvent was appropriately added and diluted so that the photocatalyst content in the sample was 1 to 20% by mass, and the measurement was performed using a wet type particle size analyzer (Nikkiso Microtrac UPA-9230).

2. Weight average molecular weight It was determined by gel permeation chromatography (GPC) using a calibration curve prepared using a polystyrene standard.
The GPC conditions are as follows.
-Equipment: Tosoh HLC-8020 LC-3A type chromatographic column: TSKgel G1000H _XL , TSKgel G2000H _XL and TSKgel G4000H _XL (all manufactured by Tosoh) were used in series.
・ Data processor: Shimadzu CR-4A type data processor ・ Mobile phase:
Tetrahydrofuran (used for analysis of phenyl group-containing silicone)
Chloroform (used for analysis of silicone containing no phenyl group)
-Flow rate: 1.0 ml / min.
-Sample preparation method It diluted with the solvent used for a mobile phase (the density | concentration was adjusted suitably in the range of 0.5-2 weight%), and used for analysis.

3. Infrared absorption spectrum Measured using a FT / IR-5300 infrared spectrometer manufactured by JASCO Corporation.
4. Measurement of ²⁹ Si nuclear magnetic resonance The measurement was performed using JNM-LA400 manufactured by JEOL.
5. Transparency Evaluation was made by measuring a Haze value using a haze meter (NDH2000) manufactured by Nippon Denshoku Industries.
6. Wax properties (easiness of spreading and wiping)
The measurement was performed according to JIS K 2236.

7. Wax properties (spreadability)
Evaluation was performed according to the following procedure.
1) A 5% by mass aqueous dispersion of modified photocatalyst weighed to 0.03 g was dropped on a glass plate with a dropper.
2) The glass plate on which the sample was dropped was dried at 105 ° C. for 30 minutes.
3) Cooled at 23 ° C. and 55% humidity for 30 minutes.
4) The dried modified photocatalyst is stretched with a spatula made of plastic, the length until the formed modified photocatalyst film starts to be interrupted is measured, and the elongation (cm) per 0.01 g of the modified photocatalyst mass is calculated. The spreadability was determined.

8. BET surface area was measured using a nitrogen adsorption device (Autosorb-1-MP) manufactured by Yuasa Ionics.
9. Contact angle of water A drop of deionized water was placed on the surface of the sample, left at 20 ° C. for 1 minute, and measured using a Kyowa Interface Science CA-X150 contact angle meter.

10. Photocatalytic activity After applying a 5% by mass ethanol solution of methylene blue to the sample surface, irradiating it with the light of FL20S BLB type black light manufactured by Toshiba Lighting & Technology Corp. for 24 hours, the degree of decomposition of methylene blue by the action of photocatalyst (to the degree of fading of the film surface) And visual evaluation), the activity of the photocatalyst was evaluated in the following three stages.
At this time, the UV intensity measured using a Topcon UVR-2 type UV intensity meter {using a Topcon UD-36 type light receiving unit (corresponding to light having a wavelength of 310 to 400 nm) as a light receiving unit} was 1 mW / cm. ² was adjusted.
A: Methylene blue was completely decomposed.
Δ: Methylene blue blue slightly remained.
X: Decomposition of methylene blue was hardly observed.

11. Deodorization by UV irradiation A 5 cm x 1 cm sample was placed in a 120 ml glass bottle, acetaldehyde was injected in an amount such that the gas concentration in the bottle became 200 ppm, and light from a FL20SBLB type black light manufactured by Toshiba Lighting & Technology Corp. was irradiated from outside the bottle for 4 hours. After irradiation, the air in the bottle was measured with a gas chromatograph G3800 (detector FID) manufactured by Yanagimoto Seisakusho.
At this time, the UV intensity measured using a Topcon UVR-2 type UV intensity meter {using a Topcon UD-36 type light receiving unit (corresponding to light having a wavelength of 310 to 400 nm) as a light receiving unit} is ² mW / cm ^2. It was adjusted to become.

12. Deodorization by sunlight irradiation A 5 cm x 1 cm sample was placed in a 120 ml glass bottle, acetaldehyde was injected in an amount such that the gas concentration in the bottle became 200 ppm, and after irradiation of sunlight from outside the bottle for 4 hours, the inside of the bottle was removed. Was measured using a gas chromatograph G3800 (detector FID) manufactured by Yanagimoto Seisakusho.
At this time, the UV intensity (using the UD-36 type light receiving unit as the light receiving unit) measured using a Topcon UVR-2 type UV intensity meter was 0.1 to 0.3 mW / cm ² . Using a glass plate so that the visible light intensity measured using a meter {using a Topcon UD-40 type light receiving unit (corresponding to light having a wavelength of 370 to 490 nm) as the light receiving unit} is 2-3 mW / cm ^2. To adjust the sunlight intensity.

13. Antifungal test A potato dextrose agar medium previously sterilized was placed in a petri dish and solidified. A test piece (5 cm × 1 cm) was placed on the agar medium. Subsequently, five platinum loops of Aspergillus niger (IFO 4414) separately cultured in 10 ml of a 0.005% by mass aqueous solution of sodium dioctyl sulfosuccinate were taken, and spores were separated by centrifugation. A bacterial solution containing the spores in 10 ml of GPLP medium is sprayed on a test piece of a petri dish, and irradiated with a fluorescent lamp (100 W) at room temperature for 14 days. The following three stages were used for evaluation.
：: No growth of hypha at all △: Some growth of hypha is observed ×: Mycelium covers 50 to 100% of the surface

14． Antibacterial test by ultraviolet irradiation A sample of 5 cm x 1 cm was put into a sterilized plastic dish, and a bacterial solution adjusted so that the number of Escherichia coli was about 10 ⁵ cells / ml was placed in each dish. 0.5 ml of each sample was dropped on the sample, and the dish was covered with a polyethylene film to block the air from the outside, thereby preventing the bacterial solution from drying on the sample sample and preventing invasion of bacteria from the outside. Then, after irradiating the light of FL20SBLB type black light made by Toshiba Lighting Tech from outside of the petri dish for 4 hours, the bacterial solution was washed out from the petri dish, transferred to the medium, and the viable cell count was measured. Based on the obtained mortality, the antibacterial property was evaluated in the following three grades.
Death rate = {(initial viable cell count−viable cell count after test) / initial viable cell count} × 100
：: Death rate of 80% or more △: Death rate of 20% or more and less than 80% ×: Death rate of less than 20% The ultraviolet intensity is a UVR-2 type UV intensity meter manufactured by Topcon. ultraviolet intensity measured with the use} (corresponding to light of wavelength 310-400 nm) was adjusted to be 2 mW / cm ^2.

15. Antibacterial test by sunlight irradiation A 5 cm x 1 cm sample was placed in a sterilized plastic dish, and a bacterial solution adjusted so that the number of Escherichia coli was about 10 ⁵ cells / ml was placed in each dish. 0.5 ml of the sample was dropped onto the sample, and the dish was covered with a polyethylene film to block the air from the outside, thereby preventing the bacterial solution from drying on the sample sample and preventing invasion of bacteria from the outside. Subsequently, after irradiating sunlight for 4 hours from outside of the petri dish, the bacterial solution was washed out from the petri dish, transferred to a culture medium, the number of viable bacteria was measured, and based on the mortality obtained by the following equation, The antibacterial properties were evaluated on the following three scales.
Death rate = {(initial viable cell count−viable cell count after test) / initial viable cell count} × 100
：: Death rate of 80% or more △: Death rate of 20% or more and less than 80% ×: Death rate of less than 20% The sunlight intensity was measured using a UVR-2 type UV intensity meter manufactured by Topcon (as a light receiving part, The UD-36 type light receiving unit is 0.1 to 0.3 mW / cm ² , the visible light intensity measured using the ultraviolet intensity meter 計 the UD-40 type light receiving unit manufactured by Topcon (wavelength 370). (Corresponding to light of ４490 nm)) The sunlight intensity was adjusted using a glass plate so that｝ was 2-3 mW / cm ² .

16. Light fastness After irradiating the sample with the light of FL20S BLB type black light manufactured by Toshiba Lighting & Technology Corp. for 30 days, the light fastness was evaluated based on the appearance (evaluated visually) of the sample in the following three grades.
At this time, the UV intensity measured using a Topcon UVR-2 type UV intensity meter {using a Topcon UD-36 type light receiving unit (corresponding to light having a wavelength of 310 to 400 nm) as a light receiving unit} is 1 mW / cm ^2. It was adjusted to become.
：: No change in appearance △: Peeling of photocatalyst layer ×: Partial decomposition of member

[Reference Example 1]
Synthesis of modified photocatalyst hydrosol (A-1).
In a reactor equipped with a reflux condenser, a thermometer and a stirrer, 50 g of dehydrated dioxane, HMS-301-100GM (trade name of methyl hydrogen siloxane-dimethyl siloxane copolymer (manufactured by Chisso), Si-H group content 4) 0.52 mmol / g, 50 g of weight average molecular weight 5400) was added, and the temperature was raised to 80 ° C. with stirring. 25 g of UNIOX PKA-5118 [trade name of polyoxyethylene allyl methyl ether (manufactured by NOF Corporation, weight average molecular weight: 800)] and 0.53 g of a 5% by weight solution of chloroplatinic (IV) acid hexahydrate in isopropanol Was added over about 1 hour with stirring at 80 ° C., and the mixture was further stirred at 80 ° C. for 2 hours, and then cooled to room temperature to obtain a Si—H group. The obtained silicon compound solution (1) was obtained.

When 100 g of water was added to 4 g of the obtained Si-H group-containing silicon compound solution (1), a slightly cloudy dispersion was obtained.
After adding and mixing 8 g of butyl cellosolve to 2.23 g of the obtained Si—H group-containing silicon compound solution (1) and adding 8 ml of a 1N aqueous sodium hydroxide solution, hydrogen gas is generated and the volume is 21 ° C. Was 45.2 ml. The Si—H group content per 1 g of the solution containing the Si—H group-containing silicon compound (1), determined from the amount of hydrogen gas generated, was 0.825 mmol / g (Si— converted to 1 g of HMS-301-100 GM). The H group content was about 3.1 mmol / g).

Subsequently, a reactor equipped with a reflux condenser, a thermometer and a stirrer was charged with Tynok A6 [trade name of anatase-type titanium oxide sol (manufactured by Taki Kagaku), ammonia-peptized type, TiO ₂ concentration of 6% by mass, average crystallite. 10 nm (value described in the catalog)] of 400 g, and 10.3 g of the synthesized Si-H group-containing silicon compound solution (1) was added thereto at room temperature at 30 ° C. with stirring over about 30 minutes, and further heated to 30 ° C. By continuing the stirring for 10 hours, a modified photocatalyst hydrosol (A-1) having very good dispersibility was obtained. At this time, the amount of hydrogen gas generated by the reaction of the Si—H group-containing silicon compound solution (1) was 80 ml at 16 ° C. When the obtained modified titanium oxide hydrosol was coated on a KBr plate and the IR spectrum was measured, disappearance of absorption (3630 to 3640 cm ⁻¹ ) of Ti—OH groups was observed.

  1 and 2 show the particle size distributions of Tynoc A6 before the modification treatment and the resulting modified photocatalyst hydrosol (A-1), respectively. The particle size distribution of the resulting modified photocatalyst hydrosol (A-1) is monodisperse (number average particle size is 13 nm), and furthermore is monodispersion (number average particle size is 10 nm) of Tynok A6 before the modification treatment. It can be seen that the particle size distribution moves in parallel to the larger particle size side.

[Reference Example 2]
Synthesis of modified photocatalyst hydrosol (A-2).
In a reactor having a reflux condenser, a thermometer and a stirrer, 474 g of LS-8600 [trade name of 1,3,5,7-tetramethylcyclotetrasiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.)] and LS-8620 [octamethyl] 76.4 g of Cyclotetrasiloxane (trade name of Shin-Etsu Chemical Co., Ltd.) and 408 g of LS-8490 [trade name of 1,3,5-trimethyl-1,3,5-triphenylcyclotrisiloxane (trade name of Shin-Etsu Chemical Co., Ltd.)] LS-7130 [trade name of hexamethyldisiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.), 40.5 g, and sulfated zirconia, 20 g, were stirred at 50 ° C. for 3 hours, and further stirred at 80 ° C. for 5 hours. . After filtering the sulfated zirconia, low boiling components were removed at 130 ° C. under vacuum, and a methylhydrogensiloxane-methylphenylsiloxane-dimethylsiloxane copolymer having a weight average molecular weight of 6,600 and a Si—H group content of 7.93 mmol / g ( 780 g of a synthetic silicone compound) were obtained.

  In a reactor equipped with a reflux condenser, a thermometer and a stirrer, 100 g of dehydrated dioxane and 100 g of the above synthetic silicone compound were put, and the temperature was raised to 90 ° C. with stirring. 160 g of UNIOX PKA-5118 [trade name of polyoxyethylene allyl methyl ether (manufactured by NOF CORPORATION), weight average molecular weight 800], 155 g of dehydrated dioxane, and dichloro-dicyclopentadienyl-platinum (II) A solution obtained by mixing 4.9 g of a 0.25 mass% dioxane solution was added at 90 ° C. with stirring over about 1 hour, and further stirred at 90 ° C. for 5 hours, and then cooled to room temperature to obtain Si. A -H group-containing silicon compound solution (2) was obtained.

When 100 g of water was added to 4 g of the obtained Si-H group-containing silicon compound solution (2), a slightly cloudy dispersion was obtained.
After adding and mixing 8 g of butyl cellosolve to 0.88 g of the obtained Si—H group-containing silicon compound solution (2) and adding 8 ml of a 1N aqueous sodium hydroxide solution, hydrogen gas is generated, and the volume is 21 ° C. Was 41.0 ml. The Si—H group content per 1 g of the Si—H group-containing silicon compound solution (2) determined from the hydrogen gas generation amount was 1.89 mmol / g (the Si—H group content in terms of 1 g of the synthetic silicone compound was about (6.81 mmol / g).

Reflux condenser, into a reactor equipped with a thermometer and a stirrer, TKS-203 [trade name of titanium oxide hydrosol (manufactured by Tayca), neutral, TiO ₂ concentration 19.2% by weight, average crystallite diameter 6 nm ( 117.2 g of water and 107.8 g of water were added thereto, and 40.5 g of the synthesized Si—H group-containing silicon compound solution (2) was added thereto at 30 ° C. over about 30 minutes with stirring. Further, by continuing stirring at 30 ° C. for 12 hours, a modified photocatalyst hydrosol (A-2) having very good dispersibility was obtained. At this time, the amount of hydrogen gas generated by the reaction of the Si—H group-containing silicon compound solution (2) was 940 ml at 20 ° C. When the obtained modified titanium oxide hydrosol was coated on a KBr plate and the IR spectrum was measured, disappearance of absorption (3630 to 3640 cm ⁻¹ ) of Ti—OH groups was observed.

The particle size distribution of the resulting modified photocatalyst hydrosol (A-2) is monodisperse (number-average particle size is 24 nm), and the monodispersion of TKS203 before modification treatment (number-average particle size is 12 nm) It was confirmed that the particle size distribution of the sample moved parallel to the larger particle size side.
The resulting modified photocatalyst hydrosol (A-2) passed the test for ease of spreading and wiping according to JIS K 2236, and was confirmed to be in a wax property. The spread test was 50 cm, showing a good result.
Furthermore, the modified photocatalyst powder (A-2 ′) was obtained by removing the solvent from the modified photocatalyst hydrosol (A-2). The BET surface area of the resulting modified photocatalyst powder (A-2 ′) was 10 m ² / g. The modified photocatalyst powder (A-2 ') was irradiated with light of a FL20S BLB type black light manufactured by Toshiba Lighting & Technology [UVR-2 type UV intensity meter manufactured by Topcon, a UD-36 type light receiver manufactured by Topcon (wavelength: 310 to 400 nm). (Adjusted so that the UV intensity measured using｝ becomes 1 mW / cm ² ) for 10 days, the BET surface area increased to 50 m ² / g.

[Reference Example 3]
Synthesis of modified photocatalyst hydrosol (A-3).
Reflux condenser, into a reactor equipped with a thermometer and a stirrer, NTB-200 [visible light responsive type titanium oxide sol trade name (manufactured by Showa Denko), TiO ₂ concentration of 2.5 weight%, an average crystallite size 10 nm ( After adding 100 g, 4.5 g of the Si—H group-containing silicon compound solution (2) synthesized in Reference Example 2 was added thereto at 30 ° C. with stirring over about 30 minutes. By continuing stirring at 12 ° C. for 12 hours, a modified photocatalyst hydrosol (A-3) having very good dispersibility was obtained. At this time, the amount of hydrogen gas generated by the reaction of the Si—H group-containing silicon compound solution (2) was 100 ml at 20 ° C.
The particle size distribution of the resulting modified photocatalyst hydrosol (A-3) is monodisperse (number average particle size is 18 nm), and the monodispersion of NTB-200 before modification treatment (number average particle size is It was confirmed that the particle size distribution (16 nm) shifted in parallel to the larger particle size side.

[Reference Example 4]
Synthesis of modified photocatalyst hydrosol (A-4).
A reactor equipped with a reflux condenser, a thermometer and a stirrer was charged with 120 g of NTB-200 (same as that used in Reference Example 3), and Aciplex-SS910 [5% by weight of perfluorocarbon sulfonic acid polymer ethanol -Aqueous solution (1: 1 by weight) (trade name of Asahi Kasei Corporation)] was added at 30 ° C. over about 30 minutes with stirring, and the mixture was further stirred at 30 ° C. for 1 hour. The dispersion was concentrated to 90 g by an evaporator (at this time, the ethanol odor disappeared from the dispersion), and 30 g of water was added to obtain a modified photocatalyst hydrosol (A-4) having very good dispersibility.
The particle size distribution of the obtained modified photocatalyst hydrosol (A-4) is monodisperse (number average particle diameter is 34 nm), and further, monodispersion of NTB-200 before modification treatment (number average particle diameter is 16 nm). It was confirmed that the particle size distribution of the sample moved parallel to the larger particle size side.

[Reference Example 5]
Synthesis of modified photocatalyst organosol (A-5).
TKS-251 [trade name of titanium oxide organosol (manufactured by Teica) in a reactor having a reflux condenser, a thermometer and a stirrer, a dispersion medium: a mixed solvent of toluene and isopropanol, a TiO ₂ concentration of 20% by mass, and an average Crystallite diameter 6 nm (catalog value)] To 40 g, 8 g of bis (trimethylsiloxy) methylsilane is added at 40 ° C. over about 5 minutes, and stirring is further continued at 40 ° C. for 12 hours to obtain very good dispersibility. A modified photocatalyst organosol (A-5) was obtained. At this time, the amount of hydrogen gas generated by the reaction of bis (trimethylsiloxy) methylsilane was 718 ml at 23 ° C. Further, when the obtained modified titanium oxide organosol was coated on a KBr plate and the IR spectrum was measured, disappearance of absorption (3630 to 3640 cm ^-1 ) of Ti-OH groups was observed.
The particle size distribution of the resulting modified photocatalyst organosol (A-5) is monodisperse (number average particle diameter is 17 nm), and the monodispersion of TKS-251 before modification treatment (number average particle diameter is It was confirmed that the particle size distribution (12 nm) shifted in parallel to the larger particle size side.

[Reference Example 6]
Synthesis of phenyl group-containing silicone (BSP-1).
After 26.0 g of phenyltrichlorosilane was added to 78 g of dioxane in a reactor having a reflux condenser, a thermometer and a stirrer, the mixture was stirred at room temperature for about 10 minutes. A mixed solution consisting of 3.2 g of water and 12.9 g of dioxane was added dropwise thereto over about 30 minutes while maintaining the reaction solution at 10 to 15 ° C., followed by stirring at 10 to 15 ° C. for about 30 minutes. The reaction solution was heated to 60 ° C. and stirred for 3 hours. The temperature of the obtained reaction solution was lowered to 25 to 30 ° C., and 392 g of toluene was added dropwise over about 30 minutes. Then, the reaction solution was again heated to 60 ° C. and stirred for 2 hours.

The temperature of the obtained reaction solution was lowered to 10 to 15 ° C., and 19.2 g of methanol was added over about 30 minutes. Thereafter, stirring was further continued at 25 to 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 obtained reaction solution at 60 ° C. under reduced pressure to obtain a phenyl group-containing silicone (BSP-1) having a ladder skeleton having a weight average molecular weight of 2,600. (In the obtained phenyl group-containing silicone (BSP-1), absorptions (1130 cm ^-1 and 1037 cm ^-1 ) derived from the stretching vibration of the ladder skeleton in the IR spectrum were observed.)
The average composition formula of the phenyl group-containing silicone (BSP-1) obtained from the measurement result of ²⁹ Si nuclear magnetic resonance was (Ph) ₁ (OCH ₃ ) _0.58 SiO _1.21 . (Here, Ph represents a phenyl group.)

[Reference Example 7]
Synthesis of modified photocatalyst hydrosol (A-6).
40 g of the synthetic silicone compound synthesized in Reference Example 2 was placed in a reactor equipped with a reflux condenser, a thermometer and a stirrer, and the temperature was raised to 80 ° C. with stirring. 200 g of UNIOX PKA-5118 [trade name of polyoxyethylene allyl methyl ether (manufactured by NOF CORPORATION), weight average molecular weight: 800], 200 g of dehydrated methyl ethyl ketone, and 5 mass% isopropanol solution of chloroplatinic acid hexahydrate 5% 0.0g was added over about 1 hour under stirring, and the mixture was further stirred at 80 ° C. for 5 hours and then cooled to room temperature, whereby the Si—H group-containing silicon compound solution (3) was added. Obtained.

When 100 g of water was added to 4 g of the obtained Si-H group-containing silicon compound solution (3), a transparent aqueous solution was obtained.
After adding and mixing 8 g of butyl cellosolve to 3.97 g of the obtained Si—H group-containing silicon compound solution (3) and adding 8 ml of a 1N aqueous sodium hydroxide solution, hydrogen gas is generated and the volume is 21 ° C. Was 21.0 ml. The Si—H group content per 1 g of the Si—H group-containing silicon compound solution (3) obtained from the hydrogen gas generation amount was 0.22 mmol / g (the Si—H group content per 1 g of the synthetic silicone compound was about 2.37 mmol / g).

Reflux condenser, into a reactor equipped with a thermometer and a stirrer, TKS-203 [trade name of titanium oxide hydrosol (manufactured by Tayca), neutral, TiO ₂ concentration 19.2% by weight, average crystallite diameter 6 nm ( 78.1 g of water and 221.9 g of water are added thereto, and 41.3 g of the synthesized Si—H group-containing silicon compound solution (3) is added thereto at 40 ° C. over about 30 minutes with stirring. After further stirring at 40 ° C. for 12 hours, methyl ethyl ketone was removed by distillation under reduced pressure, and water was added to obtain a modified photocatalyst hydrosol (A-6) having a very good dispersibility of 5% by mass. At this time, the amount of hydrogen gas generated by the reaction of the Si—H group-containing silicon compound solution (3) was 210 ml at 20 ° C. Further, when the obtained modified titanium oxide hydrosol (A-6) was coated on a KBr plate and the IR spectrum was measured, disappearance of the absorption (3630 to 3640 cm ^-1 ) of the Ti-OH group was observed.

The particle size distribution of the resulting modified photocatalyst hydrosol (A-6) was monodisperse (number-average particle diameter was 55 nm), and TKS203 before modification was 12% (number-average particle diameter was 12 nm). It was confirmed that the particle size distribution of the sample moved parallel to the larger particle size side.
The obtained modified photocatalyst hydrosol (A-6) passed the tests of ease of spreading and wiping according to JIS K 2236, and it was confirmed that it was in the form of wax. The spread test was 450 cm, which was very good.

[Reference Example 8]
Synthesis of modified photocatalyst hydrosol (A-7).
15 g of TSS4110 [trade name of visible light responsive titanium oxide sol (manufactured by Sumitomo Chemical Co., Ltd., photocatalyst concentration: 10% by mass)] and 15 g of water were placed in a reactor equipped with a reflux condenser, a thermometer, and a stirring device. 4.1 g of the Si—H group-containing silicon compound solution (3) synthesized in Reference Example 7 was added thereto at 40 ° C. with stirring over about 30 minutes, and the mixture was further stirred at 40 ° C. for 12 hours. Methyl ethyl ketone was removed by distillation, and water was added to obtain a modified photocatalyst hydrosol (A-7) having a very good dispersibility of 5% by mass. At this time, the amount of hydrogen gas generated by the reaction of the Si-H group-containing silicon compound solution (3) was 25 ml at 20 ° C.
The particle size distribution of the obtained modified photocatalyst hydrosol (A-7) is monodisperse (number average particle diameter is 29 nm), and the monodispersion of TSS4110 before modification treatment (number average particle diameter is 13 nm) It was confirmed that the particle size distribution of the sample moved parallel to the larger particle size side.
The obtained modified photocatalyst hydrosol (A-7) passed the tests of ease of spreading and wiping according to JIS K 2236, and it was confirmed that it was in the form of wax. The spread test was 400 cm, which was very good.

[Reference Example 9]
Synthesis of modified photocatalyst aqueous dispersion (A-8).
10 g of PHTOHAP PDAP-L20 [trade name of photocatalytic apatite (titanium-modified apatite) (manufactured by Taihei Kagaku Sangyo), water dispersion having a photocatalyst concentration of 20% by mass] was placed in a reactor equipped with a reflux condenser, a thermometer and a stirrer. After adding 30 g of water, 6.0 g of the Si—H group-containing silicon compound solution (3) synthesized in Reference Example 7 was added thereto at 40 ° C. with stirring for about 30 minutes. After continuing stirring for a period of time, methyl ethyl ketone was removed by distillation under reduced pressure, and water was added to obtain a 5% by mass modified aqueous photocatalyst dispersion (A-8). At this time, the amount of hydrogen gas generated by the reaction of the Si-H group-containing silicon compound solution (3) was 33 ml at 20 ° C.
The resulting aqueous dispersion of modified photocatalyst (A-8) passed the tests for ease of spreading and wiping according to JIS K 2236, and it was confirmed that it was in the form of wax. The spread test was 350 cm, which was very good.

[Example 1]
120 g of the modified photocatalyst hydrosol (A-2) obtained in Reference Example 2 was filled together with 155 g of LPG to obtain a spray can (C-1) containing a deodorant / antibacterial / mold-proof coating composition having a capacity of 500 ml.
Using a nozzle having a diameter of 0.4 mm, the obtained spray (C-1) containing the composition for deodorant / antibacterial / mildew-proof coating was applied to 5 cm × 5 cm paper for 1 second, and dried at room temperature for 2 days. FL20SBLB type black light [adjusted so that the UV intensity measured using a Topcon UVR-2 type UV intensity meter (light receiving unit: Topcon UD-36 type light receiving unit) is ² mW / cm ² ] for 24 hours Irradiation produced a photocatalyst-carrying paper sample (D-1).

When the deodorizing property of this sample (D-1) was evaluated, 200 ppm of acetaldehyde became 5 ppm after irradiation with ultraviolet light (black light). The antifungal property of this sample (D-1) was good (○), and the antibacterial property by ultraviolet irradiation was also good (○). The light resistance of this sample (D-1) was good (○).
Furthermore, when the deodorizing property was evaluated again using the sample (D-1) after the light resistance test, 200 ppm of acetaldehyde became 3 ppm after irradiation with ultraviolet light (black light), and the deodorizing performance was maintained.
When the antifungal property and the antibacterial property by ultraviolet irradiation were evaluated again using the sample (D-1) after the light resistance test, good results were both maintained.

[Example 2]
Instead of 120 g of the modified photocatalyst hydrosol (A-2) obtained in Reference Example 2, 110 g of the modified photocatalyst hydrosol (A-1) obtained in Reference Example 1 and S-753 [trade name of water-soluble acrylic resin water sol (Manufactured by Dainippon Ink), solid content 50%], except that a mixture of 10 g was used to prepare a photocatalyst-carrying paper sample (D-2).
When the deodorizing property of this sample (D-2) was evaluated, 200 ppm of acetaldehyde became 30 ppm after ultraviolet (black light) irradiation. The antifungal property of this sample (D-2) was slightly good (△), and the antibacterial property by ultraviolet irradiation was also good (○). Further, the light resistance of this sample (D-2) was good (○).
When the deodorizing property was evaluated again using the sample (D-2) after the light resistance test, 200 ppm of acetaldehyde became 15 ppm after irradiation with ultraviolet light (black light), and the deodorizing performance was maintained.
Using the sample (D-2) after the light resistance test, the antifungal property and the antibacterial property by ultraviolet irradiation were evaluated again. As a result, both properties were maintained.

[Example 3]
100 g of the modified photocatalyst hydrosol (A-2) obtained in Reference Example 2 was hand-sprayed with 2 g of Absents # 2000 [trade name of hydrophobic zeolite (manufactured by Union Showa, average particle size 4 μm)] as an adsorbent deodorant. A spray can (C-3) containing a deodorant coating composition was obtained by cladding (having light-shielding properties).
The obtained spray (C-3) containing the deodorizing coating composition was uniformly applied to 5 cm × 5 cm paper, dried at room temperature for 2 days, and irradiated with FL20SBLB type black light manufactured by Toshiba Lighting & Technology Corp. [UVR-2 type manufactured by Topcon Corporation] A photocatalyst-carrying paper sample (D-3) was prepared by irradiating a photocatalyst-carrying paper sample (D-3) with an ultraviolet intensity meter (light-receiving unit: adjusted to have an ultraviolet intensity of ² mW / cm ² measured using a Topcon UD-36 light-receiving unit) for 24 hours. did.
When the deodorizing property of this sample (D-3) was evaluated, 200 ppm of acetaldehyde became below the detection limit (1 ppm) after irradiation with ultraviolet light (black light). The light resistance of this sample (D-3) was good (良好).
Furthermore, when the deodorizing property was evaluated again using the sample (D-3) after the light resistance test, 200 ppm of acetaldehyde became below the detection limit (1 ppm) after irradiation with ultraviolet light (black light), and the deodorizing performance was maintained. .

[Example 4]
Instead of 120 g of the modified photocatalyst hydrosol (A-2) obtained in Reference Example 2, 12 g of the modified photocatalyst organosol (A-5) obtained in Reference Example 5 and the phenyl group-containing silicone obtained in Reference Example 6 ( A photocatalyst-carrying paper sample (D-4) was prepared in the same manner as in Example 1, except that a mixture of 6 g of BSP-1) dissolved in a mixed solvent of 42 g of toluene and 50 g of isopropanol was used.
When the deodorizing property of this sample (D-4) was evaluated, 200 ppm of acetaldehyde became 20 ppm after ultraviolet (black light) irradiation. The antifungal property of this sample (D-4) was good (○), and the antibacterial property by ultraviolet irradiation was also good (○). Further, the light resistance of this sample (D-4) was good (○).
When the deodorizing property was evaluated again using the sample (D-4) after the light resistance test, 200 ppm of acetaldehyde became 10 ppm after irradiation with ultraviolet light (black light), and the deodorizing performance was maintained. In addition, both the antifungal property and the antibacterial property by ultraviolet irradiation maintained favorable results.

[Example 5]
The same operation as in Example 1 was performed except that 100 g of the modified photocatalyst hydrosol (A-3) obtained in Reference Example 3 was used instead of 120 g of the modified photocatalyst hydrosol (A-2) obtained in Reference Example 2. A photocatalyst-carrying paper sample (D-5) was prepared.
When the deodorizing property of this sample (D-5) by irradiation with sunlight was evaluated, 200 ppm of acetaldehyde became 10 ppm after irradiation with sunlight. The antifungal property of this sample (D-5) was good (○), and the antibacterial property by irradiation with sunlight was also good (○). Further, the light resistance of this sample (D-5) was good (○).
When the deodorizing property was evaluated again using the sample (D-5) after the light resistance test, 200 ppm of acetaldehyde became 15 ppm after irradiation with sunlight, and the deodorizing performance was maintained. In addition, both the antifungal property and the antibacterial property by irradiation with sunlight maintained favorable results.

[Example 6]
The same operation as in Example 1 was performed, except that 100 g of the modified photocatalyst hydrosol (A-4) obtained in Reference Example 4 was used instead of 120 g of the modified photocatalyst hydrosol (A-2) obtained in Reference Example 2. A photocatalyst-carrying paper sample (D-6) was prepared.
When the deodorizing property of this sample (D-6) by irradiation with sunlight was evaluated, 200 ppm of acetaldehyde became 5 ppm after irradiation with sunlight. The antifungal property of this sample (D-6) was good (○), and the antibacterial property by sunlight irradiation was also good (○). Further, the light resistance of this sample (D-6) was good (○).
When the deodorizing property was evaluated again using the sample (D-6) after the light resistance test, 200 ppm of acetaldehyde became 7 ppm after irradiation with sunlight, and the deodorizing performance was maintained. In addition, the evaluation of the antifungal property and the antibacterial property by irradiation with sunlight showed that both of them had good results.

[Example 7]
A 10 cm × 10 cm Japanese paper was immersed in an aqueous dispersion obtained by diluting the modified photocatalyst hydrosol (A-2) obtained in Reference Example 2 with water at 2% by mass, and then dried at room temperature for 12 hours to obtain a photocatalyst-supported sample. (D-9) was prepared.
The obtained sample (D-9) was immersed in a 0.1% by mass ethanol solution of methylene blue, and then dried at room temperature for 2 hours to prepare a colored sample (D-9 ′).
The colored sample (D-9 ') was irradiated with light from a FL20SBLB type black light manufactured by Toshiba Lighting & Technology Corp. [UVR-2 type UV intensity meter manufactured by Topcon (receiver: Topcon UD-36 type light receiver)]. ² mW / cm ² ], methylene blue in the colored sample (D-9 ′) was decomposed and the color disappeared [sample (D-9 ″)]. Further, the sample was irradiated with the light for 3 months, but the appearance of the sample (D-9 ″) was not changed at all.

Example 8
The modified photocatalyst hydrosol (A-6) synthesized in Reference Example 7 was placed in a spray can, sprayed on a 10 cm × 10 cm glass plate, dried at room temperature for 30 minutes, and then wiped off with a towel to obtain a photocatalyst-supported sample (D- 10) was prepared.
The obtained sample (D-10) was very transparent (haze value: 0.1), and the contact angle of water was 10 °. The sample (D-10) had a UV intensity of 2 mW / cm measured using a light of FL20SBLB type black light manufactured by Toshiba Lighting & Technology Corp. [UVR-2 type UV intensity meter manufactured by Topcon (light receiving unit: UD-36 type light receiving unit manufactured by Topcon)]. ² was irradiated for 2 hours, the contact angle of water became 100 °, and when the film was further irradiated for 2 hours, the contact angle of water became 0 ° [Sample (D-10 ′)].
Further, the photocatalytic activity of the sample (D-10 ′) was very good (（), and the antifungal property was also good (○). In addition, the antibacterial property by ultraviolet irradiation was also a good result (結果).

[Example 9]
A photocatalyst-supported sample was prepared in the same manner as in Example 8, except that the modified photocatalyst hydrosol (A-7) obtained in Reference Example 8 was used instead of the modified photocatalyst hydrosol (A-6) obtained in Reference Example 7. (D-11) was created.
The obtained sample (D-11) was very transparent (haze value: 0.2) and the contact angle of water was 9 °. The sample (D-11) was measured using sunlight [using a UVR-2 type UV intensity meter manufactured by Topcon and using a UD-40 type light receiving unit manufactured by Topcon (corresponding to light having a wavelength of 370 to 490 nm) as a light receiving unit]. [Adjustment so that the visible light intensity becomes 0.5 to 0.6 mW / cm ² ], the contact angle of water becomes 105 ° when irradiated for 2 hours, and the contact angle of water becomes 0 ° when irradiated further for 2 hours [ Sample (D-11 ')].
Further, the photocatalytic activity of the sample (D-11 ′) was very good (（), and the antifungal property was also good (○). In addition, the antibacterial property by sunlight irradiation was also a good result (○).

[Example 10]
A photocatalyst was prepared in the same manner as in Example 8, except that the modified photocatalyst aqueous dispersion (A-8) obtained in Reference Example 9 was used instead of the modified photocatalyst hydrosol (A-6) obtained in Reference Example 7. A supported sample (D-12) was prepared.
The obtained sample (D-12) was transparent (haze value: 0.8), and had good antifungal property (（). In addition, the antibacterial property by ultraviolet irradiation was also very good (）).

[Example 11]
The modified photocatalyst hydrosol (A-7) synthesized in Reference Example 8 was put in a spray can and sprayed on a sweaty T-shirt after use. Then, sunlight [Topcon UVR-2 UV intensity meter; Using a UD-40 type light-receiving unit (corresponding to light having a wavelength of 370 to 490 nm) produced by using｝ and a visible light intensity of ² to 3 mW / cm ² ] for 3 hours, sweat odor almost disappeared. . The appearance and feel of the T-shirt at that time were not changed at all.

[Comparative Example 1]
The same operation as in Example 1 was carried out, except that 60 g of TKS203 (same as in Reference Example 2) diluted with 60 g of water was used instead of 120 g of the modified photocatalyst hydrosol (A-2) synthesized in Reference Example 2. A paper sample (D-7) was prepared, but the photocatalyst was easily dropped from the photocatalyst-carrying paper sample (D-7), and it was difficult to evaluate the performance.

[Comparative Example 2]
A photocatalyst-supporting paper sample (D-8) was prepared in the same manner as in Example 2 except that 110 g of TYNOC A6 (same as in Reference Example 1) was used instead of 110 g of the modified photocatalyst hydrosol (A-1) synthesized in Reference Example 1. )created.
When the deodorizing property of this sample (D-8) was evaluated, 200 ppm of acetaldehyde became 10 ppm after irradiation with ultraviolet light (black light). The antifungal property of this sample (D-8) was slightly good (△), and the antibacterial property by ultraviolet irradiation was also good (○). However, the light resistance of this sample (D-8) was very poor (x).
Furthermore, when the deodorizing property was evaluated again using the sample (D-8) after the light resistance test, 200 ppm of acetaldehyde became 150 ppm after irradiation with ultraviolet light (black light), and the deodorizing performance was also reduced.
When the antifungal property and the antibacterial property were evaluated again using the sample (D-8) after the light resistance test, the performances were both reduced (x).

[Comparative Example 3]
When the photocatalyst-carrying paper sample (D-8) prepared in Comparative Example 2 was evaluated for deodorization by sunlight irradiation, 200 ppm of acetaldehyde was reduced to only 140 ppm by sunlight irradiation. Moreover, the antibacterial property evaluation by sunlight irradiation was a bad result (x).

[Comparative Example 4]
Coloring (D-13 ′) was made in the same manner as in Example 7, except that TKS203 (same as in Reference Example 2) was used instead of the modified photocatalyst hydrosol (A-2) synthesized in Reference Example 2.
When this coloring (D-13 ′) was irradiated with the same light as in Example 7 for 2 days, the coloring disappeared (sample (D-13 ″)). Partial decomposition was observed, and after one month of light irradiation, the Japanese paper did not retain its original shape.

[Comparative Example 5]
In the same manner as in Example 7, untreated Japanese paper was colored with methylene blue and irradiated with light, but the coloring did not disappear.

[Comparative Example 6]
TKS203 (same as Reference Example 2) diluted with water to 5% by mass was put into a spray can, sprayed on a glass plate of 10 cm × 10 cm, dried at room temperature for 30 minutes, and then wiped with a towel. It was possible.

  The deodorant / antibacterial / mildew-proof coating composition of the present invention can be used to decompose dirt (sweat, seasoning, oil, etc.) attached to textiles such as clothing, tobacco tar and the like attached to walls, etc. It can be widely used for environmental purification of living space, such as decomposition of dirt and prevention of dirt by microorganisms on toilets and tiles.

FIG. 1 is a diagram showing the results of measuring the particle size distribution of Tynoc A6 (a commercially available titanium oxide hydrosol) before the modification treatment using a wet particle size analyzer. FIG. 2 is a view showing the result of measuring the particle size distribution of a modified photocatalyst hydrosol (A-1) obtained by modifying the TYNOC A6 in Reference Example 1 using a wet particle size analyzer.

Claims (17)

The photocatalyst (a) is formed from a triorganosilane unit represented by the formula (1), a monooxydiorganosilane unit represented by the formula (2), a dioxyorganosilane unit represented by the formula (3), and fluorination. A modified photocatalyst modified with at least one modifier compound (b) selected from the group consisting of compounds having at least one structural unit selected from the group consisting of methylene (—CF ₂ —) units ( A composition for deodorant / antibacterial / mildew-proof coating characterized by containing A).
R ₃ Si- (1)
(Wherein, R is each independently a straight-chain or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a straight-chain or branched A fluoroalkyl group, a linear or branched alkenyl group having 2 to 30 carbon atoms, a phenyl group, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group)
— (R ₂ SiO) — (2)
(In the formula, R is as defined in the formula (1).)

(In the formula, R is as defined in the formula (1).) The composition for deodorizing, antibacterial and antifungal coating according to claim 1, wherein the modified photocatalyst (A) has a wax property. 3. The composition for deodorant / antibacterial / mildew-proof coating according to claim 1, wherein the modified photocatalyst (A) increases the BET surface area by irradiating light having an energy higher than its band gap energy. object. When the modified photocatalyst (A) irradiates light having an energy higher than its band gap energy, the contact angle with water at 20 ° C. increases by 10 ° or more than before light irradiation, and the light irradiation is further performed. 4. The composition for deodorization, antibacterial and antifungal coating according to any one of claims 1 to 3, wherein the contact angle with water at 20 ° C is reduced by 10 ° or more than before light irradiation. The deodorant / antibacterial / antibacterial compound according to any one of claims 1 to 4, wherein the modifier compound (b) is a Si-H group-containing silicon compound (b1) represented by the general formula (4). A composition for fungicide coating.
_{H x R y Q z SiO (} 4-x-y-z) / 2 (4)
(Wherein, R is each independently a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a linear or branched carbon group having 1 to 30 carbon atoms) It represents a group consisting of at least 30 fluoroalkyl groups, alkenyl groups having 2 to 30 carbon atoms, phenyl groups, alkoxy groups having 1 to 20 carbon atoms, and hydroxyl groups.
In the formula, Q is a group containing at least one functional group that is selected from the group consisting of (A) to (U) below.
(A) 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, an amino group or a salt thereof, and a polyoxyalkylene group.
(I) 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.
(U) at least one spectral sensitizing group;
Also, 0 <x <4, 0 <y <4, 0 ≦ z <4, and (x + y + z) ≦ 4. ) The modifier compound (b) is a Si—H group-containing silicon compound having a functional group-providing group-containing group (Q) represented by Formula (6) and / or Formula (8). Item 6. The composition for deodorant / antibacterial / antifungal coating according to any one of Items 1 to 5.
_{H- (R 2 SiO) m -SiR} 2 -Q (6)
(Wherein, R is each independently a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a linear or branched carbon group having 1 to 30 carbon atoms) It represents a group consisting of at least 30 fluoroalkyl groups, alkenyl groups having 2 to 30 carbon atoms, phenyl groups, alkoxy groups having 1 to 20 carbon atoms, and hydroxyl groups.
In the formula, Q is a group containing at least one functional group that is selected from the group consisting of (A) to (U) below.
(A) 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, an amino group or a salt thereof, and a polyoxyalkylene group.
(I) 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.
(U) at least one spectral sensitizing group; m is an integer and 0 ≦ m ≦ 1000. )
(RHSiO) _p (R ₂ SiO) _q (RQSiO) _r (R ₃ SiO _1/2 ) _s (8)
(Wherein, R and Q are as defined in formula (6).
p is an integer of 1 or more, q and r are 0 or an integer of 1 or more, (p + q + r) ≦ 10000, and s is 0 or 2. However, when (p + q + r) is an integer of 2 or more and s = 0, the H silicone compound is a cyclic silicone compound, and when s = 2, the H silicone compound is a chain silicone compound. ) The deodorant / antibacterial / antifungal coating composition according to any one of claims 1 to 6, wherein the modifier compound (b) has a polyoxyalkylene group. The deodorant / antibacterial / mildewproof product according to any one of claims 1 to 4, wherein the modifier compound (b) is a fluororesin (b2) having a structure represented by the formula (13). Coating composition.

(In the formula, A ^{1 to} A ⁵ may be the same or different and are each selected from a fluorine atom, a hydrogen atom, a chlorine atom, an alkyl group having 1 to 6 carbon atoms, and a halo-substituted alkyl group having 1 to 6 carbon atoms. Y represents a w-valent organic group having a molecular weight of 14 to 50000. V represents an epoxy group, a hydroxyl group, an acetoacetyl group, a thiol group, a cyclic acid anhydride group, a carboxyl group, a sulfonic acid group, Represents at least one functional group selected from the group consisting of an oxyalkylene group and a hydrolyzable silyl group, k is an integer of 0 to 1,000,000, l is an integer of 1 to 100,000, and w is 1 to 1. It is an integer of 20.) 9. The composition for deodorant / antibacterial / antifungal coating according to claim 1, wherein the modified photocatalyst (A) is a visible light responsive photocatalyst. 9. The deodorant / deodorant according to any one of claims 1 to 8, wherein the photocatalyst (a) is a metal-modified apatite in which a metal oxide having a photocatalytic action in an apatite crystal structure is formed by ion exchange. An antibacterial / antifungal coating composition. The modified photocatalyst (A) is a modified photocatalyst (A ′) of the adsorption-type deodorant-photocatalyst hybrid type obtained by modifying the photocatalyst (a) with the modifier compound (b) in the presence of the adsorption-type deodorant. The composition for deodorant / antibacterial / mildew-proof coating according to any one of claims 1 to 9, characterized in that: The composition for deodorizing, antibacterial and antifungal coating according to any one of claims 1 to 11, further comprising an adsorption type deodorant. The composition for deodorizing / antibacterial / antifungal coating according to any one of claims 1 to 12, further comprising an antibacterial metal. The deodorant / antibacterial / mold-proof coating composition according to any one of claims 1 to 13, further comprising a resin having a surface energy higher than that of the modified photocatalyst (A). The composition for deodorant / antibacterial / antifungal coating according to any one of claims 1 to 14, further comprising ethanol. The composition for deodorant / antibacterial / antifungal coating according to any one of claims 1 to 15, further comprising a propellant. A deodorant / antibacterial / mildew-resistant member treated with the deodorant / antibacterial / antifungal coating composition according to claim 1.

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