JP2004300423A - Antistatic coating composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antistatic coating composition having good fixing properties to a component, capable of exhibiting an excellent antistatic function for a long period, even when applied to the organic component, and given by utilizing a photocatalyst. <P>SOLUTION: This antistatic coating composition contains a modified photocatalyst (A), wherein the modified photocatalyst (A) is obtained by modifying and treating the photocatalyst (a) with at least one kind of modifier compound (b) selected from a group comprising compounds of which the each has at least one kind of structural unit selected from a group comprising a triorganosilane unit, a monooxydiorganosilane unit, a dioxyorganosilane unit and a fluorinated methylene (-CF<SB>2</SB>-) unit. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an antistatic coating composition which provides an antistatic member having excellent antistatic properties by maintaining the surface of the member permanently hydrophilic by the action of a modified photocatalyst.

  Plastic has excellent mechanical properties, processability, moldability, colorability, chemical resistance and light weight, so it is used in many fields such as household goods, home appliances, office equipment, automobiles and packaging materials. ing. In addition, high-molecular synthetic fibers have excellent durability, and are therefore often used in clothes, carpets, and the like. Most of plastics and synthetic fibers are electrically insulating, and therefore easily charged electrostatically, causing electric shock or spark discharge, or adsorbing dust. Static electricity charged in a copying machine or the like causes an obstacle in paper feeding. Electrostatic charging and its discharge may cause malfunctions of electronic devices and destroy integrated circuits and recording media. Fluorescent lamps, cathode ray tubes of televisions and computers scanned by electron beams tend to adsorb dust due to electrostatic charging.

As a conventional antistatic technique, there is a method in which an antistatic paint to which an organic electrolyte such as a surfactant or conductive fine particles is added is applied to the surface of an article. However, when an organic electrolyte is used to exhibit an antistatic function, there is a problem that the organic electrolyte is eluted from the interior of the coating over time, and the antistatic function is reduced early. In addition, when using conductive fine particles, a large amount of conductive fine particles are added in order to exhibit an antistatic function, so that the performance of the coating film itself is deteriorated, and the color tone of the semiconductor fine particles is reduced. There is a problem that it cannot be done.
In order to solve the above problem, an antistatic method utilizing a superhydrophilization phenomenon by irradiating a photocatalytic coating film with light has been proposed.

For example, Japanese Patent Application Laid-Open No. Hei 10-237353 proposes an antistatic coating agent containing amorphous titanium peroxide, a kiesoxide such as colloidal silica, and a photocatalyst. Further, for example, Japanese Patent Application Laid-Open Nos. 9-232320 and 10-237358 propose an antistatic coating agent containing photocatalyst particles and a silicone resin film forming element.
However, according to these methods, when an organic substance is used as a base material for imparting antistatic performance, deterioration of the base material due to a photocatalytic function occurs, so that there is a problem that the method cannot be applied to an organic base material.

On the other hand, for example, in Japanese Patent Application Laid-Open No. 2001-253006, by disposing a substrate protective layer made of amorphous titanium peroxide between the photocatalyst layer and the organic substrate, decomposition of the organic substrate by the photocatalytic function is prevented. Methods of suppressing have been proposed. However, this method is not preferable because a work process for imparting an antistatic function to the substrate becomes complicated.
In addition, the antistatic coating agent using the photocatalyst causes problems such as cracking of the coating film and generation of rainbow interference fringes unless the coating film thickness is controlled to be very thin (for example, 0.5 μm or less). There is also a problem that a special coating technique is required.
For the above-mentioned reasons, there has been a long-felt need for an antistatic coating composition that can be used more easily and can keep the coating film surface permanently hydrophilic by the photocatalytic function.
That is, a composition for antistatic coating using a photocatalyst that has good fixability to a member and can exhibit an excellent antistatic function over a long period of time even when applied to an organic member has not been completed.
JP-A-10-237353 JP-A-9-232096 JP-A-10-237358 JP 2001-253006 A

  An object of the present invention is to provide an antistatic coating composition using a photocatalyst, which has good fixability to a member and can exhibit an excellent antistatic function over a long period of time even when applied to an organic member. .

The present inventors have conducted intensive studies, and as a result, have found that a composition capable of exhibiting an excellent antistatic function over a long term can be provided by an antistatic coating composition containing a modified photocatalyst modified with a specific modifier compound. This led to 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. And a 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 composition for antistatic coating according to the first aspect of the invention, wherein the modified photocatalyst (A) has a wax property.
A third aspect of the present invention is the first or second antistatic coating according to the first or second aspect of the present invention, wherein the modified photocatalyst (A) is irradiated with light having an energy higher than its band gap energy to increase the BET surface area. It is a composition for use.
A fourth aspect of the invention is that the modified photocatalyst (A) irradiates light having an energy higher than its band gap energy so that the contact angle with water at 20 ° C. increases by 10 ° or more than before the light irradiation. The composition for antistatic coating according to any one of the first to third aspects of the invention, wherein the contact angle with water at 20 ° C. is reduced by 10 ° or more than before the light irradiation by performing the light irradiation. .

A fifth aspect of the present invention is the first antistatic coating according to the first aspect, wherein the modifier compound (b) is a silicon compound having a Si—H group (b1) represented by the general formula (4). A composition.
_{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 antistatic coating composition 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 antistatic coating composition according to any one of the first to sixth aspects, wherein the modifier compound (b) has a polyoxyalkylene group.
An eighth aspect of the invention is the first to fourth antistatic coatings of the invention, wherein the modifier compound (b) is a fluororesin (b2) having a structure represented by the formula (13). It is a composition for use.

(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 invention is the antistatic coating composition according to any one of the first to eighth aspects of the invention, wherein the modified photocatalyst (A) is a visible light responsive photocatalyst.
A tenth aspect of the invention is the antistatic coating composition according to any one of the first to ninth aspects, further comprising a resin having a surface energy greater than that of the modified photocatalyst (A).
An eleventh aspect of the invention is the antistatic coating composition according to any one of the first to tenth aspects of the invention, further comprising ethanol.
A twelfth aspect of the invention is the composition for antistatic coating according to any one of the first to eleventh aspects of the invention, further comprising a propellant.
A thirteenth invention is an antistatic member treated with any one of the first to twelfth antistatic coating compositions of the invention.

  The antistatic coating composition of the present invention can provide an antistatic member capable of exhibiting excellent antistatic performance over a long period of time by light irradiation.

Hereinafter, the present invention will be described in detail.
The composition for antistatic coating of the present invention is characterized by containing a modified photocatalyst (A).
The member treated with the antistatic coating composition of the present invention can exhibit excellent antistatic 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. 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. In addition, the antistatic function described in the present invention is based on the superhydrophilization phenomenon of the surface of the coating, and is said to be realized by a photocatalytic action weaker than the photooxidative action of the photocatalyst. Have been.

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 antistatic member treated with the antistatic coating composition of the present invention is preferable because it can sufficiently exhibit an antistatic effect even in places such as indoors where ultraviolet rays are not sufficiently irradiated.

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; 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, the use of photocatalyst particles having a number average dispersed particle diameter of 100 nm or less is very preferable since a film having excellent transparency can be obtained from the resulting antistatic coating composition comprising the modified photocatalyst (A). 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 antistatic coating composition of the present invention, the photocatalyst (a) is a triorganosilane unit represented by the formula (1), a monooxydiorganosilane unit represented by the formula (2), At least one modifier compound selected from the group consisting of compounds having at least one structural unit selected from the group consisting of a dioxyorganosilane unit and a methylene fluoride (—CF ₂ —) unit represented by The modified photocatalyst (A) modified using 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.)
Those having a wax property as the modified photocatalyst (A) used in the present invention are very preferable because the coating performance of the composition for antistatic coating containing the same on a member becomes good.
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. The photocatalyst (A) is preferable because it exhibits excellent antistatic performance while being firmly fixed to the member (when the member is an organic substrate, in a state of having substrate protection properties).
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 whose contact angle with water at 20 ° C. is reduced by 10 ° or more than before light irradiation by increasing by 10 ° or more and then performing the light irradiation are preferable because the ability to increase the BET surface area by the light irradiation is large. .

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.

  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 a sol state. The smaller the number average dispersed particle diameter, the more preferable because it can cover a large area with a small amount and is less noticeable when attached to the surface.

The antistatic 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 antistatic coating composition is preferably 0.0001 to 30% by mass, more preferably 0.001 to 30% by mass. If the content of the modified photocatalyst (A) in the antistatic coating composition is less than 0.0001% by mass, a sufficient effect cannot be obtained unless a large amount of the material is sprayed. (A) unnecessarily adheres to the member in layers more than necessary and is not efficient.
Examples of the solvent used in the antistatic coating composition 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 or 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 in the antistatic coating composition of the present invention, water and / or a water-soluble organic solvent are preferable. A 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 to tetraethylene glycol monophenyl ether is preferred.
Among them, ethanol is particularly desirable from the viewpoint of safety and the like.

When the antistatic coating composition of the present invention is used as an aerosol composition containing a propellant, the modified photocatalyst (A) or the like of the present invention spreads on the member simply by spraying on the member, and easily has an antifouling effect. It is preferable because a member that expresses it 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 mixing 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 antistatic coating composition.

Since the modified photocatalyst (A) contained in the antistatic coating composition of the present invention has a film-forming property by itself, it forms a film with good adhesion to a member and can exhibit excellent antistatic performance.
In addition, the resin (F) is added to the modified photocatalyst (A) of the present invention in a mass ratio of (A) / (F) to the composition for antistatic coating of the present invention for the purpose of assisting adhesion to a member. ) = 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 antistatic coating composition 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 surface energy higher than that of 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 antistatic coating of the present invention can have a large self-gradient in the distribution of the modified photocatalyst (A).

Here, the self-gradient means that, when a film is formed from the composition for antistatic coating containing the modified photocatalyst (A) and the resin (F), the modified photocatalyst (A) in the formation process forms an interface between the film and the film. Modifier compound having a structure in which the photocatalyst surface has a very small surface energy, which means that a structure having a concentration gradient of the modified photocatalyst (A) is autonomously formed in accordance with the properties (particularly hydrophilic / hydrophobic). A large amount of the modified photocatalyst (A) modified in (b) is present on the film surface 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 that can be suitably used in the antistatic coating composition of the present invention, for example, a phenyl group-containing silicone (BP) represented by the following formula (15) is exemplified. Can be.
^{_{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.)

  Furthermore, 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, it is preferable to add a surfactant to the antistatic coating composition of the present invention for the purpose of improving the wettability to a member and improving the adhesion, coating properties, and spreadability. 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 antistatic coating composition 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, dipropylene glycol, tripropylene glycol, Propylene 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 mono Ethyl ether, acetylene alcohol, liquid paraffin, isopropyl myristate, octyl myristate, dodecyl myristate, isopropyl palmitate, diisopropyl adipate, Diisobutyl dipinate, decamethylcyclopentasiloxane, silicone oil, avocado oil, jojoba oil, lanolin, cetyl 2-ethylhexanoate, butyl stearate, hexadecyl alcohol, isostearic acid, triethyl citrate, acetyl tributyl citrate, phthalic acid Butyl, 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 antistatic coating composition of the present invention is used for treating an organic member, it does not require a base coat for protecting the organic member, and has an energy higher than the band gap energy of the modified photocatalyst (A). By irradiating light (when the modified photocatalyst (A) has a spectral sensitizing dye, light containing the absorption light of the spectral sensitizing dye), excellent stain decomposition performance is exhibited, and antistatic performance is extended for a long time. Can be expressed.

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.
The amount of the antistatic coating composition of the present invention adhered to the member is not particularly limited, but the thickness of the film is preferably about 0.05 to 10 μm. Is preferably 0.05 to 5 μm, and more preferably 0.05 to 2 μm, in order to stably adhere and hold for a long time.
At this time, the state of adhesion of the antistatic coating composition may be a continuous film, a discontinuous film, an island-like dispersion film, or the like.

  As a method for attaching the modified photocatalyst (A) to a member in the present invention, for example, after applying the above composition for antistatic coating to a member and drying, preferably 20 ° C to 500 ° C, more preferably 40 ° C A method of performing heat treatment at 250 ° C., ultraviolet irradiation, or the like can be given. 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.

When the antistatic coating composition of the present invention is used as a coating liquid, its product form can be arbitrarily selected from various forms such as a spray type, a glue type, a wet wiper type, and a squeegee type.
Furthermore, when the modified photocatalyst (A) used in the antistatic coating composition of the present invention has the above-mentioned waxy property, a method of fixing the composition while applying it to the member, or a method of applying excess to the member after excessively coating the member with a cloth or the like. The modified photocatalyst (A) can be suitably immobilized by a method of wiping off.
The substrate on which the antistatic coating composition of the present invention is applied (also the substrate used for the antistatic function-coated product of the present invention) is not particularly limited. For example, inorganic substrates, organic substrates and Organic coating substrates having an organic film on any of the surfaces of these substrates are exemplified. Examples of the inorganic substrate include, but are not particularly limited to, a metal substrate; a glass substrate; an enamel; a water glass decorative plate, an inorganic building material such as an inorganic cured product, and ceramics.

The metal substrate is not particularly limited. For example, non-ferrous metals [eg, aluminum (JIS-H4000 etc.), aluminum alloys (eg, duralumin), copper, zinc, etc.], iron, steel [eg, rolled steel (JIS) -G3101, etc.), hot-dip galvanized steel (JIS-G3302, etc.), (rolled) stainless steel (JIS-G4304, G4305, etc.), tinplate (JIS-G3303, etc.), and other metals (including alloys). No.
The glass substrate is not particularly limited, and examples thereof include sodium soda glass, Pyrex (registered trademark) glass, quartz glass, and alkali-free glass. The enamel is obtained by baking and coating a vitreous enamel on a metal surface. Examples of the base metal include a mild steel plate, a steel plate, cast iron, and aluminum, but are not particularly limited. The enamel may be a normal enamel, and is not particularly limited.

  The water glass decorative board refers to, for example, a decorative board or the like obtained by applying sodium silicate to a cement base such as slate and baking the same. The inorganic hardened material is not particularly limited. For example, fiber-reinforced cement boards (JIS-A5430 and the like), ceramic siding (JIS-A5422 and the like), wood wool cement boards (JIS-A5404 and the like), pulp cement boards ( JIS-A5414 etc.), slate / wood wool cement laminate (JIS-A5426 etc.), gypsum board products (JIS-A6901 etc.), clay roof tiles (JIS-A5208 etc.), thick slate (JIS-A5402 etc.), porcelain Quality tile (JIS-A5209 etc.), building concrete block (JIS-A5406 etc.), terrazzo (JIS-A5411 etc.), prestressed concrete double T slab (JIS-A5412 etc.), ALC panel (JIS-A5416 etc.), cavity Prestressed concrete panel (JIS-A6 11, etc.), common bricks (JIS-R1250 and the like) curing an inorganic material such, refers to a substrate in general obtained by molding.

Although it does not specifically limit as a ceramics base material, For example, alumina, zirconia, silicon carbide, silicon nitride, etc. are mentioned.
The organic substrate is not particularly limited, and examples thereof include plastic, wood, wood, paper, and the like. The plastic substrate is not particularly limited. For example, a thermosetting or thermoplastic plastic such as a polycarbonate resin, an acrylic resin, an ABS resin, a vinyl chloride resin, an epoxy resin, and a phenol resin, and a plastic such as glass fiber, nylon Fiber reinforced plastics (FRP) reinforced with fibers such as fibers and carbon fibers.

The organic film constituting the organic coating substrate is not particularly limited, for example, acrylic, alkyd, polyester, epoxy, urethane, acrylic silicone, chlorinated rubber, phenol, melamine, etc. Examples include a cured film of a coating material containing an organic resin.
The form of the substrate is not particularly limited, and examples thereof include a film, a sheet, a plate, and a fiber. Further, the base material may be a material molded body having these shapes, a material partially having at least one of the materials having these shapes or the molded body, or the like. The substrate may be composed of the above-mentioned various materials alone, a composite material obtained by combining at least two of the above-described various materials, or a laminated material obtained by laminating at least two of the above-described various materials. May be.

The antistatic coating composition of the present invention includes, for example, household goods, household appliances, office equipment, interior and exterior parts of automobiles, packaging materials, textiles such as clothes and carpets, television and computer screens and cathode ray tubes. By applying it to at least a part of various materials or articles that require antistatic treatment, such as fluorescent lamps, etc., it exhibits an excellent antistatic function stably for a long time and has the effect of reducing the adhesion of dirt etc. A member can be provided.
Preferable examples of various materials or articles requiring an antistatic treatment include home appliances such as audio equipment such as a television, a screen and a main body of a personal computer, a refrigerator, and lighting equipment. Also, building-related members or articles, for example, exterior materials (for example, exterior wall materials, flat tiles, Japanese tiles, tiles such as metal tiles, etc.), resin rain gutters such as PVC rain gutters, and metal rain gutters such as stainless steel gutters. Such as rain gutters, gates and members used for them (eg, gates, gate posts, gate walls, etc.), fences (fences) and members used therefor, garage doors, home terraces, doors, columns, carports, bicycle parking Ports, sign posts, home delivery posts, wiring equipment such as switchboards / switches, gas meters, intercoms, TV doorphones and camera lens units, electric locks, entrance poles, rims, ventilating fan outlets, glass for buildings, etc .; windows (for example, daylighting) Windows, skylights, louvers, etc.) and members used therefor (eg, window frames, shutters, blinds, etc.), automobiles, railway vehicles, aviation , Ships, machinery and equipment, road peripheral members (for example, soundproof walls, tunnel interior boards, various display devices, guardrails, car stops, railing, traffic signposts and signposts, traffic lights, post cones, etc.), advertising towers, outdoors or Indoor lighting fixtures and members for use therein (eg, glass members, resin members, metal members, ceramic members, etc.), solar cell glass, agricultural vinyl and glass houses, air conditioner outdoor units, VHF / UHF / BS / An antenna such as CS can be used.

  The antistatic coating composition of the present invention may be directly applied to at least a part of the above-described various materials or articles, but is not limited thereto. For example, application of the antistatic coating composition of the present invention. The coating may be applied to the surface of the film substrate and, if necessary, cured to form an antistatic function film on at least a part of the above-mentioned various materials or articles. Examples of the material of the base material of such a film include polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, vinyl chloride resin, acrylic resin, fluororesin, polypropylene (PP) resin, and composite resins thereof. But are not particularly limited.

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 mass%), 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. Chargeability Evaluation was made by measuring the charge half-life based on JIS-L1094.

In measuring the charging half-life, a static meter S4101 manufactured by Nippon Static was used.
12. Light fastness After irradiating the sample with light of black light (FL20S BLB type manufactured by Toshiba Lighting & Technology Corp.) for 30 days, the light fastness was evaluated based on the appearance (visual evaluation) of the sample in the following three stages.
At this time, the UV intensity was 2 mW 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}. / Cm ² .
：: 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 mass 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 resulting 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 (mass ratio: 1: 1) (trade name, manufactured by Asahi Kasei)] 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) determined 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 resulting 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.

[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) having a capacity of 500 ml containing the antistatic coating composition.
Using a nozzle diameter of 0.4 mm, the obtained spray (C-1) containing the antistatic coating composition was applied to an acrylic plate of 5 cm × 5 cm for 1 second, dried at room temperature for 2 days, and then manufactured by Toshiba Lighting & Technology, FL20SBLB type. Irradiation with black light [adjusted so that the UV intensity measured using a Topcon UVR-2 UV intensity meter (light receiving unit: UD-36 light receiving unit made by Topcon) is ² mW / cm ² ] for 48 hours Photocatalyst carrying sample (D-1) was prepared.
The chargeability of this sample (D-1) was 40 seconds as a charge half-life. The light resistance of this sample (D-1) was also good (良好).
Furthermore, when the charging property was re-evaluated using the sample (D-1) after the light resistance test, the charging half life was as good as 38 seconds.

[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 a water-soluble acrylic resin water sol] (Manufactured by Dainippon Ink), solid content 50%], and a photocatalyst-carrying sample (D-2) was prepared in the same manner as in Example 1 except that a mixture of 10 g was used.
The chargeability of this sample (D-2) was 45 seconds as the charge half-life. The light resistance of this sample (D-2) was also good (（).
Furthermore, when the charging property was re-evaluated using the sample (D-2) after the light resistance test, the charging half life was as good as 38 seconds.

[Example 3]
In place 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 were used. Photocatalyst-supported sample (D-3) was prepared in the same manner as in Example 1 except that a mixture of 6 g of BSP-1 (BSP-1) dissolved in a mixed solution of 42 g of toluene and 50 g of isopropanol was used. .
The chargeability of this sample (D-3) was 37 seconds as the charge half-life. The light resistance of this sample (D-3) was good (良好).
Furthermore, when the charging property was re-evaluated using the sample (D-3) after the light resistance test, the charging half life was as good as 35 seconds.

[Example 4]
100 g of the modified photocatalyst hydrosol (A-3) obtained in Reference Example 3 was filled together with 155 g of LPG to obtain a spray can (C-4) having a capacity of 500 ml containing the antistatic coating composition.
Using a nozzle diameter of 0.4 mm, the spray (C-4) containing the obtained antistatic coating composition was applied to an acrylic plate of 5 cm × 5 cm for 1 second, dried at room temperature for 2 days, and then exposed to sunlight [manufactured by Topcon Co., Ltd. UV intensity measured using a UVR-2 type UV intensity meter {using a UD-36 type light receiving unit (corresponding to light having a wavelength of 310 to 400 nm) as the light receiving unit} is 0.1 to 0.3 mW / cm ² , Visible light intensity measured using the same UV intensity meter {using a Topcon UD-40 type light receiving unit (corresponding to light with a wavelength of 370 to 490 nm) as the light receiving unit} was adjusted to be ² to 3 mW / cm ^2. ] For 6 hours to prepare a photocatalyst-carrying sample (D-4).
The chargeability of this sample (D-4) was 36 seconds as the charge half-life. The light resistance of this sample (D-4) was good (○).
Furthermore, when the charging property was re-evaluated using the sample (D-4) after the light resistance test, the charging half-life was as good as 35 seconds.

[Example 5]
The same operation as in Example 4 was performed except that 100 g of the modified photocatalyst hydrosol (A-4) obtained in Reference Example 4 was used instead of 100 g of the modified photocatalyst hydrosol (A-3) obtained in Reference Example 3. A photocatalyst-carrying sample (D-5) was prepared.
The chargeability of this sample (D-5) was 32 seconds as a charge half-life. The light resistance of this sample (D-5) was also good (良好).
Furthermore, when the charging property was re-evaluated using the sample (D-5) after the light resistance test, the charging half-life was as good as 33 seconds.

[Example 6]
The modified photocatalyst hydrosol (A-6) synthesized in Reference Example 7 was put into a spray can, sprayed on an acrylic plate of 10 cm × 10 cm, dried at room temperature for 30 minutes, and then wiped off with a towel to obtain a photocatalyst-supported sample (D- 9) was created.
The obtained sample (D-9) was very transparent (haze value: 0.1), and the contact angle of water was 8 °. The sample (D-9) had a UV intensity of 2 mW / cm measured using a FL20SBLB type black light manufactured by Toshiba Lighting & Technology (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 4 hours, the contact angle of water became 109 °, and the irradiation angle of water for another 20 hours became 0 ° [Sample (D-9 ′)].
Further, the photocatalytic activity of the sample (D-9 ′) was very good (（), and the chargeability was 38 seconds as the charge half-life.

[Example 7]
A photocatalyst-supported sample was prepared in the same manner as in Example 5, 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-10) was created.
The obtained sample (D-10) was very transparent (haze value: 0.2) and the contact angle of water was 12 °. The sample (D-10) 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 104 ° when irradiated for 4 hours, and the contact angle of water becomes 0 ° when irradiated for further 20 hours [ Sample (D-10 ')].
The photocatalytic activity of the sample (D-10 ′) was very good (◎), and the charging property was 41 seconds as the charging half-life.

Example 8
The modified photocatalyst hydrosol (A-6) obtained in Reference Example 7 was bar-coated on a 20 cm × 20 cm glass plate so as to have a thickness of about 2 μm. The UV intensity measured using a type 2 UV intensity meter {using a UD-36 type light receiving unit manufactured by Topcon (corresponding to light having a wavelength of 310 to 400 nm) as the light receiving unit} is adjusted to be 1 mW / cm ² ]. Irradiation for one day produced a photocatalyst-carrying sample (D-11).
The sample (11) obtained had a good transparency (hazard value: 1.8) and a contact angle of water of 0 °. The chargeability of this sample (D-7) was 31 seconds as the charge half-life.
Further, the BET surface area of the photocatalytic film peeled off from the obtained sample (D-11) using a metal spatula was 170 m ² / g. In contrast, the BET surface area of the modified photocatalyst hydrosol (A-6) film before light irradiation was 0 m ² / g, and it can be seen that the BET surface area of the film of sample (D-11) was increased by light irradiation.

[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 sample (D-6) was prepared.
Although the charging property of this sample (D-6) was 36 seconds as the charging half-life, the photocatalyst easily dropped off from the photocatalyst-supporting sample (D-6). The light resistance of this sample (D-6) was very poor (x).

[Comparative Example 2]
Photocatalyst-supported sample (D-7) by performing the same operation as in Example 2 except that 110 g of Tynoc A6 (same as in Reference Example 1) is used instead of 110 g of the modified photocatalyst hydrosol (A-1) synthesized in Reference Example 1. It was created.
The chargeability of this sample (D-7) was 43 seconds as the charge half-life. However, the light resistance of this sample (D-7) was very poor (x).
Furthermore, the chargeability was evaluated again using the sample (D-7) after the light resistance test, but the film was deteriorated and could not be measured.

[Comparative Example 3]
A photocatalyst was prepared in the same manner as in Example 4, except that 12 g of TKS203 (same as in Reference Example 2) diluted with 88 g of water was used instead of 100 g of the modified photocatalyst hydrosol (A-3) obtained in Reference Example 3. A supported sample (D-8) was prepared.
From this sample (D-8), the photocatalyst was easily dropped, and the chargeability was 120 seconds or more as the charge half-life. In addition, the light resistance of this sample (D-8) was very poor (x).

[Comparative Example 4]
TKS203 (same as Reference Example 2) diluted to 5% by mass with water was put into a spray can, sprayed on a 10 cm × 10 cm acrylic plate, dried at room temperature for 30 minutes, and then wiped with a towel. It was possible.

  The antistatic coating composition of the present invention has good fixability to a member and can exhibit an excellent antistatic function over a long period of time even when applied to an organic member.

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 (13)

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 an antistatic coating, comprising 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 antistatic coating composition according to claim 1, wherein the modified photocatalyst (A) has a wax property.   The antistatic coating composition according to claim 1 or 2, wherein the modified photocatalyst (A) increases a BET surface area by irradiating light having an energy higher than its band gap energy.   By irradiating the modified photocatalyst (A) with light having an energy higher than its band gap energy, the contact angle with water at 20 ° C. is increased by 10 ° or more than before the light irradiation, and then the light irradiation is performed. The antistatic coating composition 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 antistatic coating 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). Composition.
_{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. An antistatic coating composition 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 antistatic coating composition according to any one of claims 1 to 6, wherein the modifier compound (b) has a polyoxyalkylene group. The composition for antistatic coating 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). .

(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.)   The antistatic coating composition according to any one of claims 1 to 8, wherein the modified photocatalyst (A) is a visible light responsive photocatalyst.   The antistatic coating composition according to any one of claims 1 to 9, further comprising a resin having a surface energy higher than that of the modified photocatalyst (A).   The antistatic coating composition according to any one of claims 1 to 10, further comprising ethanol.   The antistatic coating composition according to any one of claims 1 to 11, further comprising a propellant.   An antistatic member treated with the antistatic coating composition according to claim 1.

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