JPH10316937A - Stainproofing silicone emulsion coating composition, its production and stainproof article coated therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition which can give a cured coating film excellent in stainproofness, antifogging properties, transparency, weathering resistance, durability, etc., by including a specified partially hydrolyzed organosiloxane, nonionic and/or anionic surfactants and a specified amount of an optical semiconductor and water. SOLUTION: This composition comprises a partially hydrolyzed organosiloxane represented by the average compositional formula: R<2> a SiOb (OR<1> )c (OH)d and having a weight-average molecular weight of 600-5,000 (in terms of the PS), at least either of nonionic and anionic surfactants, a nonionic surfactant desirably having an average HLB of 9 or above, an optical semiconductor having a mean primary particle diameter of desirably 0.01-0.03 μm, being desirably titanium oxide and used in an amount of 5-80 wt.% based on the total solids of the composition and water. In the formula, R<1> and R<2> are each a monovalent hydrocarbon group; 0<=a<=3; 0<b<2; 0<c<4; 0<d<4; and a+2b+c+d=4.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an antifouling property, an antifogging property,
The present invention relates to an antifouling silicone emulsion coating material composition capable of forming a film having excellent transparency, weather resistance, durability, and the like, a method for producing the same, and an antifouling coated article using the composition.

[0002]

2. Description of the Related Art It is known that active oxygen is generated when an optical semiconductor is irradiated with ultraviolet rays (photocatalytic property). Since active oxygen can oxidize and decompose organic matter, a material in which an optical semiconductor layer or a coating containing an optical semiconductor is formed on the surface of a substrate includes a carbon-based dirt component (for example, Self-cleaning effect of decomposing carbon fractions in automobile exhaust gas and tobacco tar); deodorizing effect of decomposing malodorous components represented by amine compounds and aldehyde compounds; typical of Escherichia coli and Staphylococcus aureus It is expected to have an antibacterial effect and the like for preventing the generation of bacterial components. In addition, when ultraviolet light is applied to the coating film containing the optical semiconductor, dirt such as water-repelling organic substances attached to the coating film surface is decomposed and removed by the optical semiconductor, and the contact angle of water with the coating film surface is reduced, thereby reducing the coating angle. There is also an effect that the surface is easily wetted (familiar) with water (JP-A-61-83106, WO96 / 2937).
5 and the like). From this effect, an indoor member is expected to have an antifogging effect in which glass and mirrors are hardly fogged by water droplets, and an outdoor member is expected to have an antifouling effect in which attached dirt is washed away by rainwater.

A typical optical semiconductor is titanium oxide. In order for titanium oxide to exhibit its photocatalytic performance most strongly, the crystal type must be an anatase type. A heat treatment at 400 ° C. or more is required to transform titanium oxide from an amorphous type to an anatase type. Also, when a titanium oxide thin film is formed on a substrate surface by a sol-gel method or a chemical vapor deposition method (CVD method), which is a typical metal oxide thin film manufacturing method, a heat treatment of 400 ° C. or more is also ultimately required. is necessary. Therefore, usable substrates are limited to inorganic substrates such as glass having heat resistance.

[0004] Titanium oxide fine particles or an aqueous dispersion thereof formed into anatase crystals by heat treatment at the time of formation are generally commercially available, but titanium oxide thin films having sufficient strength are obtained by grain boundary sintering of such fine particles. Since heat treatment at 300 ° C. or higher is required to form the substrate on the surface of the substrate, the substrate is still limited in heat resistance even in this case. As a method of fixing the photocatalytic titanium oxide on the surface of the substrate having a heat resistance of less than 300 ° C., for example, there is a method of fixing the titanium oxide fine particles having the anatase crystal using a low-temperature curable binder. However, when titanium oxide is combined with an organic binder, active oxygen also decomposes the organic binder, so that the organic binder cannot be expected to have durability.

On the other hand, inorganic binders are not easily attacked by active oxygen. Examples of the inorganic low-temperature curable binder include a silicone coating material.

[0006]

However, since the optical semiconductor is generally a metal oxide, it is necessary that the dispersion medium be water in order to easily disperse the optical semiconductor. When transparency is required for the coating film, it is further necessary that the optical semiconductor has ultrafine particles having an average particle diameter of 0.1 μm or less. However, since the conventional silicone coating material is an organic solvent system, it is difficult to uniformly disperse the optical semiconductor in the silicone coating material, and the optical semiconductor is easily aggregated and precipitated. It is difficult to obtain the expected photocatalytic performance sufficiently. Further, since the coating film has low transparency and easily becomes cloudy, its use is limited.

Accordingly, an object of the present invention is to cure at a temperature lower than 300 ° C., to stably and uniformly disperse the optical semiconductor, and to obtain antifouling properties and antifogging properties derived from the photocatalytic properties of the optical semiconductor. Antifouling silicone emulsion coating material composition capable of forming a coating cured film having excellent transparency, weather resistance, durability, etc., in addition to the various properties described above, a method for producing the same, and an anti-fouling method using this composition. It is to provide a stain-coated product.

[0008]

The antifouling silicone emulsion coating material composition according to the present invention comprises the following components (A), (B), (C) and (D), and the component (C) Is 5 to 80% by weight based on the total solids in the composition. (A) Average composition formula (I): R ² _a SiO _b (OR ¹ )
_c (OH) _d (where R ¹ and R ^{2 each} represent a monovalent hydrocarbon group, and a, b, c and d are a + 2b + c + d
= 4, 0 ≦ a <3, 0 <b <2, 0 <c <4, 0 <d <
And a weight average molecular weight of 600 to 5,000 in terms of polystyrene.

(B) at least one surfactant selected from the group consisting of nonionic surfactants and anionic surfactants. (C) Optical semiconductor. (D) water. The component (B) is preferably at least one nonionic surfactant.

The average HLB value of the nonionic surfactant is preferably 9 or more. The component (C) is preferably titanium oxide. The component (C) is preferably fine particles having an average primary particle diameter of 0.001 to 0.03 μm. The antifouling silicone emulsion coating material composition of the present invention preferably also contains colloidal silica.

The antifouling silicone emulsion coating material composition of the present invention preferably also contains the following component (E). (E) the average compositional formula ^{(II): HO (R 3} 2 SiO) n H
(Where R ³ represents a monovalent hydrocarbon group, and n is 3 ≦ n ≦
A linear polysiloxane diol containing both terminal hydroxyl groups, represented by the following formula:

The antifouling silicone emulsion coating material composition of the present invention comprises an alkyd resin, an epoxy resin,
It is preferable to include at least one organic resin selected from the group consisting of acrylic resin, acrylic silicone resin, phenol resin, fluororesin, polyester resin, chlorinated rubber resin, urethane resin and melamine resin.

The organic resin is preferably the following component (F). (F) a monomer represented by the general formula (III): CH ₂ ＣＲCR ⁴ (COOR ⁵ ) (where R ⁴ represents a hydrogen atom and / or a methyl group), wherein R ⁵ is substituted or unsubstituted Wherein the first (meth) acrylic acid ester is a monovalent hydrocarbon group having 1 to 9 carbon atoms, and R ⁵ is an epoxy group, a glycidyl group, or a hydrocarbon group containing at least one of them. A second (meth) acrylic acid ester which is at least one group selected from the group consisting of: and a third (meth) acrylic acid wherein R ⁵ is a hydrocarbon group containing an alkoxysilyl group and / or a halogenated silyl group. An acrylic resin that is a copolymer with an ester.

In the present specification, (meth) acrylic ester refers to either or both of acrylic ester and methacrylic ester. The antifouling silicone emulsion coating material composition of the present invention can also contain a pigment. A first method for producing an antifouling silicone emulsion coating material composition according to the present invention comprises an emulsion containing the components (A), (B) and (D), a powder of the component (C) and / or Alternatively, the method includes a step of mixing the powder dispersion with the powder dispersion obtained by dispersing the powder in the component (D).

In a second method for producing the antifouling silicone emulsion coating material composition according to the present invention, the organic solvent is removed from the mixture of the components (A), (B) and (C) containing the organic solvent. A step of obtaining a desolvate by solventing; and a step of mixing the desolvate with at least the component (D) of the additional component (B) and the component (D).

The third method for producing the antifouling silicone emulsion coating material composition according to the present invention is represented by the following general formula (IV): R ² _m Si (OR ¹ ) _4-m (where R ¹ ,
R ² represents a monovalent hydrocarbon group, m is an integer of 0 to 3), a powder of the component (C) and / or a dispersion thereof, A step of obtaining a mixture containing the components (A) and (C) by mixing the component (D) with the mixture,
Mixing the component (B) and at least the component (B) of the additional component (D).

The antifouling coated article according to the present invention comprises a coating layer comprising a cured coating of the antifouling silicone emulsion coating composition of the present invention on the surface of a substrate. The base material is an inorganic base material, an organic base material, an inorganic-organic composite base material, or a coating base having at least one inorganic coating film and / or at least one organic coating film on any one of these base materials. Each single material of the material, a composite material combining at least two of these, and
It is preferable that at least two of these are selected from the group consisting of laminated materials.

The coating film on the surface of the coating substrate may be a primer layer.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The organosiloxane partial hydrolyzate (hereinafter referred to as "organosiloxane partial hydrolyzate (A)") used as the component (A) of the composition of the present invention has -OR at the molecular terminal. It is a three-dimensionally crosslinkable silicone compound having both ^one group and an -OH group (both directly bonded to a silicon atom).

Partially hydrolyzed organosiloxane (A)
In the above formula (I), R ¹ and R ² represent a monovalent hydrocarbon group, which may be the same or different. R ² is not particularly limited as long as it is a monovalent hydrocarbon group, but is substituted or unsubstituted and has 1 carbon atom.
Preferred are monovalent hydrocarbon groups of ~ 8, such as methyl, ethyl, propyl, butyl, pentyl,
An alkyl group such as a hexyl group, a heptyl group and an octyl group;
Cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aralkyl groups such as 2-phenylethyl group and 3-phenylpropyl group; aryl groups such as phenyl group and tolyl group; alkenyl groups such as vinyl group and allyl group; A halogen-substituted hydrocarbon group such as a γ-chloropropyl group or a 3,3,3-trifluoropropyl group; a γ-methacryloxypropyl group, a γ-glycidoxypropyl group;
Examples thereof include substituted hydrocarbon groups such as a 3,4-epoxycyclohexylethyl group and a γ-mercaptopropyl group. Among these, an alkyl group having 1 to 4 carbon atoms and a phenyl group are preferable from the viewpoint of ease of synthesis or availability.

R ¹ is not particularly limited as long as it is a monovalent hydrocarbon group. For example, an alkyl group having 1 to 4 carbon atoms is preferable. The method for preparing the organosiloxane partial hydrolyzate (A) is not particularly limited,
For example, R ¹ in the above formula (I) is an alkyl group (OR ¹
Is an alkoxy group), one or more hydrolyzable organosilanes selected from the group consisting of hydrolyzable organochlorosilanes and hydrolyzable organoalkoxysilanes are known in the art. By partially alkoxylating the silanol groups of the silanol group-containing polyorganosiloxane obtained by hydrolyzing with a large amount of water by the method, the organosiloxane partial hydrolyzate (A) can be obtained.
In this preparation method, when the hydrolysis is carried out using a hydrolyzable organoalkoxysilane, an unreacted alkoxy group and a silanol are obtained by hydrolyzing only a part of the alkoxy group by adjusting the amount of water. Since an organosiloxane partial hydrolyzate (A) in which a group coexists can be obtained, the above-mentioned treatment for partially alkoxylating the silanol group of the silanol group-containing polyorganosiloxane may be omitted.

The hydrolyzable organochlorosilane is not particularly restricted but includes, for example, methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane and the like. The hydrolyzable organoalkoxysilane is not particularly limited. For example, the hydrolyzable organoalkoxysilane has the general formula (I)
Among the hydrolyzable organosilanes represented by V), those in which R ¹ is an alkyl group are exemplified. Specifically, m =
Examples of the tetraalkoxysilane of 0 include tetramethoxysilane and tetraethoxysilane, and m = 1
Examples of the organotrialkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and 3,3,3-trifluoropropyltrimethoxysilane. .
Examples of the diorganodialkoxysilane of m = 2 include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenyldimethoxysilane, and the like. Examples thereof include trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, trimethylisopropoxysilane, and dimethylisobutylmethoxysilane.

The catalyst used for partially hydrolyzing the hydrolyzable organosilane is not particularly limited. Examples of the acidic catalyst include water-soluble acids such as hydrochloric acid and nitric acid, and acidic colloidal silica. Examples of the basic catalyst include an aqueous ammonia solution and basic colloidal silica. When a hydrolyzable organoalkoxysilane in which R ¹ is a lower alkyl group is used as the hydrolyzable organosilane, a lower aliphatic alcohol is generated in the partial hydrolysis, and the lower aliphatic alcohol is an amphiphilic solvent. Yes, it reduces the stability of the emulsion, so it is desirable to remove the solvent beforehand when preparing the composition of the present invention.

Partially hydrolyzed organosiloxane (A)
A, b, c and d in the above formula (I) are numbers that satisfy the above-mentioned relationship. When a is 3 or more, there is an inconvenience that the curing of the coating film does not proceed well. b = 0
In the case of (1), there is a problem that it is a monomer and a cured film cannot be formed. When b is 2, silica (SiO
₂ (not an organosiloxane)), which has the problem of causing cracks in the cured film. When c = 0, only the R ² group and the OH group, which is a hydrophilic group, are present at the molecular end, so that the hydrophilicity of the whole molecule is increased and the long-term stability of the emulsion cannot be obtained. When c = 4, it is a monomer and there is a problem that a cured film cannot be formed. d =
0, in the molecular terminal is only hydrophobic group ² group and group OR ¹ R, is advantageous for long-term stability of the emulsion, group OR ¹ lacks the cross-linking reaction at the time of coating film curing Therefore, a sufficient cured film cannot be obtained. When d = 4, it is a monomer, and there is a problem that a cured film cannot be formed.

Partially hydrolyzed organosiloxane (A)
Has a weight average molecular weight of 600 to 500 in terms of polystyrene.
It is in the range of 0. If it is less than 600, there is a problem that cracks occur in the applied cured film, and if it is more than 5,000, there is a problem that curing does not proceed well. The organosiloxane partial hydrolyzate (A) has the above structure, and has a high reactivity because its weight average molecular weight is within the above-mentioned predetermined range. Therefore, the composition of the present invention containing the composition does not require a curing catalyst for curing the coating film, and can be cured not only by heat but also at a low temperature.
Further, the organosiloxane partial hydrolyzate (A) has a good hydrophilic-hydrophobic balance of the molecular terminal groups despite its high reactivity, so that stable emulsion can be obtained for a long period of time.

The amount of the organosiloxane partial hydrolyzate (A) in the composition of the present invention is not particularly limited, but is, for example, preferably 1 to 30% by weight, more preferably 1 to 30% by weight, based on the total amount of the composition. -20% by weight.
When the compounding amount of (A) is less than 1% by weight, the strength as a coating film is reduced, a durable coating film cannot be formed, the transparency of the coating film is reduced, and the curing is inhibited. Or tend to. If it exceeds 30% by weight, the transparency of the coating film tends to decrease, the coating film tends to crack, and the stability of the composition of the present invention tends to decrease.

Surfactant used as component (B) of the composition of the present invention (hereinafter referred to as “surfactant (B)”)
Functions as an emulsifier (emulsifier) for dispersing the organosiloxane partial hydrolyzate (A) in water as emulsion particles. Further, since the surfactant (B) also has an effect of making the surface of the cured coating applied with the composition of the present invention easily wet with water, the coating can be formed without forcibly irradiating the coating with ultraviolet rays. Demonstrates antifogging performance and antifouling performance by rainwater washing from the beginning. The surfactant (B) may be degraded on the surface of the cured coating film or may be eluted from the surface of the coating film by flowing into rainwater, but even in such a case, the optical semiconductor (described later) contained in the coating film may be used. (C) imparts water wettability to the surface of the film by exhibiting photocatalytic performance by irradiation with natural light or indoor illumination light, etc., so that the surface of the film is easily wetted by water for a long period from the initial stage of the film formation. Will be kept.

The surfactant (B) is at least one selected from the group consisting of nonionic surfactants and anionic surfactants in order to stabilize the emulsion for a long period without impairing the stability of other components. One type of surfactant is used. At least one of these surfactants
The use of a variety of nonionic surfactants is preferred. The average HLB value of the nonionic surfactant is preferably 9 or more, more preferably 10 or more, from the viewpoint of emulsion stability.

When using cationic surfactants and amphoteric surfactants other than the above surfactants, when they are used, aggregation of the optical semiconductor tends to occur, and various functions by the optical semiconductor are sufficiently obtained. It is not used in the present invention because it is difficult. The nonionic surfactant that can be used as the surfactant (B) is not particularly limited.
Polyoxyethylene alkyl ethers (for example,
Polyoxyethylene lauryl ether, etc.), polyoxyethylene alkylaryl ethers (eg, polyoxyethylene nonyl phenyl ether, etc.), polyoxyethylene sorbitan fatty acid esters (eg, polyoxyethylene sorbitan monopalmitate, etc.) Ethylene-added nonionic surfactants; oxyethylene-oxypropylene copolymers; polyhydric alcohol fatty acid partial esters; and polyoxyethylenated polyhydric alcohol aliphatic esters. Among these, a polyoxyethylene-added nonionic surfactant is preferred from the viewpoint of emulsion stability.

The anionic surfactant which can be used as the surfactant (B) is not particularly limited. For example, alkyl benzene sulfonate, alkyl naphthalene sulfonate, fatty acid salt, rosinate, dialkyl sulfosuccinic acid Salt, hydroxyalkanesulfonate,
Alkane sulfonates, alkyl sulfates, alkyl phosphates, polyoxyethylene alkyl aryl ether sulfates and the like can be mentioned.

The amount of the surfactant (B) in the composition of the present invention is not particularly limited, but is, for example, preferably 1 to 40% by weight based on the organosiloxane partial hydrolyzate (A). %, More preferably 5-35% by weight,
More preferably, the ratio is 5 to 31% by weight. If the amount is less than 1% by weight, emulsification tends to be difficult. If the content exceeds 40% by weight, the curability and weather resistance of the coating are impaired, or the surfactant (B) is decomposed by the catalytic action of the photosemiconductor to yellow or migrate to the surface of the coating film. This may cause whitening of the film, eventually deteriorating the cured film and impairing the durability of the cured film.

The optical semiconductor (hereinafter referred to as “optical semiconductor (C)”) used as the component (C) of the composition of the present invention is not particularly limited.
Zinc oxide, tin oxide, zirconium oxide, tungsten oxide, chromium oxide, molybdenum oxide, iron oxide, nickel oxide, ruthenium oxide, cobalt oxide, copper oxide, manganese oxide, germanium oxide, lead oxide, cadmium oxide, vanadium oxide, niobium oxide , Strontium titanate, etc., in addition to metal oxides such as tantalum oxide, rhodium oxide and rhenium oxide. Among them, titanium oxide, zinc oxide, tin oxide, zirconium oxide, tungsten oxide, iron oxide, and niobium oxide are preferable because they show activity even when baked and cured at a low temperature of 100 ° C. or lower. Among these, titanium oxide is particularly preferred in view of its photocatalytic performance, safety, availability, and cost. When titanium oxide is used as the optical semiconductor (C), it is better to use an anatase type crystal.
The photocatalytic performance is the strongest and is preferable in that it is expressed for a long time.

The shape of the optical semiconductor (C) is not particularly limited, and examples thereof include a granular shape and a needle shape.
From the viewpoint of mixing stability and dispersion stability, granular, particularly fine particles are preferred. The optical semiconductor (C) can be used as a raw material as long as it finally exhibits the properties of the optical semiconductor, and is not limited.

The particle diameter of the optical semiconductor (C) is not particularly limited, but in order to stably disperse and prevent precipitation of a hard cake or the like, the average primary particle diameter is 1 to 50,000 nm.
Is preferably, more preferably 1 to 50 nm, further preferably 1 to 30 nm,
When transparency of the coating film is required, the thickness is preferably 1 to 30 nm.

The optical semiconductor (C) may be used alone or in combination of two or more. It is known that the optical semiconductor (C) generates active oxygen when irradiated with ultraviolet rays (photocatalytic property). Since active oxygen can oxidize and decompose organic substances, its properties are used to make use of the properties of carbon-based dirt components attached to painted products (for example, carbon fractions contained in exhaust gas from automobiles, and dust from cigarettes). Self-cleaning effect to decompose, etc .; deodorant effect to decompose malodorous components represented by amine compounds and aldehyde compounds;
An antibacterial effect or the like for preventing the generation of bacterial components represented by Staphylococcus aureus can be obtained. Also, attached to the coating film surface,
An effect of improving the wettability of the coating film with water is also obtained by decomposing and removing dirt such as organic substances repelling water by the optical semiconductor (C). This effect is exhibited regardless of the film thickness and the amount of the optical semiconductor (C).

Commercial products of the optical semiconductor (C) can be obtained as a powder or a dispersion. Although many dispersions are aqueous dispersions, some organic solvent dispersions are also available. Since the optical semiconductor (C) dispersed in water is water-based, it has an advantage that it can be directly introduced into an emulsion. Since the photosemiconductor (C) dispersed in a non-aqueous organic solvent reduces the stability of the emulsion,
It cannot be introduced directly into the emulsion. The optical semiconductor (C) dispersed in a non-aqueous organic solvent has the general formula (I)
When used as a reactive catalyst for the hydrolyzable organosilane represented by V), it can be obtained as a mixture of the component (A) and the optical semiconductor (C) dispersed in a non-aqueous organic solvent. If the organic solvent is removed from this mixture,
Emulsification as a mixture of the component (A) and the optical semiconductor (C) becomes possible. In the optical semiconductor (C) dispersed in water, water present as a component other than the solid content can be used as a curing agent for the hydrolyzable organosilane represented by the general formula (IV).

When the optical semiconductor (C) is a powder, the method of dispersing the powder directly with a usual dyno meal, paint shaker, or the like breaks the emulsion and causes disadvantages such as phase separation, gelation, and precipitation. May occur. Therefore, as a method of dispersing the optical semiconductor (C) powder, a powder base obtained by dispersing the optical semiconductor (C) powder in water (preferably at a high concentration) via a dispersant is added to the emulsion, It is desirable to use a method of appropriately stirring. The powder base may contain a wetting agent, a viscosity control agent, and the like, in addition to the dispersing agent. In addition, as an example of the dispersant, a nonionic urethane acryl block copolymer can be exemplified, but is not limited thereto.

The method of dispersing the above-mentioned powder base is not particularly limited, and a usual dispersing method may be used. At that time, a dispersing aid, a coupling agent and the like can be used. Optical semiconductor (C)
What carried a metal may be sufficient. The metal that may be supported is not particularly limited, but includes, for example, gold, silver,
Copper, iron, zinc, nickel, cobalt, platinum, ruthenium, palladium, rhodium, cadmium and the like,
One or more of these can be appropriately selected and used. By carrying the metal, the charge separation of the optical semiconductor (C) is promoted, and the photocatalysis is more effectively exhibited. The metal-carrying optical semiconductor (C) has an oxidizing performance in the presence of light, and exhibits an effect such as deodorization and antibacterial by the oxidizing performance.

The amount of metal carried is not particularly limited,
For example, 0.1 to 10% by weight based on the optical semiconductor (C)
And more preferably 0.2 to 5% by weight. If the loading is less than 0.1% by weight, the loading effect tends not to be sufficiently obtained. Problems tend to occur.

The method for supporting the metal is not particularly limited, and examples thereof include an immersion method, an impregnation method, and a photoreduction method. Further, a clay cross-linked body in which the optical semiconductor (C) is supported between layers may be used. By introducing the optical semiconductor (C) between the layers, the optical semiconductor (C) is supported by the fine particles, and the photocatalytic performance is improved.

The compounding amount of the optical semiconductor (C) in the antifouling silicone emulsion coating material composition varies depending on the photocatalytic performance of the optical semiconductor (C), its required effect, antifouling property, intended use, and the like. Preferably 5 to 80% by weight, based on the total solids in the coating material composition,
More preferably 5 to 75% by weight, even more preferably 5 to 75% by weight.
70% by weight. If the amount is less than 5% by weight, the photocatalytic performance is weakly expressed, and the antifouling property tends not to be expected. 8
If the content exceeds 0% by weight, the ratio of the optical semiconductor (C) in the coating film increases, and the strength of the coating film decreases, a durable coating film cannot be formed, or the transparency of the coating film increases. , And curing tends to be inhibited.

The amount of the optical semiconductor (C) is not limited to the above. For example, when the optical semiconductor (C) is an anatase-type titanium oxide, the amount of the optical semiconductor (C) is preferably 50% by weight or more in order to more effectively exhibit the decomposition of organic substances and antibacterial performance. Further, in order to make the surface of the cured coating water wettable and to more effectively exhibit antifouling effects such as antifogging and washing with rainwater, the amount of the optical semiconductor (C) may be 50% by weight or less.

The amount of water (hereinafter, referred to as “water (D)”) used as the component (D) of the composition of the present invention is not particularly limited. , Preferably 50-90% by weight, more preferably 60% by weight.
The content is preferably 90 to 90% by weight, more preferably 60 to 80% by weight. If the amount of water (D) is out of the above range, the stability of the emulsion tends to be low, and disadvantages such as generation of precipitates tend to occur.

The composition of the present invention may contain colloidal silica, if necessary. Colloidal silica has an effect of imparting excellent film-forming properties to a coated film and increasing the strength and surface hardness of the coated cured film. The silica content in the colloidal silica is not particularly limited,
For example, preferably 5 to 100% by weight, more preferably 1 to 100% by weight, based on the organosiloxane partial hydrolyzate (A)
The proportion is 5 to 80% by weight. If the silica content is less than 5% by weight, the desired coating film strength tends not to be obtained,
If it exceeds 00% by weight, it becomes difficult to uniformly disperse the colloidal silica, and the organosiloxane partial hydrolyzate (A)
Of the optical semiconductor (C) may adversely affect the dispersibility of the optical semiconductor (C), causing problems such as aggregation and sedimentation of the optical semiconductor (C).

The colloidal silica is not particularly limited, and for example, those dispersed in water or those dispersed in a non-aqueous organic solvent such as alcohol can be used. Generally, such colloidal silica contains 20 to 50% by weight of silica as a solid content, and the amount of silica can be determined from this value. Since the colloidal silica dispersed in water is aqueous, it has an advantage that it can be directly introduced into an emulsion. Colloidal silica dispersed in a non-aqueous organic solvent reduces the stability of the emulsion and cannot be directly introduced into the emulsion. When the colloidal silica dispersed in the non-aqueous organic solvent is used as a reactive catalyst of the hydrolyzable organosilane represented by the general formula (IV), the component (A) dispersed in the non-aqueous organic solvent can be used. It can be obtained as a mixture with colloidal silica. If the organic solvent is removed from the mixture, emulsification as a mixture of the component (A) and colloidal silica becomes possible. In the colloidal silica dispersed in water, water present as a component other than the solid content can be used as a curing agent for the hydrolyzable organosilane represented by the general formula (IV).

Colloidal silica dispersed in water is usually
Made from water glass, it is readily available as a commercial product. Further, colloidal silica dispersed in an organic solvent can be easily prepared by replacing water in the water-dispersed colloidal silica with an organic solvent. Such an organic solvent-dispersed colloidal silica can be easily obtained as a commercial product similarly to the water-dispersed colloidal silica. The type of the organic solvent in which the colloidal silica is dispersed is not particularly limited. For example, lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol and isobutanol; ethylene glycol, ethylene glycol monobutyl ether, and acetic acid Ethylene glycol derivatives such as ethylene glycol monoethyl ether; diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; and diacetone alcohol. One or more selected from the group consisting of these can be used. Can be. In combination with these hydrophilic organic solvents, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime and the like can also be used. Of these, lower aliphatic alcohols are preferred because of ease of solvent removal.

If necessary, the composition of the present invention may contain, as a component (E), the above-mentioned linear polysiloxane diol containing a hydroxyl group at both ends (hereinafter referred to as “linear polysiloxane diol containing a hydroxyl group at both terminals (E)” or Simply referred to as “polysiloxane diol (E)”). The polysiloxane diol (E) promotes the curing of the composition to more reliably achieve low-temperature curing, and imparts toughness (flexibility) to the cured coating applied to the composition to improve the crack resistance of the coating. It is a component to make it.

In the above average composition formula (II) representing the linear polysiloxane diol (E) having both terminal hydroxyl groups, R ³ is
Is not particularly limited as long as it is a monovalent hydrocarbon group, for example, the same materials can be used as those mentioned above as R ² in formula (I). Among such linear polysiloxane diols having R ³ , dimethylsiloxane diol, from the viewpoint of not lowering the weather resistance of the cured coating, further improving the crack resistance of the coating, and being easily available, Methylphenylsiloxane diol is preferred.

The linear polysiloxane diol (E) containing hydroxyl groups at both ends is a molecule having relatively low reactivity because it has no reactive group other than the OH group at the molecular end. Therefore, in the cured film, the polysiloxane diol (E) is in a state where only the molecular terminal is bonded or not bonded to the component (A). Since the main chain of the polysiloxane diol (E) has a two-dimensional structure and exists in a relatively mobile state, it can prevent the occurrence of cracks by absorbing the curing shrinkage due to the crosslinking of the component (A). In addition, the polysiloxane diol (E) has a hydroxyl group at both ends (A)
Since it can be relatively easily bonded to the OR ¹ group of the component, the structure as a crosslinking agent between molecules of the component (A) can be formed at a low temperature. Therefore, OR ^{1 of} component (A)
If there is a hydroxyl group of the polysiloxane diol (E) corresponding to the group, curing of the coating film at a low temperature can be more reliably achieved. That is, the polysiloxane diol (E) can provide both effects of softening the coating film and accelerating the curing. These effects can be obtained by the formula (II)
Polysiloxane diol (E) in which n is in the range of 3 ≦ n ≦ 50 (preferably 5 ≦ n ≦ 45, more preferably 5 ≦ n ≦ 40) is the largest. Since polysiloxane diol (E) is linear, it is easy to absorb curing stress,
It is easy to form a network structure as a crosslinking agent. The effect as a softening agent is so large that n is large, and when n is less than 3, there is no effect as a softening agent. The smaller the value of n, the higher the reactivity of the terminal -OH group, and the higher the effect as a curing agent. When n is greater than 50, terminal -OH
Since the reactivity of the group is low, the effect as a curing agent is low and the molecule tends to be large, so that it is not taken into the component (A) and may cause phase separation or cloudiness in a coating film. .

The amount of the polysiloxane diol (E) in the composition of the present invention depends on the size of n and is not particularly limited. For example, it is preferably 1 to 70% by weight based on the component (A). And more preferably the proportion is 10 to 55% by weight. If the amount is less than 1% by weight, a sufficient network structure as a cross-linking agent cannot be formed.
By mixing the component (A) with an appropriate amount of the polysiloxane diol (E) from a component having a large value to a component having a small value of n, a cured film having higher curability at low temperatures and improved crack resistance is formed. A silicone emulsion coating material composition that can be used.

The method of blending the polysiloxane diol (E) with the composition of the present invention is not particularly limited. For example, a method of blending the component (E) before removing the solvent of the component (A), (E) A method in which the components are emulsified and then blended is exemplified. The composition of the present invention, if necessary, is selected from the group consisting of alkyd resins, epoxy resins, acrylic resins, acrylic silicone resins, phenolic resins, fluororesins, polyester resins, chlorinated rubber resins, urethane resins and melamine resins. And at least one organic resin.

These organic resins are components capable of imparting toughness (flexibility) to the cured coating film of the composition of the present invention and improving the crack resistance of the coating film. In general, the silicone resin, which is an essential component of the composition of the present invention, and the organic resin are incompatible with each other in an organic solvent system. There is a tendency. However, since the emulsion system can exist as emulsion particles independent of each other, the above-described problem is hardly caused. Therefore, as a method of blending the organic resin with the composition of the present invention, a method of mixing the organic resin which has been emulsified in advance with the composition of the present invention which is an emulsion is desirable.

When the composition of the present invention contains the above-mentioned organic resin, the amount thereof varies depending on the kind of the organic resin and is not particularly limited, but does not inhibit the curing of the component (A) and requires the necessary flexibility. As long as it is within a range in which the property is imparted, for example, preferably 1 to 50% by weight based on the component (A),
More preferably, the ratio is 5 to 20% by weight. 1% by weight
If the amount is less than the above, sufficient flexibility may not be obtained. If the amount exceeds 50% by weight, the curing of the component (A) is inhibited, and the decomposition and deterioration of the applied cured film proceeds due to the photocatalytic action of the optical semiconductor (C). As a result, the durability of the coating may be reduced.

When the composition of the present invention containing the organic resin as an additional component is used for forming a coating film on the surface of a member used in an environment where natural light is applied, such as outdoors, The organic resin is desirably the acrylic resin described above as the component (F) (hereinafter referred to as “acrylic resin (F).” The acrylic resin (F) reduces the toughness of the applied cured film of the composition of the present invention. The acrylic resin (F) has a three-dimensional skeleton of the applied cured film of the composition of the present invention (A). The condensed cross-linked product is taken into the condensed cross-linked product to make it acryl-modified, and when the condensed cross-linked product is acryl-modified, the adhesion of the coating and cured film of the composition of the present invention to the substrate is improved.

Since the acrylic resin (F) has excellent compatibility with the component (A), it can be emulsified after mixing them, and in the obtained emulsion, (A) and (F) are The coating cured film of the silicone emulsion coating material composition which exists as emulsion particles of the mixture (modified acrylic) and contains such emulsion particles is obtained by mixing the individual independent emulsions of (A) and (F). It is more excellent in flexibility, durability, adhesion and the like than the coated and cured film of the obtained silicone emulsion coating material composition.

The first (meth) acrylic acid ester, which is one of the constituent monomers of the acrylic resin (F), is represented by the formula (III) in which R ⁵ is substituted or unsubstituted and has 1 carbon atom.
To 9 monovalent hydrocarbon groups such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group,
alkyl groups such as i-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group and octyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; 2-phenylethyl group; Aralkyl groups such as phenylpropyl group and 3-phenylpropyl group; aryl groups such as phenyl group and tolyl group; halogenated hydrocarbons such as chloromethyl group, γ-chloropropyl group and 3,3,3-trifluoropropyl group A hydroxy hydrocarbon group such as a 2-hydroxyethyl group; and the like.

The second (meth) acrylic acid ester, which is another constituent monomer of the acrylic resin (F), is represented by the formula (III) wherein R ⁵ is an epoxy group, a glycidyl group and at least one of these. It is at least one selected from the group consisting of at least one group selected from the group consisting of hydrocarbon groups containing one of them (for example, γ-glycidoxypropyl group).

The third (meth) acrylic acid ester which is still another constituent monomer of the acrylic resin (F) is represented by the formula (III) wherein R ⁵ is an alkoxysilyl group and / or a halogenated silyl group. Hydrocarbon groups including, for example, trimethoxysilylpropyl group, dimethoxymethylsilylpropyl group, monomethoxydimethylsilylpropyl group, triethoxysilylpropyl group, diethoxymethylsilylpropyl group, ethoxydimethylsilylpropyl group, trichlorosilylpropyl group , A dichloromethylsilylpropyl group, a chlorodimethylsilylpropyl group, a chlorodimethoxysilylpropyl group, a dichloromethoxysilylpropyl group, or the like.

The acrylic resin (F) comprises the first, second,
The third (meth) acrylic acid ester is a copolymer of (meth) acrylic acid esters containing at least one kind in total and at least three kinds in total, and the first, second and third (meth) acrylic acids are Another one selected from esters
Or two or more, or one or more selected from (meth) acrylates other than the above.
Copolymers containing more than one species may be used.

The first (meth) acrylic acid ester is a component for improving the toughness of the cured coating film of the composition of the present invention. For this purpose, the substituted or unsubstituted hydrocarbon group of R ⁵ preferably has a certain volume or more, and preferably has 2 or more carbon atoms. The second (meth) acrylic acid ester is a component for improving the adhesion between the applied cured film of the composition of the present invention and the substrate.

The third (meth) acrylic acid ester forms a chemical bond between the acrylic resin (F) and the component (A) when the coating of the composition of the present invention is cured, whereby the acrylic resin ( F) is fixed in the applied cured film. Further, the third (meth) acrylic acid ester also has an effect of improving the compatibility between the acrylic resin (F) and the component (A). The molecular weight of the acrylic resin (F) greatly affects the compatibility between the acrylic resin (F) and the component (A). Therefore, the acrylic resin (F) is preferably 1000 to 50
000, more preferably in the range of 1,000 to 20,000 in terms of polystyrene. The polystyrene equivalent weight average molecular weight of the acrylic resin (F) is 500
If it exceeds 00, phase separation may occur and the coating film may be whitened. If the molecular weight is less than 1,000, the toughness of the coating film tends to decrease, and cracks tend to occur.

The second (meth) acrylic acid ester is desirably at least 2% by mole of the monomer in the copolymer. If it is less than 2%, the adhesion of the coating film tends to be insufficient. The third (meth) acrylic acid ester is desirably in the range of 2 to 50% by mole ratio of the monomer in the copolymer. If it is less than 2%, the compatibility between the acrylic resin (F) and the component (A) is poor, and the coating film may be whitened. On the other hand, if it exceeds 50%, the bond density between the acrylic resin (F) and the component (A) becomes too high, and the improvement in toughness, which is the original purpose of the acrylic resin, tends not to be observed.

As a method for synthesizing the acrylic resin (F), for example, a known radical polymerization method by solution polymerization, emulsion polymerization or suspension polymerization in an organic solvent, or an anion polymerization method or a cationic polymerization method can be used. , Is not specific to this. In the radical polymerization method by solution polymerization, for example, the first, second and third (meth) acrylate monomers are dissolved in an organic solvent in a reaction vessel by a known method, and the radical polymerization is started. Add the agent,
Heat and react under a stream of nitrogen. Although the organic solvent used at this time is not particularly limited, for example, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, ethylene glycol monoethyl acetate Etc. are used. Further, the radical polymerization initiator is not particularly limited, and examples thereof include cumene hydroperoxide, tertiary butyl hydroperoxide, dicumyl peroxide, ditertiary butyl peroxide, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, and azo peroxide. Bisisobutyronitrile, hydrogen peroxide- ^{Fe2 +} salt, persulfate-
NaHSO ₃ , cumene hydroperoxide-Fe ²⁺ salt,
Benzoyl peroxide-dimethylaniline, peroxide-triethylaluminum and the like are used. In order to control the molecular weight, a chain transfer agent can be added. Examples of the chain transfer agent include, but are not limited to, quinones such as monoethylhydroquinone and p-benzoquinone; mercaptoacetic acid-ethyl ester, mercaptoacetic acid-
n-butyl ester, mercaptoacetic acid-
Thiols such as 2-ethylhexyl ester, mercaptocyclohexane, mercaptocyclopentane and 2-mercaptoethanol; thiophenols such as di-3-chlorobenzenethiol, p-toluenethiol and benzenethiol; and γ-mercaptopropyltrimethoxysilane Thiol derivatives; phenylpicrylhydrazine; diphenylamine; tert-butylcatechol and the like can be used.

The composition of the present invention can contain a water-insoluble organic solvent, if necessary, for improving the molecular weight stability of the organosiloxane partial hydrolyzate (A) in the emulsion particles. The water-insoluble organic solvent that can be used is not particularly limited, but one having a solubility of 1 g or less in 100 g of water at 25 ° C., for example, benzene,
Examples include toluene and xylene. When such a water-insoluble organic solvent is used, its compounding amount is within a range that does not cause environmental problems, for example, preferably 0 to 20% by weight, more preferably 0 to 20% by weight based on the total amount of the composition. % To 10% by weight.

The composition of the present invention may contain a thickener or a protective colloid agent which is usually added for improving the stability of the emulsion, if necessary. Protective colloids can be used as viscosity enhancers for emulsion stabilization. The thickening agent or protective colloid agent is not particularly limited, but includes, for example, celluloses such as hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose; polysaccharides such as guar gum, locust bean gum; gelatin, casein Animal proteins; water-soluble polymer compounds such as soluble starches, alginic acids, polyvinyl alcohol, and sodium polyacrylate;

[0066] Nonionic urethane acrylic block copolymers can also be used as thickeners. The nonionic urethane acrylic block copolymer exhibits an associative property with the emulsion particles and forms a highly uniform network of the emulsion and the thickener, thereby improving the emulsion stability of the composition of the present invention and the present invention. Excellent flow properties, leveling properties and thick film properties can be imparted to the composition. Such a nonionic urethane acrylic block copolymer can be easily obtained as a commercial product. When the composition of the present invention comprises a nonionic urethane acrylic block copolymer,
The amount is not particularly limited, but is, for example, preferably 0.1 to 10% by weight, more preferably 1 to 5% by weight, based on the component (A). 0.1% by weight
If it is less than 10%, the network tends not to be sufficiently formed, and if it exceeds 10% by weight, the weather resistance of the cured film tends to be impaired.

The composition of the present invention can be toned by further containing a coloring agent such as a pigment or a dye, if necessary. The coated cured film formed from the composition of the present invention hardly deteriorates in coating film performance even if it contains a coloring agent.
The pigments that can be used are not particularly limited, and include, for example, organic pigments such as carbon black, quinacridone, naphthol red, cyanine blue, cyanine green, and Hansa yellow; titanium oxide, barium sulfate, red iron oxide,
Inorganic pigments such as composite metal oxides are preferred, and one or more of these pigments may be used in combination.

As a method of dispersing the pigment, a method of directly dispersing the pigment powder using a usual dyno meal, paint shaker, or the like may break the emulsion and cause problems such as phase separation, gelation, and precipitation. Therefore,
As a method for dispersing the pigment, a method in which a pigment base obtained by dispersing a pigment in water (preferably at a high concentration) via a dispersant is added to the emulsion and the mixture is appropriately stirred is preferable. Commercial pigment-based products are readily available. The pigment base may contain a wetting agent, a viscosity control agent, and the like, in addition to the dispersant. In addition, as an example of the dispersant, the nonionic urethane acryl block copolymer can be exemplified, but is not limited thereto.

The pigment-based dispersion method is not particularly limited, and a usual dispersion method may be used. At that time, a dispersing aid, a coupling agent and the like can be used. In the composition of the present invention, the compounding amount of the pigment is not particularly limited because the concealing property varies depending on the kind of the pigment.
Preferably 5 to 100% by weight based on the total amount of the components,
More preferably, the ratio is 5 to 80% by weight. When the amount of the pigment is less than 5% by weight, the concealing property tends to be deteriorated. .

The dye which can be used for toning the composition of the present invention is not particularly limited. Examples include dyes of acridine type, quinone imine type, thiazole type, methine type, nitro type, nitroso type and the like. One kind selected from these groups or a combination of two or more kinds may be used.

In the composition of the present invention, the compounding amount of the dye is not particularly limited because the coloring property varies depending on the kind of the dye. And preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight. The amount of dye is 0.1
If it is less than 50% by weight, the coloring property tends to be poor,
If the amount is more than 10% by weight, the durability of the cured film may be deteriorated or the strength of the cured film may be reduced.

The composition of the present invention may contain, if necessary, components other than those described above, for example, a leveling agent, a metal powder, a glass powder, an antibacterial agent (preferably an inorganic antibacterial agent), an antioxidant, an antistatic agent, and an ultraviolet ray. An absorbent, an antifoaming agent, a fungicide, and the like can be contained within a range that does not adversely affect the effects of the present invention. Since the composition of the present invention can be cured at low temperature and heat without a curing catalyst, it does not need to contain a curing catalyst. However, by promoting the condensation reaction of the organosiloxane partial hydrolyzate (A), the composition can be coated. A curing catalyst may be further included, if necessary, for the purpose of accelerating the heat curing of the film or curing the film at room temperature. Examples of the curing catalyst include, but are not limited to, alkyl titanates; metal carboxylate salts such as tin laurate, tin octylate, iron octylate, lead octylate, dibutyltin dilaurate, and dioctyltin dimaleate;
Amine compounds such as hexylamine and guanidine and their hydrochlorides; carboxylic acid salts of amines such as dibutylamine-2-hexoate, dimethylamine acetate and ethanolamine acetate; quaternary ammonium salts of carboxylic acids such as tetramethylammonium acetate; tetraethyl Amines such as pentamine, N-β-aminoethyl-γ-
Amine silane coupling agents such as aminopropyltrimethoxysilane and N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane; acids such as p-toluenesulfonic acid, phthalic acid and hydrochloric acid; aluminum alkoxides and aluminum chelates Aluminum compounds; alkali metal salts such as lithium acetate, potassium acetate, lithium formate, sodium formate, potassium phosphate, and potassium hydroxide; titanium compounds such as tetraisopropyl titanate, tetrabutyl titanate, and titanium tetraacetylacetonate; methyltrichlorosilane; Halogenated silanes such as dimethyldichlorosilane and trimethylmonochlorosilane are exemplified. However, other than these, there is no particular limitation as long as it is effective for accelerating the condensation reaction of the organosiloxane partial hydrolyzate (A). In addition,
When these curing catalysts are used, it is desirable to prepare an emulsion using a surfactant (B) and water (D) in advance by a conventional method.

The method of applying the composition of the present invention is not particularly limited, and examples thereof include ordinary methods such as brushing, spraying, dipping (dipping), bar, flow, roll, curtain, knife coat, and spin coat. Various coating methods can be selected. When diluting the composition of the present invention, dilution with water is desirable, but if necessary, for adjusting the leveling property or drying property of the coated surface and for improving the stability of the composition of the present invention. In addition, for example, cellosolves such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol monobutyl ether; propylene glycol ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether;
A small amount of an organic solvent such as a carbitol type such as diethylene glycol monoethyl ether and diethylene glycol monobutyl ether; and a triglycol ether type such as triethylene glycol monomethyl ether and tripropylene glycol monomethyl ether may be added to the composition.

The method of curing the composition of the present invention applied to a substrate may be a known method, and is not particularly limited. The temperature at the time of curing is also not particularly limited, and may be in a wide range from room temperature to heating temperature depending on the desired performance of the applied cured coating, the use of a curing catalyst, the heat resistance of the optical semiconductor (C) or the base material, and the like. A range can be taken. The thickness of the coating film (cured coating) formed from the composition of the present invention is not particularly limited, and is preferably, for example, about 0.1 to 50 μm, but the coating film is stably adhered and held for a long time, and In order not to cause cracks, peeling, etc., it is more preferable that
μm.

The method for producing the composition of the present invention includes:
Although not particularly limited, for example, (A), (B),
It can be obtained by mixing and stirring the components (C) and (D). The stirring method, that is, the so-called emulsifying method is not particularly limited, and a known method can be used. Examples thereof include a method of emulsifying using an emulsifying machine such as a homogenizer and a homomixer. At that time, (A), (B),
The mixing order of the components (C) and (D) is not particularly limited. For example, after the components (A), (C) and (D) are uniformly mixed, the components (B) or (B) are added thereto. A method in which the components (B) and (D) are added and emulsified by using the emulsifier described above is exemplified.

The method for producing the composition of the present invention is not limited to the above. For example, any one of the first to third manufacturing methods of the present invention may be used. The first production method is a method of obtaining an antifouling silicone emulsion coating material composition by forming an emulsion with the components (A), (B) and (D) and then adding the component (C). This is an advantageous method when the amount of the component (C) to be added to the required photocatalytic performance is appropriately selected. When removing the organic solvent of the component (A), the component (B) may be previously added as a polymerization inhibitor of the component (A) at that time, as described later.

In the second production method of the present invention, the solvent is removed from the mixture of the components (A), (B) and (C) containing the organic solvent to obtain a desolvated product. , The desolvate, the additional component (B) and the component (D)
By mixing at least the component (D) among the components, an antifouling silicone emulsion coating material composition is obtained.

In the second production method, the organic solvent contained in the mixture of the components (A), (B) and (C) to be desolvated is a hydrolyzable organoalkoxy as a raw material of the component (A). Alcohol produced as a by-product of the hydrolysis reaction of hydrolyzable organoalkoxysilane when silane was used, or contained in organic solvent-dispersed optical semiconductor (C) as component (C). Organic solvents and the like. From the viewpoint of ease of solvent removal, R ¹ of the hydrolyzable organoalkoxysilane is preferably a lower alkyl group, and the organic solvent contained in the organic solvent-dispersed optical semiconductor (C) is preferably a lower aliphatic alcohol.

The method for desolvating the organic solvent is not particularly limited. For example, a method of desolvating the organic solvent under the conditions of heating and normal pressure, normal temperature and reduced pressure or heating and reduced pressure can be used. From the viewpoint of inhibiting the polymerization of the components, it is desirable to remove the solvent by heating at a temperature as low as possible and under reduced pressure. In the first production method, the period from desolvation of the component-containing solution to the emulsification of the component-containing solution, and in the second production method, the component-containing solution or the components (A), (B),
For the purpose of suppressing the reactivity of the component (A) during the period from desolvation of the mixture of the component (C) to emulsification, and for maintaining the curing performance of the cured film, if necessary, the above-mentioned polymerization inhibitor may be used. The same surfactant (B) can be used. For the above purpose, a nonionic surfactant having an HLB value of 5.0 to 20.0 can also be used depending on the type of the organic solvent to be desolvated. When the HLB value is out of the above range, not only is there no effect of suppressing the polymerization, but also the polymerization may be accelerated in some cases. However, when a nonionic surfactant having an HLB value of less than 9 is used as a polymerization inhibitor, the HL as an average of all nonionic surfactants contained in the finally obtained composition of the present invention.
It is preferable to adjust the B value to be 9 or more.

In preparing the composition of the present invention,
When a surfactant is used as a polymerization inhibitor, a surfactant of the same type is used in the step (B) of preparing the composition.
It is desirable to use it as a component. The amount of the polymerization inhibitor to be used is not particularly limited, but is, for example, preferably 1 to 30% by weight, more preferably 2 to 30% by weight based on the component (A).
15% by weight. If the amount is less than 1% by weight, the effect is not seen, and if it exceeds 30% by weight, the curability and weather resistance of the coating are impaired. The amount of the surfactant (B) in the composition of the present invention is the amount including the surfactant used as the polymerization inhibitor, and finally the total amount of the surfactant (B) in the composition. Is adjusted so that the amount falls within the range.

In the third production method of the present invention, the hydrolyzable organosilane of the general formula (IV) and the optical semiconductor (C)
And / or its dispersion and water (D) are mixed (in this case, a catalyst such as an acid or an alkali may be added as necessary). Then, the hydrolyzable organosilane is partially hydrolyzed by water (D) (this partial hydrolysis is
When a catalyst such as an acid or an alkali is added in the mixing step, the action is accelerated by the action) to produce an organosiloxane partial hydrolyzate (A), whereby the organosiloxane partial hydrolyzate (A) is formed. A mixture containing the optical semiconductor (C) is obtained. Thereafter, the mixture is mixed with the surfactant (B), and if no water or a required amount of water (D) remains in the above step, water (D) is added here to prevent the water (D). A fouling silicone emulsion coating composition is obtained.

As the dispersion of the optical semiconductor (C) powder used in the third manufacturing method, one of a dispersion of the optical semiconductor (C) powder in water and a dispersion of the optical semiconductor (C) in an organic solvent is used. Yes, or a combination of both. Specific examples of the hydrolyzable organosilane of the general formula (IV) used in the third production method include the hydrolyzable organoalkoxysilanes described above as a raw material of the organosiloxane partial hydrolyzate (A). However, the present invention is not limited to this.

In the third production method, the above-mentioned general formula (I
The amount of water (D) used when mixing the hydrolyzable organosilane of V), the powder of the optical semiconductor (C) and / or its dispersion, and water (D) is not particularly limited. However, for example, OR in the hydrolyzable organosilane
The ratio is preferably from 0.3 to 2.0 mol, more preferably from 0.4 to 1.0 mol, per 1 mol equivalent of ^one group.
When the optical semiconductor (C) dispersed in water is used as the dispersion liquid of the optical semiconductor (C) powder, the above-mentioned molar amount of water (D) may be different from the solid content in the water-dispersed optical semiconductor (C). Is the amount including water present as a component of When the optical semiconductor (C) dispersed in an organic solvent is used as the dispersion liquid of the optical semiconductor (C) powder, a desolvation step for removing the organic solvent is required later. When the molar amount is less than 0.3 mol, when the organic solvent is removed, the low molecular weight silicone compound in the molecular weight distribution of the organosiloxane partial hydrolyzate (A) tends to be removed from the system together with the organic solvent. On the other hand, when the molar amount of water (D) exceeds 2.0 mol, the storage stability of the organosiloxane partial hydrolyzate (A) decreases, and gelation may occur.

In the case where the desolvation step is required in the third production method as described above, the desolvation method can be the same as that described in the second production method. Also, in the third production method, a polymerization inhibitor can be used if necessary, and the purpose of use, specific examples, amounts used, and the like are the same as those described in the second production method.

In the third production method, when mixing the hydrolyzable organosilane, the powder of the optical semiconductor (C) and / or a dispersion thereof, and water (D), if necessary, Adjustments may be made. The substrate on which the composition of the present invention is applied (which is also the substrate used for the coated article of the present invention) is not particularly limited, and includes, for example, an inorganic substrate, an organic substrate, an inorganic-organic composite substrate, Further, a coating substrate having at least one inorganic coating film and / or at least one organic coating film on any one of these surfaces may be used.

The inorganic substrate is not particularly restricted but includes, for example, a metal substrate; a glass substrate; an enamel; a water glass decorative plate; The metal substrate is not particularly limited. For example, non-ferrous metals [for example, aluminum (JIS-H4000 etc.), aluminum alloys (duralumin etc.), copper, zinc etc.], iron, steel [for example, rolled steel (JIS) -G3101 etc.), hot-dip galvanized steel (JIS
-G3302 etc.), (rolled) stainless steel (JIS-G
4304, G4305, etc.), tinplate (JIS-G3)
303 etc.) and other metals in general (including alloys).

The glass substrate is not particularly restricted but includes, for example, sodium glass, Pyrex glass, quartz glass and alkali-free glass. The enamel is obtained by baking and coating a glassy 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 it. The inorganic hardened material is not particularly limited. For example, a fiber reinforced cement board (J
IS-A5430, etc.), ceramic siding (JIS-
A5422), wood wool cement board (JIS-A5404)
Pulp cement board (JIS-A5414 etc.), slate / wood wool cement laminate board (JIS-A5426)
Gypsum board products (JIS-A6901 etc.), clay roof tiles (JIS-A5208 etc.), thick slate (JIS-A6901 etc.)
A5402), ceramic tile (JIS-A5209)
Etc.), concrete blocks for construction (JIS-A540)
6), terrazzo (JIS-A5411, etc.), prestressed concrete double T slab (JIS-A5412)
Etc.), ALC panel (JIS-A5416 etc.), hollow prestressed concrete panel (JIS-A6511)
Etc.), and all types of base materials obtained by curing and molding inorganic materials such as ordinary bricks (JIS-R1250 etc.).

In the conventional silicone coating, the base material needs to be filled in advance because it is easily attacked by alkali components solute from a water glass decorative plate or an inorganic cured product and cannot have long-term durability. The antifouling silicone emulsion coating material composition of the present invention has a feature that long-term durability can be obtained since the surfactant (B) is introduced, so that it is not easily attacked by an alkali component.

The ceramic substrate is not particularly limited, and examples thereof include alumina, zirconia, silicon carbide, silicon nitride and the like. As an organic substrate,
Although not particularly limited, for example, plastic, wood,
Examples include wood and paper. As a plastic substrate,
Although 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 these plastics are reinforced with an organic fiber such as a nylon fiber. Fiber reinforced plastic (FRP). Since the composition of the present invention is aqueous and has a small amount of organic solvent, it can be applied to a substrate which is relatively easily attacked by an organic solvent such as plastic, and has an antifogging effect and a stain preventing effect on its surface. Is obtained.

The inorganic-organic composite base material is not particularly limited.
Fiber reinforced plastics (FRP) reinforced with inorganic fibers such as carbon fibers, and the like. The organic film constituting the coating substrate is not particularly limited, for example, acrylic, alkyd, polyester, epoxy, urethane, acrylic silicone, chlorinated rubber, phenol, melamine, etc. A cured film of a coating material containing an organic resin may be used.

The inorganic coating constituting the coating substrate is not particularly limited, and includes, for example, a cured coating of a coating material containing an inorganic resin such as a silicone resin. When applying the composition of the present invention to a substrate, depending on the material and surface condition of the substrate, it may be difficult to obtain adhesion when the composition of the present invention is applied as it is. A primer layer may be previously formed on the surface before forming a cured coating film of the composition of the present invention. The primer layer is not particularly limited, regardless of whether it is organic or inorganic. Examples of the organic primer layer include a nylon resin, an alkyd resin, an epoxy resin, an acrylic resin, and an organic modified silicone resin (for example, an acrylic silicone resin). , A cured resin layer of an organic primer composition containing at least one organic resin selected from the group consisting of a chlorinated rubber resin, a urethane resin, a phenol resin, a polyester resin, and a melamine resin in a solid content of 10% by weight or more. Examples of the inorganic primer layer include an inorganic resin such as a silicone resin having a solid content of 90%.
And a cured resin layer of an inorganic primer composition containing at least% by weight.

The thickness of the primer layer is not particularly limited, but is preferably, for example, 0.1 to 50 μm,
-10 μm is more preferred. If the thickness is too thin, adhesion may not be obtained, and if it is too thick, foaming or the like may occur during drying. A substrate having at least one organic primer layer and / or inorganic primer layer on its surface is included in the category of the coated substrate. That is, the coating film on the surface of the coating substrate may be the primer layer.

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 molded body of a material having these shapes, or a structure partially provided with at least one of the material having the shape or the molded body. The base material may be made 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 composition and the coated product of the present invention exhibit excellent antifouling performance stably for a long period of time to reduce the adherence of dirt and to make it easy to remove even if dirt adheres. For example, by equipping at least a part of various materials or articles with a cured coating film of the composition of the present invention, the composition can be suitably used for the following applications.

Building-related members or articles, for example, exterior materials (for example, exterior wall materials, tiles such as flat tiles, Japanese tiles, metal tiles, etc.), and metal such as resin rain gutters such as PVC rain gutters and stainless steel rain gutters. Rain gutters such as rain gutters, gates and members for use therein (for example, gates, gate posts, gate walls, etc.), fences (fences) and members for use therein, garage doors,
Home terrace, door, pillar, car port, bicycle parking port, sign post, home delivery post, wiring equipment such as switchboard and switch, gas meter, interphone, TV door phone body and camera lens, electric lock, entrance pole,
Entrance, ventilation fan outlet, glass for buildings, etc .; windows (for example, daylighting windows, skylights, louvers, etc.) and members used therefor (for example, window frames, shutters, blinds, etc.), automobiles, railway vehicles, Aircraft, ships, machinery,
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, outdoor or indoor lighting fixtures and Members for use (for example, glass members, resin members, metal members,
Ceramics, etc.), glass for solar cells, agricultural vinyl and glass houses, outdoor units for air conditioners, VHF
Antennas such as UHF, BS and CS.

The composition of the present invention may be directly applied to at least a part of the above-mentioned various materials or articles and cured, but is not limited thereto. The antifouling film applied and cured on the surface of the above may be attached to at least a part of the above-mentioned various materials or articles. As the material of the base material of such a film, for example, polyethylene terephthalate (PET) resin, polybutylene terephthalate (PB)
T) Resins such as a resin, a vinyl chloride resin, an acrylic resin, a fluororesin, a polypropylene (PP) resin, and a composite resin thereof, but are not particularly limited.

[0098]

The present invention will be described in detail below with reference to examples and comparative examples. In Examples and Comparative Examples, all “parts” represent “parts by weight” and all “%” represent “% by weight” unless otherwise specified. The molecular weight was measured by GPC (gel permeation chromatography) using a standard polystyrene calibration curve with HLC8020 manufactured by Tosoh Corporation as a measurement model. In addition, this invention is not limited to a following example.

Prior to the examples and comparative examples, the components used for them were prepared as follows. First, a preparation example of the component (A) will be described. <Preparation Example A-1> In a flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel and a thermometer,
1000 parts of water and 50 parts of acetone are weighed, and 44.8 parts (0.3 mol) of methyltrichlorosilane, 38.7 parts (0.3 mol) of dimethyldichlorosilane and phenyltrichlorosilane are mixed in the mixed solution. A solution consisting of 6 parts (0.4 mol) and 200 parts of toluene was hydrolyzed at 60 ° C. while dripping under stirring. After 40 minutes from the end of the dropping, stirring was stopped, the reaction solution was transferred to a separating funnel and allowed to stand, and then the lower layer of hydrochloric acid aqueous solution separated into two layers was separated and removed. Then, toluene of the upper organopolysiloxane was removed. Water and hydrochloric acid remaining in the solution were removed by distillation under reduced pressure together with excess toluene by stripping under reduced pressure to obtain a 50% toluene solution of an organopolysiloxane having a reactive molecular terminal silanol group.

In a mixed solution obtained by adding 5 parts of methyltrimethoxysilane and 5 parts of dimethyldimethoxysilane to 100 parts of this solution, a solution consisting of 0.6 parts of dibutyltin dilaurate and 10 parts of toluene was added dropwise while stirring. The alkoxylation of the silanol groups was performed at 60 ° C. Forty minutes after the completion of the dropwise addition, stirring was stopped, and dibutyltin dilaurate and methanol were removed by distillation together with excess toluene to obtain an 80% toluene solution of a partially hydrolyzed organosiloxane having a weight average molecular weight of 2,000. This is called A-1.

<Preparation Example A-2> 70 parts of methyltrimethoxysilane, 30 parts of dimethyldimethoxysilane and 30 parts of tetraethoxysilane were mixed, then diluted with 28.3 parts of isopropyl alcohol, and further diluted with 0.01N hydrochloric acid. A solution obtained by diluting 7.2 parts with 40 parts of water was added, and the mixture was stirred and hydrolyzed at room temperature. The obtained liquid was heated in a thermostat at 60 ° C. to obtain a 30% mixed alcohol solution of a partially hydrolyzed organosiloxane having a weight average molecular weight of 1500. This is called A-2.

<Preparation Example A-3> In 100 parts of methyltrimethoxysilane, methanol-dispersed titanium oxide (trade name "Queen Titanic 11-1020G", manufactured by Catalyst Kasei Co., Ltd., solid content 20%, average 1) was added as an optical semiconductor. Next particle size 5
After mixing 50 parts of nm), the mixture was diluted with 10.3 parts of methanol, then 7.2 parts of 0.01 N hydrochloric acid diluted with 30 parts of water was added, and the mixture was stirred and hydrolyzed at room temperature.
The obtained liquid was heated in a 60 ° C. constant temperature bath to obtain a 30% methanol solution of a titanium oxide-mixed organosiloxane partial hydrolyzate having a weight average molecular weight of 1,000. This is called A-3.

<Preparation Example A-4> In 100 parts of methyltrimethoxysilane, 40 parts of water-dispersed acidic colloidal silica (trade name "Snowtex O", manufactured by Nissan Chemical Industries, Ltd., solid content: 20%) and methanol are dispersed. Organosilica sol (acid colloidal silica) (trade name "MA-ST",
After mixing 40 parts (Nissan Chemical Industries, Ltd., solid content 30%), the mixture was diluted with 51 parts of methanol, stirred, and hydrolyzed at room temperature. The obtained liquid was heated in a thermostat at 60 ° C. to obtain a 30% methanol solution of a partially hydrolyzed colloidal silica mixed organosiloxane having a weight average molecular weight of 1600. This is called A-4.

<Preparation Example A-5> 70 parts of methyltrimethoxysilane, 30 parts of dimethyldimethoxysilane and 30 parts of tetraethoxysilane were mixed, then diluted with 48.3 parts of isopropyl alcohol, and further diluted with 0.01 N hydrochloric acid. A solution prepared by diluting 7.2 parts with 20 parts of water was added, and the mixture was stirred and hydrolyzed at room temperature. The obtained liquid was heated in a thermostat at 60 ° C. to obtain a 30% mixed alcohol solution of a partially hydrolyzed organosiloxane having a weight average molecular weight of 680. This is called A-5.

<Preparation Example A-6> 1000 parts of water and 50 parts of acetone were weighed and placed in a flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel and a thermometer, and methyltrichlorosilane 44 was added to the mixed solution. .
8 parts (0.3 mol) and 38.7 dimethyldichlorosilane
Part (0.3 mol) and phenyltrichlorosilane 84.6
(0.4 mol) and 200 parts of toluene were hydrolyzed at 60 ° C. while dripping with stirring. One hour after the completion of the dropwise addition, the stirring was stopped, the reaction solution was transferred to a separating funnel and allowed to stand, and then the lower hydrochloric acid aqueous solution separated into two layers was separated and removed. Then, the toluene of the upper organopolysiloxane was removed. Water and hydrochloric acid remaining in the solution were removed by distillation under reduced pressure together with excess toluene by stripping under reduced pressure to obtain a 50% toluene solution of an organopolysiloxane having a reactive molecular terminal silanol group.

In a mixed solution obtained by adding 5 parts of methyltrimethoxysilane and 5 parts of dimethyldimethoxysilane to 100 parts of this solution, a solution comprising 0.6 parts of dibutyltin dilaurate and 10 parts of toluene was added dropwise while stirring. The alkoxylation of the silanol groups was performed at 60 ° C. Forty minutes after the completion of the dropwise addition, stirring was stopped, and dibutyltin dilaurate and methanol were removed by distillation together with excess toluene to obtain an 80% toluene solution of a partially hydrolyzed organosiloxane having a weight average molecular weight of 4,500. This is called A-6.

It has been confirmed that the organosiloxane partial hydrolyzate obtained above satisfies the above average composition formula (I). <Comparative Preparation Example A-1> 1000 parts of water and 50 parts of acetone were weighed and placed in a flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel, and a thermometer. Part (0.
3 mol) and 38.7 parts of dimethyldichlorosilane (0.3
Mol) and 84.6 parts (0.4) of phenyltrichlorosilane.
Mol) and 200 parts of toluene were hydrolyzed at 100 ° C. while dripping under stirring. After 2 hours from the end of the dropwise addition, stirring was stopped, and the reaction solution was transferred to a separating funnel and allowed to stand.
Next, water and hydrochloric acid remaining in the toluene solution of the organopolysiloxane in the upper layer were removed by distillation together with excess toluene by vacuum stripping, thereby removing the toluene of the reactive molecular terminal silanol group-containing organopolysiloxane. A 50% solution was obtained.

In a mixed solution obtained by adding 5 parts of methyltrimethoxysilane and 5 parts of dimethyldimethoxysilane to 100 parts of this solution, a solution comprising 0.6 parts of dibutyltin dilaurate and 10 parts of toluene was added dropwise with stirring. The alkoxylation of the silanol groups was performed at 60 ° C. Forty minutes after the completion of the dropping, stirring was stopped, and dibutyltin dilaurate and methanol were removed by distillation together with excess toluene to obtain an 80% toluene solution of a partially hydrolyzed organosiloxane having a weight average molecular weight of 8,000. This is designated as Comparative A-1.

<Comparative Preparation Example A-2> 70 parts of methyltrimethoxysilane, 30 parts of dimethyldimethoxysilane and 30 parts of tetraethoxysilane were mixed, then diluted with 58.3 parts of isopropyl alcohol, and further diluted with 0.01 part.
A solution prepared by diluting 7.2 parts of normal hydrochloric acid with 10 parts of water is added.
Stir and hydrolyze at room temperature. The obtained liquid was heated in a thermostat at 60 ° C. to obtain a 30% mixed alcohol solution of a partially hydrolyzed organosiloxane having a weight average molecular weight of 500. This is designated as Comparative A-2.

Next, a preparation example of the component (F) which is an organic resin will be described. <Preparation Example F-1> In a flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel, a nitrogen gas inlet / outlet, and a thermometer, n-butyl methacrylate (B
MA) 5.69 parts (40 mmol), trimethoxysilylpropyl methacrylate (SMA) 1.24 parts (5 m
mol), glycidyl methacrylate (GMA) 0.7
1 part (5 mmol) and 0.784 parts (4 mm) of γ-mercaptopropyltrimethoxysilane as a chain transfer agent.
ol) in 8.49 parts of toluene was added to 0.025 parts (0.1%) of azobisisobutyronitrile.
A solution of 5 mmol) dissolved in 3 parts of toluene was added dropwise under a nitrogen stream and reacted at 70 ° C. for 2 hours. As a result, a 40% toluene solution of an acrylic resin having a weight average molecular weight of 1,000 was obtained. This is called F-1.

Preparation conditions for F-1: Monomer molar ratio BMA / SMA / GMA = 8.0 /
1.0 / 1.0 Weight-average molecular weight 1000 Solid content 40% Next, emulsification will be described. <Example 1> 80 of component (A) obtained in Preparation Example A-1
% Toluene solution (A-1) as a polymerization inhibitor in 50 parts
Polyoxyethylene nonyl, a nonionic surfactant
2 parts of phenyl ether (HLB value 12.6) were added,
After stirring uniformly, use a rotary evaporator to remove the solvent.
Was distilled off. Nonionic surfactant is added to the obtained residue.
As polyoxyethylene nonyl phenyl ether (H
(LB value: 13.5) 5 parts was added, and the mixture was stirred uniformly. this
After adding 290 parts of water to the homogenizer under stirring,
00kg / cm ^Two ) The silicone e
A marjon was obtained and further dispersed in water as an optical semiconductor under stirring
Titanium oxide (trade name “STS-0” manufactured by Ishihara Sangyo Co., Ltd.)
1 ", solid content 30%, average primary particle diameter 7 nm) 10 parts
Addition of the antifouling silicone emulsion coat
A toting material composition (1) was obtained. <Example 2> In Example 1, water and water-dispersed titanium oxide were used.
Change the amount of tongue to 250 parts and 50 parts respectively
By performing the same operation as in Example 1 except that
Antifouling silicone emulsion coating material composition
(2) was obtained. <Example 3> In Example 1, water and water-dispersed oxide
Change the amount of tongue to 200 parts and 100 parts respectively
By performing the same operation as in Example 1 except that
Antifouling silicone emulsion coating material composition
The product (3) was obtained. <Example 4> In Example 1, water and water-dispersed titanium oxide were used.
Change the amount of tongue to 100 parts and 200 parts respectively
By performing the same operation as in Example 1 except that
Antifouling silicone emulsion coating material composition
A product (4) was obtained. Example 5 80 of the component (A) obtained in Preparation Example A-1
% Toluene solution (A-1) as a polymerization inhibitor in 50 parts
Polyoxyethylene nonyl, a nonionic surfactant
2 parts of phenyl ether (HLB value 12.6) were added,
After stirring uniformly, use a rotary evaporator to remove the solvent.
Was distilled off. Nonionic surfactant is added to the obtained residue.
As polyoxyethylene nonyl phenyl ether (H
(LB value: 13.5) 5 parts was added, and the mixture was stirred uniformly. this
Water-dispersed titanium oxide as an optical semiconductor (Ishihara Sangyo Co., Ltd.)
Made, trade name "STS-01", solid content 30%, average primary
(Particle size 7 nm) 300 parts were added under stirring, and then homogenized.
Iser (300kg / cm ^Two )
Antifouling silicone emulsion coating material composition
(5) was obtained. <Example 6> In Example 5, the addition of water-dispersed titanium oxide was carried out.
Same as Example 5 except that the addition amount was changed to 440 parts.
By performing the operation, the antifouling silicone emulsion
A coating material composition (6) was obtained. <Example 7> 80 of component (A) obtained in Preparation Example A-1
% Toluene solution (A-1) in 50 parts of anionic surfactant
4 parts of sodium dodecylbenzenesulfonate as a surfactant
And stirred uniformly. To this, 290 parts of water is added under stirring.
And then homogenizer (300kg / cm ^Two ) Process
And then use a rotary evaporator to
The silicone emulsion was distilled off to obtain a silicone emulsion, which was further stirred.
Water-dispersed titanium oxide as an optical semiconductor under stirring (Ishihara Sangyo
Co., Ltd., trade name "STS-01", solid content 30%, flat
By adding 10 parts of (average primary particle diameter 7 nm), antifouling
Silicone emulsion coating material composition (7)
I got <Example 8> In Example 7, water and water-dispersed titanium oxide were used.
Change the amount of tongue to 250 parts and 50 parts respectively
By performing the same operation as in Example 7 except that
Antifouling silicone emulsion coating material composition
(8) was obtained. <Example 9> In Example 7, water and water-dispersed titanium oxide were used.
Change the amount of tongue to 200 parts and 100 parts respectively
By performing the same operation as in Example 7 except that
Antifouling silicone emulsion coating material composition
A product (9) was obtained. <Example 10> In Example 7, water and water-dispersed oxidation were used.
The amount of titanium added was changed to 100 parts and 200 parts, respectively.
The same operation as in Example 7 was performed except for the change.
Antifouling silicone emulsion coating material composition
A product (10) was obtained. <Example 11> 8 of component (A) obtained in Preparation Example A-1
50% of a 0% toluene solution (A-1) is added to an anionic interface
4 parts of sodium dodecylbenzenesulfonate as activator
Add and stir uniformly. Water dispersion as an optical semiconductor
Titanium oxide (trade name “STS-0” manufactured by Ishihara Sangyo Co., Ltd.)
1 ", solid content 30%, average primary particle diameter 7 nm) 300 parts
Is added under stirring, and then homogenizer (300 kg / c
m ^Two ) Process, then turn the rotary evaporator
The antifouling silicone is removed by using
An emulsion coating material composition (11) was obtained. <Example 12> In Example 11, water-dispersed titanium oxide was used.
Example 11 except that the addition amount of was changed to 440 parts.
By performing the same operation, the antifouling silicone emulsion
A John coating material composition (12) was obtained. <Example 13> 8 of component (A) obtained in Preparation Example A-1
50% of a 0% toluene solution (A-1) is added to an anionic interface
4 parts of sodium dodecylbenzenesulfonate as activator
Add and stir uniformly. Add 100 parts of water to this with stirring
After adding, homogenizer (300kg / cm ^Two )processing
And then use a rotary evaporator to
The ene was distilled off to obtain a silicone emulsion,
Water-dispersible pigment slurry [titanium oxide powder as optical semiconductor
(Ishihara Sangyo Co., Ltd., trade name "ST-01", average primary)
50 parts, nonionic urethane acrylic
Rock Copolymer (Rohm and Haas Co., Ltd.
Product name "RM-830", solid content 30%, butylcarbite
5 parts of water / water = 28/72 (weight ratio) aqueous solution)
To disperse 5 parts for 1 hour with a paint shaker
Obtained by adding 50 parts and stirring.
Antifouling silicone emulsion coating material composition
A product (13) was obtained. <Example 14> 3 of component (A) obtained in Preparation Example A-2
100% of 0% mixed alcohol solution (A-2)
Polyoxyethylene, a nonionic surfactant as a stabilizer
2 parts of rennonyl phenyl ether (HLB value 9.7)
Add and stir uniformly, then use a rotary evaporator.
The alcohol was distilled off. In 32 parts of the obtained residue,
Polyoxyethylene nonyl as a nonionic surfactant
5 parts of phenyl ether (HLB value 13.6) were added,
Stir evenly. 100 parts of water were added thereto with stirring.
After that, a homogenizer (300 kg / cm ^Two ) Do the processing
To obtain a silicone emulsion,
Water-dispersed titanium oxide as an optical semiconductor by Ishihara Sangyo Co., Ltd.
Made, trade name "STS-01", solid content 30%, average primary
By adding 50 parts (particle diameter 7 nm), the antifouling silicone
Obtain corn emulsion coating material composition (14)
Was. Example 15 3 of component (A) obtained in Preparation Example A-2
100% of 0% mixed alcohol solution (A-2)
Methanol-dispersed titanium oxide (Catalyst Chemical Co., Ltd.)
Made, trade name "Queen Titanic 11-1020
G ", solid content 20%, average primary particle diameter 5 nm) 50 parts
Added under stirring, and further added as a nonionic interface
Polyoxyethylene nonylphenyl ether as activator
(HLB value of 13.6) was added and stirred uniformly.
Evaporate the alcohol using a rotary evaporator
Was. A nonionic surfactant was added to 42 parts of the obtained residue.
To polyoxyethylene nonyl phenyl ether (HL
B value 18) 5 parts were added and stirred uniformly. Water 1
After adding 50 parts under stirring, a homogenizer (300 k
g / cm ^Two ) By treating, anti-fouling silicone
An emulsion coating material composition (15) was obtained. <Example 16> A mixture of (A) and (C) obtained in Preparation Example A-3
Titanium oxide mixed organosiloxane partial addition
100 parts of 30% methanol solution of hydrolyzate (A-3)
In addition, as a polymerization inhibitor, a nonionic surfactant
Oxyethylene nonyl phenyl ether (HLB value 1
2.6) Add 2 parts, stir evenly, and add
The alcohol was distilled off using a porator. Obtained residue
32 parts of distillate were treated with polyoxy as nonionic surfactant
Ethylene nonyl phenyl ether (HLB value 13.7)
5 parts were added and stirred uniformly. 100 parts of water are stirred into this
After adding under stirring, homogenizer (300 kg / c
m ^Two ) Treating the product with an antifouling silicone emulsion
A John coating material composition (16) was obtained. <Example 17> 8 of component (A) obtained in Preparation example A-1
Nonionic interface was added to 50 parts of 0% toluene solution (A-1).
Polyoxyethylene nonylphenyl ether as an activator
(HLB value of 13.7) was added and stirred uniformly.
Was. This is mixed with water-dispersed acidic colloidal silica (trade name "Suno
-Tex O ", manufactured by Nissan Chemical Industries, Ltd., solid content 20
%) And 50 parts of water were added under stirring.
Jinizer (300kg / cm ^Two ) Process, then
The toluene is distilled off using a rotary evaporator.
To obtain a silicone emulsion.
Water-dispersed titanium oxide (made by Ishihara Sangyo Co., Ltd.) as a conductor
Name "STS-01", solid content 30%, average primary particle size 7
nm) by adding 30 parts.
A marsion coating material composition (17) was obtained. <Example 18> Colloidal silica obtained in Preparation Example A-4
30% meth of partially mixed organosiloxane hydrolyzate
100 parts of the ethanol solution (A-4) as a polymerization inhibitor
Polyoxyethylene nonylph, a nonionic surfactant
3 parts of phenyl ether (HLB value: 5.7)
And then use a rotary evaporator to remove methanol.
Was distilled off. 33 parts of the obtained residue contain nonionic
Polyoxyethylene nonylphenyl ate as a surfactant
Add 3 parts of ter (HLB value 13.7) and stir well
Made uniform. After 100 parts of water was added thereto with stirring,
Modifier (300kg / cm ^Two ) To do the processing
To obtain a silicone emulsion,
Water-dispersed titanium oxide (made by Ishihara Sangyo Co., Ltd.) as a conductor
Name "STS-01", solid content 30%, average primary particle size 7
nm) by adding 30 parts.
A marsion coating material composition (18) was obtained. <Example 19> 8 of component (A) obtained in Preparation Example A-1
Weight average molecular weight was added to 50 parts of a 0% toluene solution (A-1).
Mw = 800 (n ≒ 11) linear dimethyl polysiloxane
20 parts sundiol, poly as nonionic surfactant
Oxyethylene nonyl phenyl ether (HLB value 1
3.7) 4 parts were added and stirred uniformly. Water 14
After adding 0 parts under stirring, a homogenizer (300 kg
/ Cm ^Two ) Process, then rotary evaporator
The toluene is distilled off using a
Water-dispersed titanium oxide as an optical semiconductor under stirring.
(Ishihara Sangyo Co., Ltd., trade name "STS-01", solid
30%, average primary particle diameter 7 nm) 50 parts
Prevents linear dimethylpolysiloxanediol from mixing
Soil silicone emulsion coating material composition (1
9) was obtained. <Example 20> 8 of component (A) obtained in Preparation Example A-1
Nonionic interface was added to 50 parts of 0% toluene solution (A-1).
Polyoxyethylene nonylphenyl ether as an activator
(HLB value of 11.0) 4 parts and stir evenly
Was. After adding 140 parts of water to this with stirring, the mixture is homogenized.
The (300kg / cm ^Two ) Process and then the rotor
The toluene is distilled off using a reevaporator,
A corn emulsion was obtained. This is mixed with the optical semiconductor under stirring.
And water-dispersed titanium oxide (trade name “S” manufactured by Ishihara Sangyo Co., Ltd.)
TS-01 ", solid content 30%, average primary particle diameter 7 nm)
After adding 50 parts, a linear dimethylpolysiloxane
Diol emulsion [weight average molecular weight Mw = 800
(N ≒ 11) linear dimethylpolysiloxanediol
50 parts of polyoxyethylene as a nonionic surfactant
Rennonyl phenyl ether (HLB value 11.0) 5 parts
And uniformly stirred, and then 45 parts of water are added under stirring.
And then homogenizer (300kg / cm ^Two ) Process
And emulsified by adding 40 parts under stirring.
By doing so, the linear dimethylpolysiloxane diol
Mixed antifouling silicone emulsion coating material composition
A product (20) was obtained. <Example 21> 3 of component (A) obtained in Preparation Example A-2
100 parts by weight of a 0% mixed alcohol solution (A-2)
Linear dimethyl ester having an average molecular weight Mw = 800 (n ≒ 11)
Lisiloxane diol 3 parts, weight average molecular weight Mw = 30
00 (n ≒ 40) linear dimethylpolysiloxane geo
1 part, a nonionic surfactant as a polymerization inhibitor
Polyoxyethylene nonyl phenyl ether (HLB)
Value 12.6) Add 2 parts, stir evenly, then rotary
The alcohol was distilled off using an evaporator. Obtained
In 36 parts of the residue, polio was added as a nonionic surfactant.
Xyethylene nonyl phenyl ether (HLB value 13.
7) 5 parts were added and the mixture was stirred well to make it uniform. Water on this
After adding 150 parts under stirring, the homogenizer (300
kg / cm ^Two ) Silicone emulsion
And then oxidized in water as an optical semiconductor under stirring
Titanium (trade name "STS-01", manufactured by Ishihara Sangyo Co., Ltd.)
30 parts of solid content, average primary particle diameter 7 nm)
Can be mixed with linear dimethylpolysiloxanediol.
Antifouling silicone emulsion coating material composition
(21) was obtained. <Example 22> 8 of component (A) obtained in Preparation Example A-1
Nonionic interface was added to 50 parts of 0% toluene solution (A-1).
Polyoxyethylene nonylphenyl ether as an activator
(HLB value of 13.7) was added and stirred uniformly.
Was. After 150 parts of water was added thereto with stirring, the mixture was homogenized.
The (300kg / cm ^Two ) Process and then the rotor
The toluene is distilled off using a reevaporator,
A corn emulsion is obtained, which is further converted into an optical semiconductor under stirring.
Water-dispersed titanium oxide (trade name "ST" manufactured by Ishihara Sangyo Co., Ltd.)
S-01 ", solid content 30%, average primary particle diameter 7 nm) 5
By adding 0 parts, antifouling silicone emulsion
A coating material composition was obtained. 100 parts of this composition
And an acrylic emulsion (Nippon Shokubai Co., Ltd.)
Product name "Akset EX35", solid content 42%) 6 parts
Acrylic resin mixed antifouling silicone by mixing
Emulsion coating material composition (22)
Was. <Example 23> 8 of component (A) obtained in Preparation example A-1
Preparation Example F-1 was added to 50 parts of a 0% toluene solution (A-1).
40% toluene solution of obtained acrylic resin (F-1)
20 parts, polyoxyethylene as nonionic surfactant
Nonyl phenyl ether (HLB value 13.7) 4 parts
Add and stir uniformly. Add 150 parts of water to this with stirring
After adding, homogenizer (300kg / cm ^Two )processing
Emulsification, then rotary evaporation
The toluene is distilled off using a
Aqueous dispersion as an optical semiconductor under stirring.
Titanium (manufactured by Ishihara Sangyo Co., Ltd., trade name: STS-0
1 ", solid content 30%, average primary particle diameter 7 nm) 50 parts
Addition of acrylic-modified antifouling silicone emuls
Thus, a coating material composition (23) was obtained. <Example 24> Colloidal silica obtained in Preparation Example A-4
30% meth of partially mixed organosiloxane hydrolyzate
In 100 parts of the ethanol solution (A-4), obtained in Preparation Example F-1
40% toluene solution of acrylic resin (F-1) 10
Parts, linear with weight average molecular weight Mw = 800 (n ≒ 11)
3 parts of dimethylpolysiloxanediol, used as polymerization inhibitor
Nonionic Surfactant Polyoxyethylene Noni
3 parts of phenyl ether (HLB value 5.7) were added,
After uniform stirring, use a rotary evaporator to
Ethanol and toluene were distilled off. The obtained residue 39
In part, polyoxyethylene as nonionic surfactant
Nonylphenyl ether (HLB value 13.7) 3 parts
And stirred well to homogenize. 100 parts of water are stirred into this
After adding under stirring, homogenizer (300 kg / c
m ^Two ) The silicone emulsion is
Water-dispersed titanium oxide as an optical semiconductor under stirring
(Ishihara Sangyo Co., Ltd., trade name "STS-01", solid content
(30%, average primary particle diameter 7 nm)
From colloidal silica and linear dimethyl polysiloxane
Diol-modified acrylic-modified antifouling silicone emulsion
A coating composition (24) was obtained. <Example 25> 8 of component (A) obtained in Preparation Example A-1
Nonionic interface was added to 50 parts of 0% toluene solution (A-1).
Polyoxyethylene nonylphenyl ether as an activator
(HLB value of 13.7) was added and stirred uniformly.
Was. After 150 parts of water was added thereto with stirring, the mixture was homogenized.
The (300kg / cm ^Two ) Process and then the rotor
The toluene is distilled off using a reevaporator,
A corn emulsion is obtained, which is further converted into an optical semiconductor under stirring.
Water-dispersed titanium oxide (trade name "ST" manufactured by Ishihara Sangyo Co., Ltd.)
S-01 ", solid content 30%, average primary particle diameter 7 nm) 5
0 parts, water-dispersible pigment slurry as pigment (Dainichi Seika
Co., Ltd., trade name "EP-62White", titanium oxide
70% of a white pigment was added in order to obtain a white pigment.
Antifouling silicone emulsion coating material composition
(25) was obtained. <Example 26> 3 of component (A) obtained in Preparation Example A-5
100 parts of 0% mixed alcohol solution (A-5)
Polyoxyethylene, a nonionic surfactant as a stabilizer
Rennonyl phenyl ether (HLB value 12.6) 2 parts
After stirring uniformly, turn the rotary evaporator
The alcohol was distilled off. 32 parts of residue obtained
In addition, as a nonionic surfactant, polyoxyethylene
Add 5 parts of phenyl ether (HLB value 13.7)
And stirred uniformly. Add 100 parts of water to this with stirring
After that, homogenizer (300kg / cm ^Two ) Process
To obtain a silicone emulsion and further agitate
Water-dispersed titanium oxide as optical semiconductor under (Ishihara Sangyo Co., Ltd.)
Made, trade name "STS-01", solid content 30%, average primary
By adding 50 parts (particle diameter 7 nm), the antifouling silicone
Obtaining a corn emulsion coating material composition (26)
Was. <Example 27> 8 of component (A) obtained in Preparation Example A-6
50% of a 0% toluene solution (A-6) was added to an anionic interface
4 parts of sodium dodecylbenzenesulfonate as activator
Add and stir uniformly. Add 250 parts of water under stirring
After adding, homogenizer (300kg / cm ^Two )processing
And then use a rotary evaporator to
The ene was distilled off to obtain a silicone emulsion,
Water-dispersed titanium oxide as an optical semiconductor under stirring (Ishihara Sangyo
Co., Ltd., trade name "STS-01", solid content 30%, flat
Addition of 50 parts of an average primary particle diameter of 7 nm)
Silicone emulsion coating material composition (2
7) was obtained. <Example 28> 8 of component (A) obtained in Preparation Example A-1
50% of a 0% toluene solution (A-1) is added to an anionic interface
4 parts of sodium dodecylbenzenesulfonate as activator
Add and stir uniformly. Add 100 parts of water to this with stirring
After adding, homogenizer (300kg / cm ^Two )processing
And then use a rotary evaporator to
The ene was distilled off to obtain a silicone emulsion,
Water-dispersible pigment slurry [titanium oxide powder as optical semiconductor
(Ishihara Sangyo Co., Ltd., trade name "ST-11", average primary)
50 parts, nonionic urethane acryl
Block copolymer (Rohm and Haas,
Product name "RM-830", solid content 30%, butylcarb
5 parts of tall / water = 28/72 (weight ratio) aqueous solution) and water
Dispersing 45 parts for 1 hour with a paint shaker
50 parts were added and stirred.
More antifouling silicone emulsion coating material
The product (28) was obtained. <Example 29> Component (A) 3 obtained in Preparation Example A-2
100% of 0% mixed alcohol solution (A-2)
Toluene dispersed zinc oxide (Sumitomo Osaka Cement Co., Ltd.)
Co., Ltd., trade name "ZS-300", solid content 31%, flat
32.3 parts were added under stirring.
Furthermore, nonionic surfactants such as poly
Oxyethylene nonyl phenyl ether (HLB value 1
2.6) Add 2 parts, stir evenly, and add
The alcohol was distilled off using a porator. Obtained residue
42 parts of distillate were treated with polyoxy as nonionic surfactant
Ethylene nonyl phenyl ether (HLB value 13.7)
5 parts were added and stirred uniformly. 150 parts of water was stirred for this.
After adding under stirring, homogenizer (300 kg / c
m ^Two ) Treating the product with an antifouling silicone emulsion
A John coating material composition (29) was obtained. <Example 30> 8 of component (A) obtained in Preparation Example A-1
50% of a 0% toluene solution (A-1) is added to an anionic interface
4 parts of sodium dodecylbenzenesulfonate as activator
Add and stir uniformly. Add 100 parts of water to this with stirring
After adding, homogenizer (300kg / cm ^Two )processing
And then use a rotary evaporator to
The ene was distilled off to obtain a silicone emulsion,
Water-dispersible pigment slurry (0.5% platinum supported as optical semiconductor)
50 parts of titanium oxide powder, nonionic urethane acrylic
Block copolymer (Rohm and Haas,
Product name "RM-830", solid content 30%, butylcarb
5 parts of tall / water = 28/72 (weight ratio) aqueous solution) and water
Dispersing 45 parts for 1 hour with a paint shaker
50 parts were added and stirred.
More antifouling silicone emulsion coating material
The product (30) was obtained. In addition, it was used for preparation of this composition.
The 0.5% platinum-supported titanium oxide powder is 5% platinum chloride
Titanium oxide powder (made by Ishihara Sangyo Co., Ltd., trade name)
"ST-01", average primary particle diameter 7 nm)
・ After drying, irradiate with ultraviolet light for 2 hours,
This is one in which 0.5% of platinum is supported on tan. <Example 31> 8 of component (A) obtained in Preparation Example A-1
Weight average molecular weight was added to 50 parts of a 0% toluene solution (A-1).
Mw = 800 (n ≒ 11) linear dimethyl polysiloxane
10 parts sundiol, dimethyldisiloxane di with n = 2
All [HO ((CH _Three ) _Two SiO) _Two H] 10 parts, no
Polyoxyethylene nonylph as a nonionic surfactant
4 parts of phenyl ether (HLB value 13.7) were added,
Stir together. After adding 140 parts of water to this under stirring,
Homogenizer (300kg / cm ^Two ) Process, then
Distill off toluene using a rotary evaporator
To obtain a silicone emulsion,
Water-dispersed titanium oxide (made by Ishihara Sangyo Co., Ltd.)
Product name "STS-01", solid content 30%, average primary particle size
7 nm) by adding 50 parts.
Polysiloxane diol mixed antifouling silicone emulsion
A coating material composition (31) was obtained. <Example 32> 8 of component (A) obtained in Preparation Example A-1
Weight average molecular weight was added to 50 parts of a 0% toluene solution (A-1).
Mw = 800 (n ≒ 11) linear dimethyl polysiloxane
10 parts of sundiol, weight average molecular weight Mw = 450 (n
≒ 4) Linear methylphenyl polysiloxane diol
10 parts, polyoxyethylene as nonionic surfactant
Nonyl phenyl ether (HLB value 13.7) 4 parts
Add and stir uniformly. Add 140 parts of water under stirring
After adding, homogenizer (300kg / cm ^Two )processing
And then use a rotary evaporator to
The ene was distilled off to obtain a silicone emulsion,
Water-dispersed titanium oxide as an optical semiconductor under stirring (Ishihara Sangyo
Co., Ltd., trade name "STS-01", solid content 30%, flat
The addition of 50 parts of an average primary particle diameter of 7 nm)
Dimethylpolysiloxanediol mixed antifouling silicone
An emulsion coating material composition (32) was obtained. <Example 33> Component (A) 3 obtained in Preparation Example A-2
100 parts by weight of a 0% mixed alcohol solution (A-2)
Linear dimethyl ester having an average molecular weight Mw = 800 (n ≒ 11)
Lisiloxane diol 3 parts, weight average molecular weight Mw = 42
00 (n ≒ 55) linear dimethylpolysiloxane di
1 part, a nonionic surfactant as a polymerization inhibitor
Polyoxyethylene nonyl phenyl ether (HLB)
Value 12.6) Add 2 parts, stir evenly, then rotary
The alcohol was distilled off using an evaporator. Obtained
In 36 parts of the residue, polio was added as a nonionic surfactant.
Xyethylene nonyl phenyl ether (HLB value 13.
7) 5 parts were added and the mixture was stirred well to make it uniform. Water on this
After adding 150 parts under stirring, the homogenizer (300
kg / cm ^Two ) Silicone emulsion
And then oxidized in water as an optical semiconductor under stirring
Titanium (trade name "STS-01", manufactured by Ishihara Sangyo Co., Ltd.)
30 parts of solid content, average primary particle diameter 7 nm)
Can be mixed with linear dimethylpolysiloxanediol.
Antifouling silicone emulsion coating material composition
(33) was obtained. <Example 34> Component (A) 3 obtained in Preparation Example A-2
100% of 0% mixed alcohol solution (A-2)
Polyoxyethylene, a nonionic surfactant as a stabilizer
Added 2 parts of renlauryl ether (HLB value 9.7)
After stirring uniformly, use a rotary evaporator
The alcohol was distilled off. Noni was added to 32 parts of the obtained residue.
Polyoxyethylene lauryl ether as an on-surfactant
Add 5 parts of H-tel (HLB value 13.6) and stir evenly
did. After 100 parts of water was added thereto with stirring, the mixture was homogenized.
Iser (300kg / cm ^Two ) By processing
A cone emulsion is obtained, and further, with an optical semiconductor under stirring.
And water-dispersed titanium oxide (trade name “S” manufactured by Ishihara Sangyo Co., Ltd.)
TS-01 ", solid content 30%, average primary particle diameter 7 nm)
By adding 50 parts, an antifouling silicone emulsion
A coating composition (34) was obtained. <Comparative Example 1> In Example 1, the water-dispersed titanium oxide was completely
The same operation as in Example 1 is performed except that no addition was made.
By comparison, silicone emulsion coating
A lubricating material composition (1) was obtained. <Comparative Example 2> In Example 1, water and water-dispersed titanium oxide were used.
The added amount of tongue was changed to 200 parts and 5 parts, respectively.
Except for this, the same operation as in Example 1 was performed to
Comparative silicone emulsion coating material composition
(2) was obtained. <Comparative Example 3> In Example 5, the addition of water-dispersed titanium oxide
Same as Example 5 except that the addition amount was changed to 600 parts.
By performing the operation, the silicone emulsion for comparison
A coating material composition (3) was obtained. <Comparative Example 4> 80 of component (A) obtained in Preparation Example A-1
50% toluene solution (A-1) in 50 parts of water-dispersed titanium oxide
(Ishihara Sangyo Co., Ltd., trade name "STS-01", solid content
30 parts, average primary particle diameter 7 nm) 50 parts and water 150
Part was added under stirring, and then homogenizer (300 kg /
cm ^Two ) By treating, the antifouling silicone emma
I tried to obtain a luzon coating material composition,
Titanium oxide aggregated-phase separated-precipitated, uniform dispersion system
Was not obtained. <Comparative Example 5> Weight average molecule obtained in Comparative Preparation Example A-1
80 of the 8000 organosiloxane partial hydrolyzate
50% toluene solution (Comparative A-1) in 50 parts
Sodium dodecylbenzenesulfonate 4 as surfactant
Was added and stirred uniformly. Stir 250 parts of water
After addition under the homogenizer (300 kg / cm ^Two )
Process and use a rotary evaporator to remove
The silicone emulsion was distilled off to obtain a silicone emulsion, which was further stirred.
Under stirring, water-dispersed titanium oxide (trade name, manufactured by Ishihara Sangyo Co., Ltd.)
"STS-01", solid content 30%, average primary particle diameter 7n
m) By adding 50 parts, the silicone emuls
A composition coating material (5) was obtained. <Comparative Example 6> Commercially available acrylic emulsion (Nippon Shokubai
Co., Ltd., trade name "Acreset EX35", solid content 4
Water dispersion titanium oxide (Ishihara Sangyo Co., Ltd.)
Made, trade name "STS-01", solid content 30%, average primary
By adding 33.3 parts of (particle diameter 7 nm) and mixing.
Acrylic emulsion coating material composition for comparison
(6) was obtained. <Comparative Example 7> Weight average molecule obtained in Comparative Preparation Example A-2
30% of the organosiloxane partial hydrolyzate in an amount of 500
100 parts of the mixed alcohol solution (Comparative A-2)
Methanol-dispersed titanium oxide as a conductor (Catalyst Chemical Co., Ltd.)
Made, trade name "Queen Titanic 11-1020
G ", solid content 20%, average primary particle diameter 5 nm) 50 parts
Added under stirring, and further added as a nonionic interface
Polyoxyethylene nonylphenyl ether as activator
(HLB value 12.6) was added and stirred uniformly.
Evaporate the alcohol using a rotary evaporator
Was. A nonionic surfactant was added to 42 parts of the obtained residue.
To polyoxyethylene nonyl phenyl ether (HL
B value: 13.7) 5 parts were added, and the mixture was stirred uniformly. to this
After 150 parts of water was added with stirring, a homogenizer (30 parts) was added.
0kg / cm ^Two ) By processing, the silicon for comparison
Thus, an emulsion coating material composition (7) was obtained. <Comparative Example 8> In Example 7, an anionic surfactant was used.
Of sodium dodecylbenzenesulfonate used as a material
Quaternary ammonium salt as a cationic surfactant
Type cationic surfactant (trade name: Adecamine 4MAC)
-30, manufactured by Asahi Denka Kogyo Co., Ltd.)
The same operation as in Example 7 was performed to obtain a comparative silicone.
Thus, an emulsion coating material composition (8) was obtained. <Comparative Example 9> In Example 7, an anionic surfactant was used.
Of sodium dodecylbenzenesulfonate used as a material
Laurilamidopropyl solid as an amphoteric surfactant
In (trade name: Adeka Ankhort PB-30L, Asahi Denka
(Manufactured by Kogyo Co., Ltd.)
By performing the above operation, the silicone emulsion for comparison
A coating material composition (9) was obtained.

The characteristics of the emulsion coating material compositions of the examples and comparative examples obtained above were evaluated by the following methods. (Emulsification stability): One and three months after emulsification, the emulsified state of the coating material composition of each example was visually observed and evaluated according to the following criteria.

：: Uniform white milky liquid, no coagulated precipitate. Δ: Uniform white milky liquid, but a slight amount of coagulated precipitate. X: Heterogeneous phase separation has occurred, and there is a precipitate. (Film-forming property): The coating material composition of each example was applied to the surface of a Pyrex glass plate using a bar coater so that the dry coating thickness became 1 μm, dried at room temperature, and the state of the dry coating was visually observed. It was observed and evaluated according to the following criteria.

○: Continuous transparent film. ×: discontinuous opaque film (white turbidity due to phase separation and aggregation; white turbidity due to coarse particles such as pigments is excluded). (Transparency): The coating material composition of each example was applied to the surface of a Pyrex glass plate using a bar coater so that the dry coating thickness became 1 μm, and dried at room temperature, and the transparency of the dry coating was measured with a Haze meter. Was measured. (Heat curability): The coating material composition of each example was applied to the surface of a Pyrex glass plate with a bar coater so that the dry coating thickness became 1 μm, dried at room temperature, and cured at 150 ° C. for 30 minutes. The cured film thus formed was rubbed with the tip of a nail, and the rubbed cured film was visually observed and evaluated according to the following criteria.

：: No scratch mark remains. ×: Scar marks remain. If no scratch marks remain, set the pencil hardness of the cured film to J
It measured according to IS-K5400. (Room-temperature curability): A curing catalyst-containing coating obtained by further adding 5 parts of a 10% by weight aqueous solution of potassium acetate (curing catalyst) to 100 parts of component (A) in the coating material composition of each example. The material composition was dried on a Pyrex glass plate with a bar coater and the dry coating thickness was 1 μm.
And dried at room temperature.
The cured film formed by curing for 1 week in a thermo-hygrostat set at 90 ° C. and a humidity of 90% was rubbed with the tip of a nail, and the cured film rubbed was visually observed and evaluated according to the following criteria. .

：: No scratch mark remains. ×: Scar marks remain. If no scratch marks remain, set the pencil hardness of the cured film to J
It measured according to IS-K5400. (Crack resistance): The coating material composition of each example was applied to the surface of an alumina plate with a bar coater so that the dry coating thickness became 1 μm, 5 μm or 20 μm, dried at room temperature, and then dried at 150 ° C. The appearance of the cured film formed by curing for 30 minutes was visually observed and evaluated according to the following criteria.

○: No crack. Δ: Fine cracks are locally generated. ×: Cracks occurred on the entire surface. (Adhesion): A curing catalyst-containing coating material obtained by further adding 5 parts of a 10% by weight aqueous solution of potassium acetate (curing catalyst) to 100 parts of the component (A) in the coating material composition of each example. The composition was applied to one side of a 30 mm × 30 mm Pyrex glass plate with a bar coater so that the dry coating thickness became 1 μm, dried at room temperature, and then set at a temperature of 40 ° C. and a humidity of 90%. The adhesiveness of the cured film formed by curing in a wet tank for one week was evaluated by a cross-cut adhesive tape (using a cellophane tape) peel test. (Photocatalytic decomposition action): In the coating material composition of each example,
A curing catalyst-containing coating material composition obtained by further adding 5 parts of a 10% by weight aqueous solution of potassium acetate (curing catalyst) to 100 parts of the component (A) in the composition is 30 mm × 30 m.
Apply to one side of Pyrex glass plate of m size with a bar coater so that the dry coating thickness is 1 μm,
After drying at room temperature, a test piece obtained by curing for 1 week in a thermo-hygrostat set at a temperature of 40 ° C. and a humidity of 90% was placed in a closed glass container having a volume of 300 ml. Acetaldehyde gas was injected so as to have a concentration of 50 ppm, irradiated with 10 W black light for 60 minutes, and subjected to gas chromatography (GC14 GC14).
The acetaldehyde removal rate was measured using A). (Wetness to water): 10% by weight based on 100 parts of component (A) in the coating material composition of each example
A curing catalyst-containing coating material composition obtained by further adding 5 parts of an aqueous potassium acetate (curing catalyst) solution is 30 mm × 3
A 1 mm dry Pyrex glass plate is coated on one side with a bar coater so as to have a dry coating thickness of 1 μm, dried at room temperature, and dried in a constant temperature and humidity chamber set at a temperature of 40 ° C. and a humidity of 90%. The wettability of the cured film formed by curing for weeks on water was evaluated by measuring the contact angle between water and the cured film. The contact angle was the initial value after the coating film was formed, and the ultraviolet light was irradiated for 1 hour using an ultraviolet irradiation device (Handy UV300, manufactured by Oak Manufacturing Co., Ltd.)-
Those which were repeated 0 times were measured. (Weather resistance): The coating material composition of each example was applied to the surface of a Pyrex glass plate with a bar coater so that the dry coating thickness became 1 μm, and dried at room temperature.
A test specimen obtained by curing at 150 ° C. for 30 minutes was subjected to an accelerated weathering test for 1200 hours using a Sunshine Super Long Life Weather Meter (manufactured by Suga Test Instruments Co., Ltd., model number “WEL-SUN-HC”), Observation of the coating film showed that there was no change, and that it was good.

The composition of the coating material composition of each example is shown in Table 1.
Tables 7 to 14 show the evaluation results. Next, a coated product was produced as follows. (Examples 35 to 58, Comparative Examples 10 to 21) The antifouling silicone emulsion coating material composition (2) obtained in Example 2 and the antifouling silicone emulsion coating material composition obtained in Example 24 ( 24), each of the comparative silicone emulsion coating material compositions (1) obtained in Comparative Example 1 was added with (A) in these compositions.
Each curing catalyst-containing coating material composition was obtained by further adding 5 parts of a 10% by weight aqueous solution of potassium acetate (curing catalyst) to 100 parts of the components.

Each of the obtained curing catalyst-containing coating material compositions was coated with a bar coater on the following substrate and dried to a thickness of 1 μm.
Alternatively, each coated product was obtained by applying the coating so as to have a thickness of 20 μm, drying at room temperature, and then curing for 1 week in a constant temperature and humidity chamber set at a temperature of 40 ° C. and a humidity of 90%. The coating properties (adhesion,
Acetaldehyde removal rate, wettability-contact angle) were evaluated. In addition, as an additional evaluation item, the test piece was left standing for 1 hour after the test with boiling tap water for 1 hour, and the appearance of the coating film was visually observed, and those having no change were evaluated as good.

The following substrates were used. Stainless steel plate: SUS304 plate (150mm × 70mm
× 0.5 mm). Organic coating plate: Thermosetting acrylic resin-coated aluminum plate (150 mm x 70 mm x 2 mm). PC board: polycarbonate board (150 mm x 70 mm x
5 mm).

Slate board: fiber reinforced cement board (150
mm × 70 mm × 3 mm). Inorganic coated plate: 30 of component (A) obtained in Preparation Example A-2
% Alcohol solution (A-2) was applied to a Pyrex glass plate (100 mm x 100 mm x 1 mm) by bar coater coating so that the dry coating film thickness was 1 m, dried at room temperature, and then at a temperature of 150C for 20 minutes. Cured one.

FRP board: Glass fiber reinforced acrylic board (1
50 mm x 70 mm x 5 mm). If necessary,
An epoxy-based sealer (trade name “Epolo E Sealer” manufactured by Isamu Paint Co., Ltd.) was used as a primer. Tables 15 to 20 show the evaluation results of the coated products.

[0123]

[Table 1]

[0124]

[Table 2]

[0125]

[Table 3]

[0126]

[Table 4]

[0127]

[Table 5]

[0128]

[Table 6]

[0129]

[Table 7]

[0130]

[Table 8]

[0131]

[Table 9]

[0132]

[Table 10]

[0133]

[Table 11]

[0134]

[Table 12]

[0135]

[Table 13]

[0136]

[Table 14]

[0137]

[Table 15]

[0138]

[Table 16]

[0139]

[Table 17]

[0140]

[Table 18]

[0141]

[Table 19]

[0142]

[Table 20]

[0143]

The antifouling silicone emulsion coating material composition of the present invention is an emulsion, in which the optical semiconductor is stably and uniformly dispersed, so that it has antifouling properties, antifogging properties, antibacterial properties and deodorizing properties. And the like, which can sufficiently exhibit various properties derived from the photocatalytic action of the optical semiconductor and can form a highly transparent coated cured film.

Since the antifouling silicone emulsion coating material composition of the present invention is inorganic, the applied cured film is not exposed to ultraviolet light, and the active oxygen generated by the photocatalytic action of the optical semiconductor contained in the film is not affected. The coating film performance is not easily impaired because it is not easily attacked by water, and is excellent in weather resistance, durability and the like. Since the antifouling silicone emulsion coating material composition of the present invention is aqueous, there are few environmental problems. Further, it is stable as an emulsion over a long period of time, and can be adjusted to various colors.

The antifouling silicone emulsion coating composition of the present invention can be used even if a curing catalyst is not used.
Heat curing at a temperature lower than 0 ° C is possible,
If a curing catalyst is used, curing can be performed at room temperature. Therefore, it can be used in a wide range of drying and curing conditions or a wide temperature range. Therefore, not only can a substrate having a shape difficult to apply heat uniformly, a substrate having a large size or a substrate having poor heat resistance be coated, but also when performing a coating operation outdoors or the like. Since it can be painted even when it is difficult to apply heat, its industrial value is high.

Since the antifouling silicone emulsion coating material composition of the present invention does not need to contain a curing catalyst, the cost can be reduced and the curing hardly proceeds during storage (pot life is long). According to the present invention,
According to the method for producing the antifouling silicone emulsion coating material composition, since the composition containing the optical semiconductor can be satisfactorily emulsified, the above-mentioned excellent antifouling silicone emulsion coating material composition is preferably used. Can be manufactured.

The cured coating film of the antifouling coating product of the present invention is formed from the antifouling silicone emulsion coating material composition in which the optical semiconductor is uniformly dispersed. Are uniformly dispersed, so that various properties derived from the photocatalytic action of the optical semiconductor, such as antifouling property, antifogging property, antibacterial property, deodorizing property, etc., can be sufficiently exhibited, and transparency is high. . In addition, since the coating is formed from the inorganic antifouling silicone emulsion coating material composition, even when irradiated with ultraviolet light, active oxygen generated by the photocatalytic action of the optical semiconductor contained in the coating. The coating film performance is not easily impaired because it is not easily attacked by water, and is excellent in weather resistance, durability and the like.

The antifouling coated product of the present invention can be produced by using the above antifouling silicone emulsion coating material composition capable of toning to various colors, so that it has high designability.
Wide range of use. Since the antifouling coated product of the present invention can be produced using the above antifouling silicone emulsion coating material composition which can be cured by heating at a temperature lower than 300 ° C. and at room temperature, a wide range of dry curing conditions Alternatively, it can be manufactured in a temperature range. Therefore, it is possible to use a base material having a shape that is difficult to apply heat evenly, a base material having a large size, a base material having poor heat resistance, and the like, and it can be manufactured even in a work site where heat is hard to be applied such as outdoors. Therefore, its industrial value is high.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09D 133/08 C09D 133/08 161/06 161/06 161/28 161/28 163/00 163/00 167/02 167/02 167/08 167/08 175/04 175/04 (72) Inventor Minoru Inoue 1048 Odakadoma, Kadoma City, Osaka Prefecture Matsushita Electric Works, Ltd. In-company (72) Inventor Hiroji Kishimoto 1048 Odakadoma, Kadoma-shi, Osaka Matsushita Electric Works, Ltd.

Claims (16)

[Claims] 1. The following (A), (B), (C) and (D)
An antifouling silicone emulsion coating material composition comprising a component, wherein the amount of the component (C) is 5 to 80% by weight based on the total solids in the composition. (A) Average composition formula (I): R ² _a SiO _b (OR ¹ )
_c (OH) _d (where R ¹ and R ^{2 each} represent a monovalent hydrocarbon group, and a, b, c and d are a + 2b + c + d
= 4, 0 ≦ a <3, 0 <b <2, 0 <c <4, 0 <d <
And a weight average molecular weight of 600 to 5,000 in terms of polystyrene. (B) at least one surfactant selected from the group consisting of nonionic surfactants and anionic surfactants. (C) Optical semiconductor. (D) water. 2. The antifouling silicone emulsion coating material composition according to claim 1, wherein the component (B) is at least one nonionic surfactant. 3. The antifouling silicone emulsion coating material composition according to claim 1, wherein the nonionic surfactant has an average HLB value of 9 or more. 4. The antifouling silicone emulsion coating material composition according to claim 1, wherein the component (C) is titanium oxide. 5. The component (C) has an average primary particle size of 0.0
The antifouling silicone emulsion coating material composition according to any one of claims 1 to 4, wherein the composition is fine particles having a particle size of 01 to 0.03 µm. 6. The method according to claim 1, further comprising colloidal silica.
The antifouling silicone emulsion coating material composition according to any one of the above. 7. The antifouling silicone emulsion coating material composition according to claim 1, further comprising the following component (E). (E) the average compositional formula ^{(II): HO (R 3} 2 SiO) n H
(Where R ³ represents a monovalent hydrocarbon group, and n is 3 ≦ n ≦
A linear polysiloxane diol containing both terminal hydroxyl groups, represented by the following formula: 8. At least one organic compound selected from the group consisting of alkyd resins, epoxy resins, acrylic resins, acrylic silicone resins, phenolic resins, fluororesins, polyester resins, chlorinated rubber resins, urethane resins and melamine resins. The antifouling silicone emulsion coating material composition according to any one of claims 1 to 7, further comprising a resin. 9. The antifouling silicone emulsion coating material composition according to claim 8, wherein the organic resin is the following component (F). (F) a monomer represented by the general formula (III): CH ₂ ＣＲCR ⁴ (COOR ⁵ ) (where R ⁴ represents a hydrogen atom and / or a methyl group), wherein R ⁵ is substituted or unsubstituted Wherein the first (meth) acrylic acid ester is a monovalent hydrocarbon group having 1 to 9 carbon atoms, and R ⁵ is an epoxy group, a glycidyl group, or a hydrocarbon group containing at least one of them. A second (meth) acrylic acid ester which is at least one group selected from the group consisting of: and a third (meth) acrylic acid wherein R ⁵ is a hydrocarbon group containing an alkoxysilyl group and / or a halogenated silyl group. An acrylic resin that is a copolymer with an ester. 10. The antifouling silicone emulsion coating material composition according to claim 1, further comprising a pigment. 11. An emulsion containing the following components (A), (B) and (D), a powder of the following component (C) and / or a powder dispersion obtained by dispersing the powder in the following component (D): A method for producing an antifouling silicone emulsion coating material composition, comprising a step of mixing with a liquid. (A) Average composition formula (I): R ² _a SiO _b (OR ¹ )
_c (OH) _d (where R ¹ and R ^{2 each} represent a monovalent hydrocarbon group, and a, b, c and d are a + 2b + c + d
= 4, 0 ≦ a <3, 0 <b <2, 0 <c <4, 0 <d <
And a weight average molecular weight of 600 to 5,000 in terms of polystyrene. (B) at least one surfactant selected from the group consisting of nonionic surfactants and anionic surfactants. (C) Optical semiconductor. (D) water. 12. A step of desolvating the organic solvent from a mixture of the following components (A), (B) and (C) containing an organic solvent to obtain a desolvated substance; Mixing a component (B) and at least a component (D) of the following component (D): (A) Average composition formula (I): R ² _a SiO _b (OR ¹ )
_c (OH) _d (where R ¹ and R ^{2 each} represent a monovalent hydrocarbon group, and a, b, c and d are a + 2b + c + d
= 4, 0 ≦ a <3, 0 <b <2, 0 <c <4, 0 <d <
And a weight average molecular weight of 600 to 5,000 in terms of polystyrene. (B) at least one surfactant selected from the group consisting of nonionic surfactants and anionic surfactants. (C) Optical semiconductor. (D) water. 13. Formula (IV): R ² _m Si (OR ¹ ) _4-m
(Where R ¹ and R ^{2 each} represent a monovalent hydrocarbon group;
By mixing the hydrolyzable organosilane represented by the following formula (C), a powder of the following component (C) and / or a dispersion thereof, and the following component (D): And a step of obtaining a mixture containing the component (C); and a step of mixing the mixture with at least the component (B) of the following component (B) and an additional component (D). A method for producing a coating material composition. (A) Average composition formula (I): R ² _a SiO _b (OR ¹ )
_c (OH) _d (where R ¹ and R ^{2 each} represent a monovalent hydrocarbon group, and a, b, c and d are a + 2b + c + d
= 4, 0 ≦ a <3, 0 <b <2, 0 <c <4, 0 <d <
And a weight average molecular weight of 600 to 5,000 in terms of polystyrene. (B) at least one surfactant selected from the group consisting of nonionic surfactants and anionic surfactants. (C) Optical semiconductor. (D) water. 14. An antifouling coated product comprising a coating layer comprising a cured coating of the antifouling silicone emulsion coating material composition according to any one of claims 1 to 10 on the surface of a substrate. 15. The substrate according to claim 15, wherein the substrate is an inorganic substrate, an organic substrate,
An inorganic-organic composite substrate, a single material of a coating substrate having at least one layer of an inorganic film and / or at least one layer of an organic film on the surface of any of these substrates,
The antifouling property according to claim 14, wherein the antifouling property is selected from the group consisting of a composite material obtained by combining at least two of these, and a laminated material obtained by laminating at least two of these. Painted. 16. The antifouling coated article according to claim 15, wherein the coating film on the surface of the coating substrate is a primer layer.