JPH1121509A - Coating material for repairing roofing material of building - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coating material which can give coating films having good adhesion to roofing materials such as ones made of slate or mortar and being flexible and capable of following the expansion or contraction of a base material upon a change in atmospheric temperature by selecting a coating material containing a specified curable polyorganosiloxane, a specified phenyl- containing silane, a specified partial alkoxysilane hydrolyzate, a pigment and a catalyst and having a specified viscosity. SOLUTION: This material contains a curable polyorganosiloxane represented by the formula: R<1> a SiX<1> b O(4-(a+b))/2 , a phenyl-containing silane represented by the formula: PhSi(OR<2> )3 ; a partial hydrolyzate of an alkoxysilane represented by the formula: R<3> n Si(OR<4> )4-n , a pigment (e.g. titanium oxide) and a catalyst (e.g. dibutyltin dilaurate) and has a viscosity (at 25 deg.C) of 2-5,000 cP. In the formulae, R<1> is a monovalent organic group or H; X<1> is OH or a hydrolyzable group; 0.8<a<2; and 0.3<=b<2; R<2> is a 1-4C alkyl; R<3> is a monovalent (halo) hydrocarbon residue; R<4> is R<2> ; and n is 0-2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a paint for repairing building roofing materials, and more particularly, to a coating material for building roofing materials such as slate and mortar and a building roof repairing agent mainly comprising shirasu balloon. It has good adhesion and flexibility, can follow the expansion and contraction of the base material due to changes in temperature, etc., has excellent heat insulation and heat insulation considering radiation, convection, conduction, reflection by sunlight, and furthermore, weather resistance And paints having excellent stain resistance.

[0002]

[Technical Background of the Invention and its Problems] Protection against slate, steel plate roofs, and concrete roofing materials used for rooftops, etc., which are strongly exposed to the direct sunlight, are combined from various aspects such as heat insulation, heat insulation, and waterproofing. There has been a need for a combination method. Therefore, the inner and middle insulation of the lower surface of the slab is made of organic foam on the flat roof,
Intense thermal radiation of summer sunlight causes large thermal stress on the roof slab, causing cracks and causing water leakage. In order to solve such a drawback of the inside and middle heat insulation, a method of external heat insulation in which a heat insulating material is arranged on the upper surface of a roof slab is used. In the case of external heat insulation, a heat insulation and waterproofing method is used in which a waterproof layer and a heat insulating material are combined, and two types of methods are employed in which the heat insulating material is disposed above or below the waterproof material. However, since the current state of external insulation is only heat conduction and waterproofing, the exposed surface on the outside becomes extremely hot due to the intense irradiation heat of the irradiated sun, and the contact surface between the surface and the waterproof layer and the insulating material becomes extremely hot. However, the waterproof layer is peeled, deteriorated and deformed, causing water leakage, and is not a reliable method and material. On the other hand, slate is made of asbestos fiber solidified with cement and formed into a plate shape, and is used as a roofing material with excellent strength, lightness, durability, economy, etc.
Although widely used for roofs such as warehouses and railway platforms, the surface of a highly durable slate deteriorates due to various chemical and physical factors due to long-term exposure to the natural environment, and asbestos fibers are reduced. It will be deposited in an unstable state. Under these conditions, additional chemical,
Due to the physical effects, the asbestos fibers are finely dispersed and released into the atmosphere. It is widely recognized that asbestos fiber is a carcinogen that causes lung cancer, etc., and asbestos released into the air and suspended may cause harm to human health. There has been a need for measures to prevent traces of asbestos from the roof from scattering, albeit in a trace amount. Further deterioration of the slate roofing material may result in loss of strength and damage, and even when dismantling and removing aged slate roofing material, it prevents scattering of a large amount of asbestos dust generated at the time of removal. This is almost impossible technically, and it is not economically preferable to replace the slate roofing material by stopping the production line of the factory. A method of coating the surface of a slate roofing material with an organic or inorganic coating agent on the assumption that the deteriorated slate roofing material is used as it is (Japanese Patent Laid-Open No. 4-5)
No. 5550) has been proposed, but satisfactory characteristics have not been obtained. Further, in Japanese Patent Application Laid-Open No. 6-100796, a polymer mortar obtained by mixing a shirasu balloon, white cement, silica sand, hydrous magnesium silicate, and methylcellulose with an acrylic or vinyl acetate water-soluble polymer (Japanese Patent Publication No. 61-6861). Although a heat insulation and insulation method for a building using the method has been proposed, it is not preferable because it causes problems in weather resistance and stain resistance. In addition, if the weather resistance and stain resistance of the surface of the coating film become defective, the surface of the film becomes discolored or blackened, thereby affecting the heat shielding properties and the heat insulating properties.

[0003]

The object of the present invention is to provide a coating film having good adhesiveness and flexibility to a building roofing material such as slate and mortar, and a building roofing repair agent mainly comprising a shirasu balloon, and having a high temperature. It provides a paint that can follow the expansion and contraction of the base material due to changes, etc., has excellent heat insulation and heat insulation considering radiation, convection, conduction and reflection by sunlight, and also has excellent weather resistance and stain resistance. .

[0004]

According to the present invention, as a result of various studies to achieve the above object, it has been found that, by combining a specific siloxane component, a pigment and a catalyst, the composition can be cured and dried at room temperature and cured by accelerated heating at a relatively low temperature. Not only is the cured coating excellent in weather resistance and stain resistance, but it is also good for building roofing materials It can follow the expansion and contraction of the base material due to changes, etc.
The present inventors have found that a paint having convection, conduction, and reflection can be provided, and have accomplished the present invention. That is, the paint of the present invention comprises the following components (A) to (E) and has a viscosity at 25 ° C. of 2 to 5000 cP. (A) General formula R ¹ _a SiX ¹ _b O _{(4- (a + b)) / 2} (wherein, R ¹ represents a monovalent organic group or a hydrogen atom, and X ¹
Represents a hydroxyl group or a hydrolyzable group, and a and b
Is a number having the following relationship. 0.8 <a <2 0.3 ≦ b <2) Curable polyorganosiloxane (B) represented by the general formula PhSi (OR ² ) ₃ (wherein R ² represents an alkyl group having 1 to 4 carbon atoms) A phenyl group-containing silane represented by the general formula R ³ Si (OR ⁴ ) _4-n (wherein R ³ is a monovalent monovalent hydrogen residue optionally substituted with a halogen atom, and R ⁴ is A partially hydrolyzed product of an alkoxysilane represented by an alkyl group having 1 to 4 carbon atoms and n is an integer of 0 to 2) (D) pigment (E) catalyst

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The polyorganosiloxane of the component (A) used in the present invention is represented by the following general formula. R ¹ _a SiX ¹ _b O _{(4- (a + b)) / 2} (wherein, R ¹ represents a monovalent organic group or a hydrogen atom, and X ¹
Represents a hydroxyl group or a hydrolyzable group, and a and b are numbers having the following relationship. 0.8 <a <20.3 ≦ b <2) Here, R ¹ represents a monovalent organic group or a hydrogen atom. Examples of the monovalent organic group include alkyl groups such as methyl, ethyl, propyl, butyl, and hexyl; alkenyl groups such as vinyl and allyl; aryl groups such as phenyl, tolyl and xylyl; and aralkyl groups such as phenethyl and β-phenylpropyl. Aminoalkyl groups such as N- (β-aminoethyl) -γ-aminopropyl, epoxy group-containing groups such as γ-glycidoxypropyl and 3,4-epoxycyclohexyl, and (meth) such as γ-methacryloxypropyl. Acrylic group-containing groups, mercaptoalkyl groups such as γ-mercaptopropyl, cyanoalkyl groups such as cyanoethyl,
Examples thereof include chloroalkyl groups such as β-chloroethyl and γ-chloroethyl, and fluoroalkyl groups such as 3,3,3-trifluoropropyl. Among these, the alkyl group is preferable because the gloss and weather resistance of the coating are good,
Particularly, a methyl group is preferable. X ^{1 in the} component (A) represents a hydroxyl group or a hydrolyzable group. As the hydrolyzable group, an alkoxy group, an acyloxy group, a ketoxime group,
Examples include an amide group, an alkenyloxy group, and a halogen atom. A hydroxyl group or an alkoxy group is preferable, and a hydroxyl group, a methoxy group, or an ethoxy group is particularly preferable, since a by-product generated during the curing reaction has a low odor and excellent curability and film properties. Further, a and b need to be numbers having the following relationship. When 0.8 <a <2 0.3 ≤ b <2 a is 0.8 or less, the cured film becomes brittle, and when it is 2 or more, a good cured film is not obtained, and oil oozes out into the film, so that dirt is easily involved. Not suitable for the purpose of the present invention. If b is less than 0.3, the curing speed is too slow to be suitable for practical use, and a film having good abrasion resistance and gloss cannot be obtained. If it is more than 2, the cured film becomes brittle and is not suitable for the purpose of the present invention. The component (A) can be used as a liquid or a solid as long as it can be dissolved and mixed with the component (C). The component (A) has a good viscosity of 5 cP or more in order to easily obtain a clear coating without stickiness and good tackiness to the base material.
0cP or less is preferable. Such a polyorganosiloxane can be obtained by a known method, and is obtained by hydrolyzing and partially hydrolyzing a hydrolyzable organosilane such as organoalkoxysilane or organochlorosilane as a raw material.

The phenyl group-containing silane represented by the general formula PhSi (OR ² ) ₃ , which is the component (B) used in the present invention, is an important component for imparting strength, adhesion and gloss. . Where R ²
Represents an alkyl group having 1 to 4 carbon atoms. A phenyl group-containing silane having no hydrolyzable group is not incorporated as a skeleton into a film-forming component and is not useful for improving the strength and adhesion of a film. These silanes include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane and the like, and among them, availability is easy, and the reactivity with the components (A) and (C) is balanced. From the viewpoint of ease, phenyltrimethoxysilane and phenyltriethoxysilane are particularly preferred.

[0007] The partially hydrolyzed product (liquid silicone resin) of the alkoxy represented by the general formula R ³ Si (OR ⁴ ) _4-n , which is the component (C) used in the present invention, is used in the present coating composition. It is one of the important components used for adjusting hardness and as a reactive diluting solvent.
In the formula, R ³ is a substituted or unsubstituted monovalent hydrocarbon residue, specifically, an alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl,
An aryl group such as tolyl, xylyl, biphenyl, naphthyl and the like can be mentioned, and an alkyl group is preferable, and a methyl group is particularly preferable because it is easily available and has a property of easily dissolving the component (A). In the formula, R ⁴ is an alkyl group having 1 to 4 carbon atoms. When the carbon number is 5 or more,
When the partial hydrolyzate is used as a reactive-reactive diluent, the reaction rate of the partial hydrolyzate is slow, and the formation of a coating film is undesirably slow. As the alkyl group having 1 to 4 carbon atoms, any of a straight-chain or branched-chain alkyl group may be used, and among them, methyl and ethyl groups are particularly preferable.

The pigment used as the component (D) in the present invention includes organic pigments such as carbon black, quinacridone, naphthol red, cyanine blue, cyanine green and Hansa yellow, titanium oxide, barium sulfate, red iron oxide, and composite metal. Oxide inorganic pigments are good, and one or two or more selected from these groups may be used in combination. The amount of the pigment to be added is not particularly limited because the concealing property varies depending on the type of the pigment.However, the amount of the component (A), the component (B) and the component (C) is 50 to 1200 with respect to 100 parts by weight of the total component.
The weight is good, preferably 80 to 500 parts by weight. If the amount is less than 50 parts by weight, the concealing property deteriorates, and if it exceeds 500 parts by weight, the smoothness of the coating film deteriorates, which is not preferable. Dispersion of the pigment may be performed by an ordinary method. At that time, a dispersant, a dispersing aid, a thickener, an antifoaming agent, and the like can be used.

As the curing catalyst of the component (E) used in the present invention, general curing catalysts used for condensation-curable silicone compositions can be used. These include organic amines such as triethanolamine; tin octylate; Carboxylic acid metal salts such as zinc octylate; organic tin compounds such as dibutyltin dilaurate and dibutyltin dioctoate; titanates such as tetrabutyl titanate and tetrapropyl titanate; quaternary ammonium compounds such as quaternary ammonium carboxylate; Examples include amine-based silane coupling agents such as γ-aminopropyltriethoxysilane and N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, which are easy to handle.
Dibutyltin dilaurate and dibutyltin dioctoate are preferred. Two or more of these catalysts may be used in combination. The amount of the catalyst is preferably 0.2 to 20 parts by weight based on 100 parts by weight of the mixture comprising the components (A), (B) and (C), based on the curing speed of the paint and the pot life.
Particularly, 2 to 8 parts by weight is preferable.

Further, a general solvent may be used in the paint of the present invention. As the solvent component, component (A),
There is no particular limitation as long as it dissolves and disperses the components (B) and (C), and alcohols such as methanol, ethanol and isopropanol; and ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, tetrahydrofuran and dioxane Ether alcohols and ethers; ketones such as acetone, methyl ethyl ketone and diethyl ketone; esters such as methyl acetate, ethyl acetate and n-butyl acetate;
Aliphatic hydrocarbons such as n-hexane, gasoline, rubber volatile oil, mineral spirit, and kerosene can be exemplified. The paint of the present invention has a viscosity at 25 ° C of 2 to 5000 cP.
Is effective from the viewpoints of workability and finish of the coating film, and more preferably 5 to 100 cP.

As a method of coating the surface of the substrate, a method such as brush coating, spray coating, roller coating and the like can be used. The coating composition of the present invention is cured by being air-dried for several hours to several days after application to form a good coating.

The amount of the coating composition of the present invention comprising component (A), component (B) and component (C) is 1000 parts by weight of component (A) and 5 to 150 parts by weight of component (B). The components are 10 to 350 parts by weight. That is, the amount of the component (A), the component (B) and the component (C) is 5 to 150 parts by weight per 1000 parts by weight of the component (A).
Parts by weight, preferably 10 to 350 parts by weight of the component (C). (A) Ingredient
If the amount of the component (B) is less than 5 parts by weight with respect to 1000 parts by weight, there is a problem in the adhesion at the time of film formation. The component (B) is 150
Exceeding the weight part is not preferable because cracks occur in the coating.
If the component (C) is less than 10 parts by weight, the coating becomes brittle, and
If the amount exceeds 50 parts by weight, there is a disadvantage that the toughness of the coating film is lost and it is impossible to cope with the expansion and contraction of the substrate.

[0013] A primer may be used to more effectively adhere the paint to the substrate. As the type of the primer, if it does not affect the effect of the present invention,
A commonly used one may be used.

[0014]

(Synthesis of component (A))

Synthesis Example 1 A flask equipped with a stirrer, a heating jacket, a condenser, and a dropping funnel was charged with methyltrimethoxysilane.
952 g (7 mol), 198 g of phenyltrimethoxysilane (1
mol), 516 g (4 mol) of dimethyldichlorosilane and 1500 ml of toluene, and 234 g of water (13 mol
l) was gradually added dropwise using a dropping funnel. After dropping,
The reaction solution was maintained at a temperature of about 110 ° C. for 1 hour and heated under reflux. Cool the reaction to room temperature, transfer to a separatory funnel,
After standing to separate the organic layer and the aqueous layer, the lower aqueous layer was removed to obtain a toluene solution of polyorganosiloxane.
A saturated saline solution was added to the organic layer and the mixture was stirred well, and then allowed to stand to separate an aqueous layer. After repeating this salting-out operation twice, water was added and the organic layer was washed twice with the same operation. This organic layer was placed in a flask equipped with a stirrer, a heating jacket and a moisture meter, and the volatile components were distilled off under reduced pressure at 30 mmHg and 80 ° C. for 3 hours to obtain 860 g (A-1) of a polyorganosiloxane having a viscosity of 1000 cP. Was. Synthesis Example 2 A flask equipped with a stirrer, a heating jacket, a condenser, and a dropping funnel was charged with methyltriethoxysilane.
1780g (10mol), trimethylchlorosilane 216g (2mo
l) and 2,000 ml of toluene, and add
0 g (60 mol) was gradually added dropwise using a dropping funnel. After the completion of the dropwise addition, the mixture was maintained at a reaction liquid temperature of about 110 ° C. for 1 hour and heated under reflux. The reaction solution was cooled to room temperature, transferred to a separating funnel and allowed to stand to separate an organic layer and an aqueous layer, and then the lower aqueous layer was removed to obtain a toluene solution of polyorganosiloxane. A saturated saline solution was added to the organic layer and the mixture was stirred well, and then allowed to stand to separate an aqueous layer. After repeating this salting-out operation twice, water was added and the organic layer was washed twice with the same operation. The organic layer was placed in a flask equipped with a stirrer, a heating jacket and a moisture meter, and volatile components were distilled off under reduced pressure at 30 mmHg and 80 ° C. for 3 hours to obtain a polyorganosiloxane. To this, potassium hydroxide was added to 50 ppm, and the mixture was heated at 180 ° C. for 5 hours to further condense. This was neutralized with ethylene chlorohydrin and 760 g of silanol-containing polyorganosiloxane having a viscosity of 8000 cP (A-2)
I got Synthesis Example 3 A flask equipped with a stirrer, a heating jacket, a condenser, and a dropping funnel was charged with methyltriethoxysilane.
160.2 g (0.9 mol), 12 g of dimethyldimethoxysilane
(0.1 mol), 200 g of methanol and 5 g of acetic acid, and gradually heated with stirring. When the liquid temperature reaches 64 ° C, water
16.2 g (0.9 mol) were slowly added. In addition, liquid temperature 64 ° C
For 6 hours to carry out hydrolysis and condensation reactions.
Next, after the volatile components were distilled off under the conditions of normal pressure and a liquid temperature of 130 ° C., the pressure was gradually reduced, and the degree of pressure reduction was 30 Torr, and the liquid temperature was 130 ° C.
After further evaporating the volatile components under reduced pressure under the conditions described above, return to normal pressure,
48 g of liquid polyorganosiloxane having a viscosity of 20 cP (A-3)
I got

The following phenyl group-containing silanes of component (B) were used. B-1 Ph-Si (OMe) ₃ B-2 Ph-Si (OEt) ₃ [Synthesis of the component (C)] Synthesis Example 4 A flask equipped with a stirrer, a heating jacket, a condenser and a dropping funnel was charged with methyltrimethoxy. Silane
136 g (1 mol), 200 g of methanol and 1.5 g (0.01 mol) of methyltrichlorosilane were charged, and stirred and mixed at room temperature. Thereto, 15.3 g (0.85 mol) of city water was gradually dropped. Further, the mixture was kept at a liquid temperature of 64 ° C. for 4 hours to carry out hydrolysis and condensation reactions. Then, after evaporating the volatile components under the conditions of normal pressure and a liquid temperature of 130 ° C., gradually reducing the pressure, gradually evaporating the volatile components under a reduced pressure of 30 Torr and a liquid temperature of 130 ° C. And 61 g (C-1) of a liquid polyorganosiloxane having a viscosity of 10 cP was obtained. Synthesis Example 5 Methyltriethoxysilane was added to a flask equipped with a stirrer, a heating jacket, a condenser, and a dropping funnel.
178 g (1 mol), 200 g of methanol and 1.5 g (0.01 mol) of methyltrichlorosilane were charged, and stirred and mixed at room temperature. Thereto, 19.8 g (1.1 mol) of city water was gradually dropped. Further, the mixture was kept at a liquid temperature of 64 ° C. for 4 hours to carry out hydrolysis and condensation reactions. Then, after evaporating the volatile components under the conditions of normal pressure and a liquid temperature of 130 ° C., gradually reducing the pressure, gradually evaporating the volatile components under a reduced pressure of 30 Torr and a liquid temperature of 130 ° C. And 71 g (C-2) of a liquid polyorganosiloxane having a viscosity of 50 cP was obtained. Table 1 shows the polyorganosiloxanes (A-1 to 3), the component (B), the alkoxy-containing polyorganosiloxanes (C-1 to 2), the catalyst, the solvent, and the white pigment (titanium oxide) synthesized in the above synthesis examples.
By mixing according to the formula shown in Examples 1 to 3, respectively.
5 and Comparative Examples 1 to 5 were obtained. The pigment was dispersed in a Glen Mill and blended in the paint. Using these paints, the following test pieces were prepared and evaluated. Table 1 shows the results.

Preparation of Test Specimen 1 A paint was applied to a 5 × 15 cm slate plate using a roller, and dried and cured at room temperature for 1 week to obtain a test specimen. Preparation of Test Piece 2 A repair agent using a Shirasu balloon was applied to a 5 × 15 cm slate plate, and dried and cured at room temperature for one week. A primer based on triethoxysilane / γ-glycidoxypropyltrimethoxysilane was applied to this, and after one hour, a paint was sprayed using an air gun and cured at room temperature for one week to prepare a test piece. Preparation of Test Piece 3 An aluminum plate having a size of 15 × 15 cm was degreased and washed using isopropyl alcohol. A paint was sprayed on this with an air gun, and the coating was allowed to stand at 25 ° C. and 60% RH for 24 hours to form a coating, thereby obtaining a test piece.

[Weather Resistance] After exposure for 1000 hours using a sunshine weatherometer, the appearance was visually observed and evaluated according to the following four grades. ◎: Transparency of the film was ensured, and there was no whitening or peeling. ：: Transparency of the film was secured, and there was no peeling. Δ: Whitening of the coating was observed, but no peeling was observed. ×: Whitening and peeling of the coating occurred. [Water resistance] After running tap water on the test piece for 12 hours, the appearance was visually observed and evaluated according to the following four grades. ◎: Transparency of the film was ensured, and there was no whitening or peeling. ：: Transparency of the film was secured, and there was no peeling. Δ: Whitening of the coating was observed, but no peeling was observed. ×: Whitening and peeling of the coating occurred. [Warm water resistance] The test piece was immersed in warm water of 50 ° C for 10 days, and the appearance was visually observed and evaluated according to the following four grades. ◎: Transparency of the film was ensured, and there was no whitening or peeling. ：: Transparency of the film was secured, and there was no peeling. Δ: Whitening of the coating was observed, but no peeling was observed. ×: Whitening and peeling of the coating occurred. [Adhesion] Cross-cut peeling test The adhesion to the substrate was examined by a cross-cut cellophane adhesive tape (cellophane tape) peel test, and evaluated by the number of cross-cuts remaining on the substrate among 100 cross-cuts. [Heat Barrier Property] A substrate was placed on an Atlas HPUV (HPUV indoor light exposure system), and the surface temperature after irradiation for 30 minutes was measured.

[0018]

[Table 1]

[0019]

As described above, the paint according to the present invention comprises:
It is composed of the components (A) to (E) and can be cured and dried at room temperature, and can be cured by heating at a relatively low temperature.The cured film is not only excellent in weather resistance and stain resistance, but also For building roofing materials and building roof repair agents, the coating film has good adhesion and is flexible, and can follow the expansion and contraction of the base material due to changes in temperature, radiation, convection, Since it is a paint having conductivity and reflection and is effective for protecting the base material and extending the life of resources, its industrial and industrial value is extremely large.

Continued on the front page (72) Inventor Yoshitaka Yamanaka 1-448 Ishidacho, Mizuho-ku, Nagoya-shi, Aichi Prefecture Within Cementtex Corporation (72) Inventor Yoshiaki Takezawa 6-2-31 Roppongi, Minato-ku, Tokyo Inside Toshiba Silicone Corporation (72) Inventor Yoshiharu Moriya 6-2-31 Roppongi, Minato-ku, Tokyo Inside Toshiba Silicone Corporation

Claims (1)

[Claims] Claims: 1. A composition comprising the following components (A) to (E):
A paint for repairing building roofing materials, which has a viscosity at 2C of 2 to 5000 cP. (A) General formula R ¹ _a SiX ¹ _b O _{(4- (a + b)) / 2} (wherein, R ¹ represents a monovalent organic group or a hydrogen atom, and X ¹
Represents a hydroxyl group or a hydrolyzable group, and a and b
Is a number having the following relationship. 0.8 <a <2 0.3 ≦ b <2) Curable polyorganosiloxane (B) represented by the general formula PhSi (OR ² ) ₃ (wherein R ² represents an alkyl group having 1 to 4 carbon atoms) A phenyl group-containing silane represented by the general formula R ³ Si (OR ⁴ ) _4-n (wherein R ³ is a monovalent monovalent hydrogen residue optionally substituted with a halogen atom, and R ⁴ is A partially hydrolyzed product of an alkoxysilane represented by an alkyl group having 1 to 4 carbon atoms and n is an integer of 0 to 2) (D) pigment (E) catalyst