JP2000007980A - Coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coating composition which can give a coating film improved in the easiness with which adhering water drops slip off and water repellency by incorporating the reaction product of an aqueous solution of a copolymer obtained by copolymerizing a specified monomer with a functional- group-containing α,β-ethylenically unsaturated monomer and other α,β- ethylenically unsaturated monomers with an epoxy-terminated siloxane polymer and an acid compound. SOLUTION: A monomer of formula I (wherein R1 is H or methyl; R2 is phenyl or a 1-6C alkyl; n1 is 1-10; and n2 is 5-200) in an amount of 3-70 wt.% is copolymerized with 1-25 wt.% α,β-ethylenically unsaturated monomer having at least one functional group selected among carboxyl, sulfo, and amino and 5-95 wt.% other copolymerizable α,β-unsaturated monomers to obtain a copolymer. The reaction product obtained by reacting an aqueous solution or dispersion of this copolymer with an epoxy-terminated siloxane polymer of formula II (wherein R is a 1-6C alkyl; (m) is 6-150 on the average; and (n) is 0-6) and an acid compound in an equivalent ratio of the epoxy groups to the acid groups of 0.5/1 to 10/1 is incorporated with other necessary components to obtain the objective coating composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a building, an automobile,
The present invention relates to a coating composition which is hardly wetted by glass, paper, industrial products and the like, and which can form a water-slidable surface on which adhered water drops easily slide. The coating composition of the present invention is particularly useful as an aqueous coating composition for drying at room temperature.

[0002]

2. Description of the Related Art Conventionally, in order to make the surface of an object less wet, that is, to impart water repellency to the surface of the object, the surface of the object is made of a hydrophobic material such as a silicon compound or a resin, a fluororesin, or a polyolefin. Coating has been performed. When water adheres to the surface of the object subjected to the surface hydrophobization treatment in this way, the water is repelled to form spherical water droplets, and large water droplets fall under their own weight, while small water droplets remain strongly adhered to the object surface. Yes, a phenomenon that does not fall even when the attachment surface is tilted vertically is often observed. In such a case, a dry surface without water droplets cannot be obtained unless the water droplets are forcibly removed by a mechanical method such as wiping off water droplets.

Accordingly, the present applicant has studied to develop a material capable of forming a water-slidable surface on which water droplets can easily slide down by its own weight even if the contact angle of the attached water droplets is not so large. A film formed by crosslinking and curing a reaction product obtained by reacting a fluoropolymer having a siloxane polymer with a certain epoxy-terminated siloxane polymer in the presence of a sulfonic acid compound together with a crosslinking agent meets the above-mentioned object. He suggested to the headline.

On the other hand, in recent years, paints have been made more water-soluble from the viewpoints of air pollution prevention and hygiene at the time of painting, and also from the viewpoint of disaster prevention. It is. However, it is usually difficult to make the above-mentioned materials water-soluble, and a coating film obtained from an aqueous solution or dispersion of a copolymer having a conventionally known water-repellent property, such as a polydimethylsiloxane monomer as a copolymer component, Although showing a high contact angle of 90 ° or more, small water droplets still adhered to the surface of the object, and no water fell even when the adhered surface was tilted vertically. further,
Siloxane polymer as an additive component in ordinary water-based paints
And the like, the hydrophobicity of the siloxane polymer is strong,
There was a problem that compatibility with an aqueous solution or aqueous dispersion of a copolymer as a film-forming component in a coating material was not obtained, and a uniform coating film could not be formed.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found that a monomer having a water repellency and a monomer having a hydrophilic group are essential. An aqueous coating composition obtained by blending a reaction product of a certain epoxy-terminated siloxane polymer and an acid in an aqueous solution or aqueous dispersion of the coalesced coating has excellent water-sliding and water-repelling properties without impairing compatibility and the like. The inventors have found that a film can be formed, and have reached the present invention.

That is, the present invention relates to (A) (a)
3 to 70% by weight of a monomer represented by

[0007]

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(Wherein R ¹ represents a hydrogen atom or a methyl group,
The R ² may be the same or different phenyl group or an alkyl group having 1 to 6 carbon atoms, n ¹ is 1 to 10 integer, n ² is 5-2
00 indicates an integer. (B) 1 to 25% by weight of an α, β-ethylenically unsaturated monomer having one kind of functional group selected from the group consisting of a carboxyl group, a sulfonic acid group and an amino group; 5-9 polymerizable α, β-ethylenically unsaturated monomers
(B) (g) a copolymer aqueous solution or aqueous dispersion obtained by copolymerizing a monomer mixture containing 6% by weight;

[0009]

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(Wherein, R represents an alkyl group having 1 to 6 carbon atoms, the average number of m is 6 to 150, and n is an integer of 0 to 6).
And (h) an acid compound.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the aqueous copolymer solution or aqueous dispersion (A) comprises a monomer (a) represented by the above formula (I), a carboxyl group, a sulfonic acid group and an amino group. Monomer containing α, β-ethylenically unsaturated monomer (b) having one selected functional group and other copolymerizable α, β-ethylenically unsaturated monomer (c) It is obtained by copolymerizing a body mixture.

The monomer (a) represented by the above formula (I) is
It imparts water repellency to the copolymer and enhances compatibility with the reaction product (B) described below. The monomer (a)
In, R ¹ is hydrogen atom or a methyl group, R ²
Is a phenyl group or an alkyl group having 1 to 6 carbon atoms, but they need not always be the same. n1 is an integer of ¹ to 10, n2 is 5 to ²⁰⁰ , preferably 15 to
It is an integer of 150. If n ² is less than 5, sufficient water repellency cannot be obtained, while if it exceeds 200, the copolymer becomes insufficient in hydrophilicity and poor in water solubility or water dispersibility, which is not desirable. As specific examples of the monomer (a), commercially available products include “Silaplane FM-0711”, “Silaplane FM-0721”, and “Silaplane FM-072”.
5 "(all manufactured by Chisso Corporation) and the like.

Α, β- having one kind of functional group selected from the group consisting of the above-mentioned carboxyl group, sulfonic acid group and amino group
The ethylenically unsaturated monomer (b) improves the water solubility or water dispersibility of the copolymer. Examples of the monomer having a carboxyl group include (meth) acrylic acid, crotonic acid, and itacone. Acid, maleic acid, fumaric acid,
2-carboxylethyl (meth) acrylate, 2-carboxylpropyl (meth) acrylate, 5-carboxylpentyl (meth) acrylate, an unsaturated monomer having a hydroxyl group and a bifunctional carboxylic anhydride (for example, maleic anhydride, itaconic anhydride) , Succinic anhydride, phthalic anhydride, etc.), and the monomer having a sulfonic acid group includes, for example, 2- (meth) acryloxyethylsulfonic acid. Examples of the monomer having an amino group include dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth).
Acrylate and t-butylaminoethyl (meth) acrylate.

The other copolymerizable α, β-ethylenically unsaturated monomers (c) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, (meth)
N-propyl acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, (meth) 2-ethylhexyl acrylate, n-octyl (meth) acrylate, (meth)
Decyl acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, (meth)
Methoxyethyl acrylate, ethoxyethyl (meth) acrylate, methoxybutyl (meth) acrylate, ethoxybutyl (meth) acrylate, (meth) acrylic acid 2
-Hydroxyethyl, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyether polyols such as polyethylene glycol and polypropylene glycol, and (meth) acrylic acid (Meth) acrylic acid esters such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, cyclohexyl vinyl ether, and phenyl vinyl ether. ; Vinyl acetate, vinyl propionate, vinyl lactate, vinyl butyrate,
Vinyl esters such as vinyl caproate; propenyl esters such as isopropenyl acetate, (meth) acrylonitrile, styrene, α-methylstyrene, vinyltoluene, and α-chlorostyrene.
The species or two or more species can be appropriately selected and used according to the purpose.

The copolymerization ratio of the above monomers is such that the monomer (a) is 3 to 70% by weight, preferably 5 to 40% by weight,
The monomer (b) is 1 to 25% by weight, preferably 5 to 15% by weight, and the monomer (c) is 1 to 25% by weight, preferably 5 to 5%.
It is 15% by weight, and the monomer (d) is 5 to 96% by weight, preferably 45 to 90% by weight. When the amount of the monomer (a) is less than 3% by weight, sufficient water repellency cannot be obtained, and the compatibility with the reaction product (B) described below is reduced. It is not preferable because water solubility or water dispersion becomes difficult. When the amount of the monomer (b) is less than 1% by weight, the water solubility or water dispersibility of the copolymer aqueous solution (water dispersion) becomes poor. On the contrary, when the amount exceeds 25% by weight, the phase with the reaction product (B) becomes poor. It is not preferable because the solubility is lowered.

From the viewpoint of improving water solubility or water dispersibility, a monomer having an alkoxysilyl group (d) is used in the monomer mixture used for producing the aqueous copolymer solution or aqueous dispersion (A). ) Can be contained in an amount of 1 to 40% by weight.

The monomer (d) having an alkoxysilyl group has an alkoxysilyl group represented by the following formula (IV):

[0018]

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Wherein R ⁴ is an alkyl group having 1 to 10 carbon atoms, and R ⁵ and R ⁶ are the same or different and each represents a phenyl group, an alkyl group having 1 to 6 carbon atoms or an alkoxyl group having 1 to 10 carbon atoms. , N ⁵ each represent an integer of 1 to 4. When n ⁵ is 2 or more, R ⁵ and R ⁶ may be the same or different.) Typical examples thereof are as follows. Examples include the monomers represented by the formulas (V) and (VI).

[0020]

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(Where A is

[0022]

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Is shown. R ⁷ represents a hydrogen atom or a methyl group,
R ⁸ represents a divalent saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms. R ⁴ , R ⁵ , R ⁶ and n ⁵ each have the same meaning as described above. )

[0024]

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(In the formula, R ⁹ represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and n ⁶ represents 0 or 1. R ⁴ , R
⁵ , R ⁶ and n ⁵ each have the same meaning as described above. In the above formulas (V) and (VI), as the divalent saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms represented by R ⁸ and R ⁹ , a linear or branched alkylene group, for example, methylene , Ethylene, propylene, 1,2-, 1,3- or 2,3-butylene, tetramethylene, ethylethylene,
Pentamethylene, hexamethylene group and the like.
As the alkyl group having 1 to 6 carbon atoms represented by R ⁵ and R ⁶ , a linear or branched alkyl group, for example, methyl, ethyl, n-propyl, isopropyl, n-, i-, se
c- or tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, 1-
Methyl pentyl and the like. Examples of the alkyl group having 1 to 10 carbon atoms represented by R ⁴ include, in addition to those exemplified as the alkyl groups having 1 to 6 carbon atoms represented by R ⁵ and R ⁶ , n-heptyl, 2-ethylhexyl, n- Octyl, n-nonyl, n-decyl and the like can be mentioned. R
^As the alkoxyl group having 1 to 10 carbon atoms represented by ⁵ and R ⁶ , a linear or branched alkoxyl group, for example, methoxy, ethoxy, n-propoxy, isopropoxy,
n-, i-, sec- or tert-butoxy, n-pentoxy, isopentoxy, n-hexyloxy, isohexyloxy, n-octyloxy and the like.

In the monomer of the above formula (V), A is

[0027]

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For example, β- (meta)
Acryloyloxyethoxysilane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane,
γ- (meth) acryloyloxypropylmethyldimethoxysilane, γ- (meth) acryloyloxypropylmethyldiethoxysilane and the like can be preferably exemplified.

In the monomer of the above formula (V), A is

[0030]

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For example,

[0032]

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And the like.

Examples of the monomer of the formula (VI) include vinyltrimethoxysilane and vinyltriethoxysilane.

The monomer mixture used for producing the aqueous copolymer solution or aqueous dispersion (A) may further contain a monomer (e) represented by the following formula (III) if necessary.
0% by weight can be contained.

[0036]

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(Wherein R ³ represents a hydrogen atom or a methyl group;
X a is a hydrogen atom or a fluorine atom, n ³ is an integer of 1 to 8, n ⁴ represents respectively an integer of 1 to 30. ) In the monomer (e) represented by the above formula (III), R ³
Is a hydrogen atom or a methyl group, and X is a hydrogen atom or a fluorine atom. n ³ is an integer of 1 to 8, n ⁴ is 1 to 3
It is an integer of 0. When n ⁴ exceeds 30, poor mixing properties and copolymerizability with other monomers, also undesirable because the water-soluble or water-dispersible poor due to the lack of hydrophilicity.

Specific examples of the monomer (e) include, for example, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth)
Commercially available products such as acrylate, 2- (pentadecafluorooctyl) ethyl (meth) acrylate, and 2- (nonadecafluorodecyl) ethyl (meth) acrylate, such as “FAMAC” (manufactured by Nippon Mektron), “Viscoat 8FM”, Viscort 17FM "(all manufactured by Osaka Organic Chemical Industry Co., Ltd.).

The monomer mixture used for producing the aqueous copolymer solution or the aqueous dispersion (A) may further include a monomer (f) having a carbonyl group in view of water resistance and the like.
Can be contained as required in an amount of 1 to 30% by weight.

Examples of the monomer (f) having a carbonyl group include acrolein, diacetone acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formyl styrene, and vinyl alkyl ketone having 4 to 7 carbon atoms ( For example, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone) and the like. Of these, diacetone acrylamide and diacetone methacrylamide are particularly preferred.

Aqueous solution or aqueous dispersion of copolymer (A)
Is obtained by using a mixture of the above monomers (a) to (c) and, if necessary, monomers (d) to (f) and, after solution polymerization, solubilizing or dispersing in water using a neutralizing agent. And a method such as an emulsion polymerization method using a surfactant.

From the viewpoints of water repellency and water resistance of the resulting coating film, the method described in the following, that is, the above monomer mixture is subjected to radical polymerization in an organic solvent in the presence of a polymerization initiator to prepare a copolymer solution After it is obtained, water and a neutralizing agent are added thereto to make it water-soluble or water-dispersed.

As the organic solvent used in the radical polymerization, alcohols, cellosolves, carbitols, cellosolve acetates and the like can be used. In particular, alcohols having 1 to 8 carbon atoms are used in the organic solvent. It is desirable to contain 5% by weight or more, preferably 100% by weight or more. Examples of the radical polymerization initiator include azo-based polymerization initiators such as 2,2-azobisisobutyronitrile and 2,2-azobis (2,4-dimethylvaleronitrile), or lauryl peroxide, t-butyl per 2 -Peroxide initiators such as ethylhexanate and benzoyl peroxide can be used. The concentration of the radical polymerization initiator is preferably from 0.3 to 10 parts by weight based on 100 parts by weight of the monomer.

When the monomer (b) has a carboxyl group or a sulfonic acid group, it may be, for example, monomethylamine, dimethylamine, trimethylamine or monoethylamine when the monomer (b) has a carboxyl group or a sulfonic acid group. Amines such as, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, monobutylamine, dibutylamine, tributylamine, monoethanolamine, diethanolamine, triethanolamine, dimethylaminoethanol, diethylaminoethanol, etc .; Sodium, potassium hydroxide and the like can be used. When the monomer (b) has an amino group, for example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid and the like, formic acid, acetic acid, propionic acid and trimethyi Acetate, (meth) acrylic acid, and organic acids such as lactic acid can be used.

On the other hand, the above method uses water as a medium
The monomer mixture is dispersed and emulsified using an emulsifier, and a water-soluble polymerization initiator is added thereto, followed by heating at 50 to 90 ° C. for emulsion polymerization. When a redox initiator is used, the reaction can be performed at room temperature. Examples of the emulsifier include anionic surfactants such as higher alcohol sulfates and alkyl sulfonates, and various alkyl ethers and alkyl esters of polyoxyethylene.
A nonionic surfactant such as an alkyl allyl ether and a reactive surfactant having a polymerizable unsaturated group are used. As the polymerization initiator, for example, hydrogen peroxide, ammonium persulfate, cumene hydroperoxide, or a water-soluble redox initiator is used.

In the present invention, the aqueous copolymer solution or aqueous dispersion (A) produced as described above is used as a vehicle component,
Further, it contains a reaction product (B) of an epoxy-terminated siloxane polymer (g) and an acid compound (h). The reaction product (B) contributes to the improvement of the slipperiness.

Epoxy-terminated siloxane polymer (g)
Is represented by the following general formula (II)

[0048]

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Wherein R is an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, m is the average degree of polymerization of dimethylsiloxane units, and 6 to 3
00, preferably a number in the range of 6-100, and n is an integer of 0-6, preferably 1-5. The siloxane polymer (g) is generally 300 to 30,000,
Preferably it may have a number average molecular weight in the range of 500 to 20,000.

The acid compound (h) which can be reacted with the siloxane polymer (g) can be any known low molecular weight acid without particular limitation. Examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, and formic acid. And organic acids such as acetic acid, propionic acid, trimethylacetic acid, (meth) acrylic acid, lactic acid, and sulfonic acid compounds. Sulfuric acid and sulfonic acid compounds are suitable. The sulfonic acid compound has the following formula: R ¹⁰ —SO ₃ H (where R ¹⁰ is an organic residue, for example, an aliphatic hydrocarbon group,
Represents an aromatic hydrocarbon group or the like, the aliphatic hydrocarbon group,
The aromatic hydrocarbon group may be optionally substituted by a halogen atom or the like), specifically, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid,
Examples thereof include 2,4- or 2,5-dimethylbenzenesulfonic acid, naphthalene-α-sulfonic acid, and naphthalene-β-sulfonic acid. Of these, methanesulfonic acid is preferable.

The reaction product (B) was prepared by mixing the siloxane polymer (g) and the acid compound (h) with an equivalent ratio of epoxy group in (g) / acid group in (h) of 0.5 /. 1 to 10/1,
Preferably, it can be obtained by reacting at a ratio of 1/1 to 8/1. In the reaction product (B),
Unreacted epoxy group-containing siloxane polymer (g) may be present. The unreacted acid compound (h) may remain in the reaction product (B), but it is preferable that the unreacted acid compound (h) is not substantially contained. The reaction between the siloxane polymer (g) and the acid compound (h) can be carried out, for example, by subjecting the two to room temperature to 100 ° C. in the presence of an organic solvent, if necessary.
By mixing them. Of course, both may be mixed and heated. Examples of the organic solvent include toluene, xylene, cyclohexane, petroleum ether, gasoline, kerosene, naphtha, chloroform, carbon tetrachloride, ethylene dichloride, 2-ethylhexanol, diethyl ether, methyl ethyl ketone, methyl isobutyl ketone, Isopropyl alcohol, butano
, Dioxane, mineral oil and the like.

The reaction product (B) obtained as described above is
It can be used as it is or by adjusting the solid content concentration by diluting or partially removing the solvent with an organic solvent, and removing unreacted acid compounds.

In the present invention, the above reaction product (B) is used in an amount of 1 to 40 parts by weight, preferably 5 to 40 parts by weight, based on 100 parts by weight of the solids of the aqueous copolymer solution or aqueous dispersion (A). Contains 20 parts by weight. If the content is less than 1 part by weight, the expression of water slippage is insufficient, and if it exceeds 40 parts by weight, the strength and hardness of the obtained coating film become insufficient, which is not preferable.

In the aqueous coating composition of the present invention, when a carbonyl group is introduced into the aqueous copolymer solution or the aqueous dispersion (A), at least two carbonyl groups per molecule are used as a crosslinking agent.
It may contain hydrazine derivative having the number of -NH-NH ₂ containing group. Here, the -NH-NH ₂ containing group, hydrazide group, include semicarbazide group.

The hydrazine derivative includes, for example, a saturated aliphatic carboxylic acid dihydrazide having 2 to 18 carbon atoms such as oxalic acid dihydrazide, malonic acid dihydrazide, glutaric acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, and sebacic acid dihydrazide. Monoolefinically unsaturated dicarboxylic acid dihydrazide such as maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide; phthalic acid, terephthalic acid or isophthalic acid dihydrazide, and pyromellitic acid dihydrazide, trihydrazide or tetrahydrazide; nitrilotrihydrazide, citric acid Trihydrazide, 1,2,
Reaction of 4-benzenetrihydrazide, ethylenediaminetetraacetic acid tetrahydrazide, 1,4,5,8-naphthoic acid tetrahydrazide, and a low polymer having a lower alkyl ester group of carboxylic acid with hydrazine or hydrazine hydrate (hydrazine hydride) Polyhydrazide (see Japanese Patent Publication No. 52-22878); dihydrazide carbonate, bissemicarbazide; diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate, and polyisocyanate compounds derived therefrom. A polyfunctional semicarbazide obtained by excessively reacting an N, N-substituted hydrazine such as N, N-dimethylhydrazine or the above-mentioned dihydrazide, the polyisocyanate compound and a polyetherpolyol or polyethylene glycol.
Aqueous polyfunctional semicarbazide or an aqueous polyfunctional semicarbazide obtained by excessively reacting the above-mentioned dihydrazide with an isocyanate group in a reaction product with an active hydrogen compound containing a hydrophilic group such as a rumonoalkyl ether; Mixture with aqueous polyfunctional semicarbazide (JP-A-8-151358)
And JP-A-8-245878).

The hydrazine derivative is such that the amount of the —NH—NH ₂ group in the hydrazine derivative is 0.01 to ₂ mol per 1 mol of the carbonyl group contained in the aqueous copolymer solution or the aqueous dispersion (A); Preferably, it is blended so as to be 0.05 to 1.5 mol.

The coating composition of the present invention may further contain, if necessary, a pigment, a filler, an aggregate, a pigment dispersant, a wetting agent, a defoaming agent, a plasticizer, a film-forming aid, an organic solvent, and a preservative. , Fungicides,
A coating additive such as a pH adjuster, a rust preventive, a curing catalyst, and a crosslinking agent other than those described above can be appropriately selected and combined and blended.

The coating composition of the present invention thus obtained is
It can be applied to various substrate surfaces. As the substrate surface, for example, a metal (for example, an automobile outer panel, a vehicle, an aluminum fin,
Passage sign boards, microwave antennas, large water pipes, traffic lights, etc.), inorganic materials (for example, concrete,
Mortars, tiles, toilets, bathtubs, tiles, etc.), glass (eg, car windshields, windshields, windowpanes, mirrors, etc.), plastics (eg, films or sheets for greenhouse horticulture, toilets, washbasins) , Artificial organs, etc.), wood, paper (corrugated ball) or the like, or its painted surface.

The coating of the coating composition of the present invention on the surface of these substrates can be performed, for example, by spray coating, brush coating, or roller coating.
The coating can be carried out by a method known per se such as coating, dip coating, roll coating, curtain coating, and the like. In addition, the thickness of the applied coating film can be appropriately selected according to the application, but is usually 1 to 100 μm, preferably about 10 to 50 μm as a dry film thickness.

The drying of the coated surface is not particularly limited and can be carried out usually at a temperature of 0 to 300 ° C., preferably 0 to 100 ° C. With the composition of the present invention, it is possible to form a coating film that can sufficiently exhibit the intended performance even when dried at room temperature.

[0061]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. “Parts” and “%” mean “parts by weight” and “% by weight”, respectively.

Production Example 1 of Copolymer Aqueous Dispersion (A) 79 parts by weight of isopropyl alcohol were charged into a flask, and the temperature was raised while stirring to the reflux temperature (about 84 ° C.). Then, while keeping the temperature at the reflux temperature, the following monomer mixture was added dropwise for 4 hours.

Styrene 10 parts n-Butyl methacrylate 58 parts Acrylic acid 7 parts KBM-502 (Note 1) 15 parts Silaprene FM-0711 (Note 2) 10 parts Azobisisobutyronitrile 1 part Thereafter, the temperature is maintained at the reflux temperature. After aging for 2 hours, the mixture was cooled to room temperature to obtain a nearly colorless and transparent viscous copolymer solution having a nonvolatile content of 56%. Subsequently, the obtained copolymer solution was transferred to a diluting tank, 820 parts of deionized water and 9.8 parts of triethylamine were added, and the temperature was raised to 50 ° C.
After stirring for 2 hours while maintaining the temperature, the mixture was cooled to obtain a nearly colorless translucent aqueous dispersion (A-1) having a nonvolatile content of 10%.

(Note 1) KBM-502: an alkoxysilyl group-containing monomer manufactured by Shin-Etsu Chemical Co., Ltd. (Note 2) Silaprene FM-0711: manufactured by Chisso Corporation
Polydimethylsiloxane group-containing monomer, molecular weight of 1,000
0 Preparation Example 2 Preparation Example 1 was carried out in the same manner as in Preparation Example 1 except that the following monomer mixture was used as the monomer mixture to be dropped, and a pale milky white aqueous dispersion (A-
2) was obtained.

Styrene 10 parts n-Butyl methacrylate 65 parts Acrylic acid 7 parts 2-hydroxyethyl acrylate 8 parts Silaprene FM-0711 10 parts Azobisisobutyronitrile 1 part Production Example 3 Drops are added in Production Example 1. The same procedure as in Production Example 1 was carried out except that the following monomer mixture was used as the monomer mixture, and a light milky-white aqueous dispersion (A-
3) was obtained.

Styrene 10 parts n-Butyl methacrylate 48 parts Acrylic acid 7 parts KBM-503 (Note 3) 15 parts Silaprene FM-0711 10 parts FAMAC (Note 4) 10 parts Azobisisobutyronitrile 1 part (Note) 3) KBM-503: an alkoxysilyl group-containing monomer manufactured by Shin-Etsu Chemical Co., Ltd. (Note 4) FAMAC: Nippon Mektron, perfluoroalkyl methacrylate, fluorine concentration: 60.7% by weight Production Example 4 In Production Example 1, the same procedure as in Production Example 1 was carried out except that the following monomer mixture was used as the monomer mixture to be added dropwise, and after dispersion in water, 5.2 parts of adipic dihydrazide was added to the dispersion to give a 10% non-volatile content. Light Milky White Aqueous Dispersion (A-4)
I got

Styrene 10 parts n-Butyl methacrylate 48 parts Diacetone acrylamide 10 parts Acrylic acid 7 parts KBM-502 15 parts Silaprene FM-0711 10 parts Azobisisobutyronitrile 1 part Production Example 5 Isopropyl alcohol in a flask 79 parts by weight were charged, and the temperature was raised while stirring to the reflux temperature (about 84 ° C.). Then, while keeping the temperature at the reflux temperature, the following monomer mixture was added dropwise for 4 hours.

Styrene 10 parts N-butyl methacrylate 58 parts Acrylic acid 7 parts KBM-502 15 parts Silaplane FM-0711 10 parts Azobisisobutyronitrile 1 part After aging for 2 hours while maintaining the reflux temperature, room temperature The mixture was cooled to obtain a nearly colorless and transparent viscous copolymer solution having a nonvolatile content of 56%. This was then transferred to a dilution tank, to which 899 parts of deionized water and then 9.8 parts of triethylamine were added to add 5 parts.
After the temperature was raised to 0 ° C. and the mixture was stirred for 2 hours, the temperature was further raised to 83 ° C., and while maintaining the same temperature, the solvent was removed by a vacuum pump, followed by cooling. (A-5) was obtained.

Production Example 6 The same procedure as in Production Example 1 was carried out except that the following monomer mixture was used as the monomer mixture to be dropped, and a pale milky white aqueous dispersion having a nonvolatile content of 10% ( A-
6) was obtained.

Styrene 10 parts n-butyl methacrylate 48 parts methyl methacrylate 20 parts acrylic acid 7 parts vinyltrimethoxysilane 15 parts azobisisobutyronitrile 1 part Production Example 7 28.5 parts of deionized water in a flask "Newcol
707SF "(Nippon Emulsifier Co., Ltd., anionic surfactant having a polyoxyethylene chain, nonvolatile content 30%)
One part was charged, and the temperature was raised to 85 ° C. after replacement with nitrogen. To this, 3% of the pre-emulsion obtained by emulsifying the following composition and 25% of 10.5 parts of a solution in which 0.5 parts of ammonium persulfate was dissolved in 10 parts of deionized water were added, and added. After minutes, the remaining pre-emulsion and the remaining aqueous solution of ammonium persulfate were added dropwise over 4 hours.

Deionized water 55.8 parts N-butyl methacrylate 94.3 parts Diacetone acrylamide 3 parts 2-hydroxyethyl acrylate 2.5 parts Acrylic acid 0.2 parts Newcol 707SF 6.6 parts After keeping this at 85 ° C. for another 2 hours,
The temperature was lowered to 40-60 ° C. Then, pH 8 with ammonia water
To 9, and 1.6 parts of adipic dihydrazide were mixed to obtain a copolymer aqueous dispersion (A-7) having a nonvolatile content of 50%.

Preparation of Reaction Product (B) Preparation Example 1 192 parts of isopropyl alcohol was added to a flask,
Among them, 120 parts of "Silaprene FM-0511" (manufactured by Chisso Corporation, polydimethylsiloxane having an epoxy group at one end, R in the formula (II) is a methyl group, molecular weight 1,000) and 7.7 parts of methanesulfonic acid Were mixed at room temperature and stirred. Since the liquid temperature in the flask rose to about 70 ° C,
The mixture was stirred until the temperature dropped to 20 ° C. to obtain a reaction product (B-1) having a nonvolatile content of 40%.

Preparation Example 2 In Preparation Example 1, one-terminal epoxy group-containing polydimethylsiloxane in which R is an n-butyl group is substituted for the one-terminal epoxy group-containing polydimethylsiloxane in which R is a methyl group (molecular weight: 1,000). Was used in the same manner as in Preparation Example 1 except that the reaction product (B-2) having a nonvolatile content of 40% was obtained.

Preparation Example 3 192 parts of isopropyl alcohol was added to a flask,
120 parts of “Silaplane FM-0511” and 3 parts of concentrated sulfuric acid were mixed therein at room temperature and stirred. Since the temperature of the liquid in the flask rose to about 60 ° C., the mixture was stirred until the temperature dropped to 20 ° C., and the reaction product (B-
3) was obtained.

Preparation of Water-based Paints Examples 1 to 9 and Comparative Examples 1 to 3 The components (A) and (B) obtained in the above Preparation Examples and Preparation Examples were blended in the composition shown in Table 1, and mixed and stirred. Thus, each water-based paint was obtained. Each obtained water-based paint was applied to a glass plate at 100 μm
Each was coated with an applicator having a gap of 2 mm and dried at 20 ° C. for 1 day to obtain each test coated plate, which was then subjected to the following performance tests. Table 2 shows the results.

(Performance Test) (* 1) Appearance of coating film: The appearance of the coating film of each test coated plate was visually evaluated.

◎: No repelling and no smudge, good gloss. ○: No repelling, but somewhat glossy. ×: Repelling, not evenly formed. (* 2) Water repellency: each Water droplets of 0.03 cc of deionized water were formed on the test coated plate, and the contact angles of the water droplets were measured using a contact angle meter DCCA type manufactured by Kyowa Chemical Industry Co., Ltd. The larger the contact angle, the better the water repellency.

(* 3) Water slip: 0.0% on each test coated plate
A drop of 3 cc of deionized water was formed, the plate was slowly tilted, the angle at which the drop began to slide was measured, and the angle was defined as the sliding angle. The smaller the sliding angle, the better the water sliding.

(* 4) Persistence: Tap water was allowed to flow on each test coated plate for 30 minutes, followed by drying for one day.
The test of (* 3) was performed, and the contact angle and the sliding angle were measured, respectively. The smaller the difference from the initial value, the better the durability.

[0080]

According to the present invention, the water-repellent group introduced by the monomer (a) in the aqueous copolymer solution or the aqueous dispersion (A) not only imparts water repellency, but also provides smoothness. The compatibility with the reaction product (B), which is an aqueous component, is increased, the monomer (b) is given water solubility / water dispersibility, and when an alkoxysilyl group is introduced, it is hydrolyzed. Water solubility or water dispersibility can be significantly improved. In addition, the reaction product (B) hardly wets the water,
In addition, it is possible to provide a water-sliding property in which the attached water droplet easily slides down only by slightly tilting the coating film surface from the horizontal surface. As shown in the examples, even if the water contact angle is not so large as about 65 to 85 °, the water droplet having a mass of 30 mg attached to the coating film moves the coating film surface from the horizontal plane by 3 degrees as shown in the examples.
Just by tilting at an angle within 0 °, it starts to slide under its own weight.

Accordingly, the coating composition of the present invention is capable of forming a coating film having excellent slipperiness and water repellency, and is particularly useful as an aqueous coating composition for drying at room temperature.

[0082]

[Table 1]

[0083]

[Table 2]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 183/07 C09D 183/07 C09K 3/18 104 C09K 3/18 104 (72) Inventor Naoki Miyata Kanagawa 4-17-1, Higashi-Yawata, Hiratsuka-shi Kansai Paint Co., Ltd. F-term (reference) 4H020 BA33 4J027 AC03 AC04 AC06 AF05 AJ01 AJ02 AJ08 BA02 BA03 BA04 BA05 BA06 BA07 BA08 BA10 BA12 BA13 BA14 CA10 CA25 CB03 CB05 CB09 CD08 4J038 CC031 CC031 CC081 CC101 CE051 CF011 CF021 CG141 CG161 CH031 CH041 CH121 CH131 CH141 CJ181 CL001 DL052 GA06 GA09 GA13 GA15 JB17 JC13 KA03 MA08 MA14 NA07 PB05 PC02 PC03 PC04 PC10 4J100 AB02Q AB03Q AB04Q AB08Q08 AE02 AG08A08 A08Q08 A08Q08 A08Q08 AL09Q AM02Q BA05Q BA16R BA29R BA56R BA76P BC04Q BC43P BC43Q CA05 JA01

Claims (9)

[Claims] (A) (a) 3 to 70% by weight of a monomer represented by the following formula (I): (Wherein, R ¹ is a hydrogen atom or a methyl group, R ² is the same or different and is a phenyl group or an alkyl group having 1 to 6 carbon atoms, n ¹ is an integer of ¹ to 10, and n ² is 5 to ²⁰⁰ (B) 1 to 25% by weight of an α, β-ethylenically unsaturated monomer having one kind of functional group selected from the group consisting of a carboxyl group, a sulfonic acid group and an amino group, and (C) 5 to 9 other copolymerizable α, β-ethylenically unsaturated monomers
(B) (g) a copolymer aqueous solution or aqueous dispersion obtained by copolymerizing a monomer mixture containing 6% by weight, and (B) a compound represented by the following formula (II): (Wherein, R represents an alkyl group having 1 to 6 carbon atoms, the average number of m is 6 to 150, and n is an integer of 0 to 6). A coating composition comprising a reaction product with an acid compound. 2. An aqueous solution or aqueous dispersion of a copolymer (A).
The coating composition according to claim 1, wherein the monomer mixture used in the production of (i) contains 1 to 40% by weight of a monomer (d) having an alkoxysilyl group. 3. A copolymer aqueous solution or aqueous dispersion (A)
The monomer mixture used for the production of the compound represented by the following structural formula (II)
The coating composition according to claim 1, comprising 1 to 30% by weight of the monomer (e) represented by I). Embedded image (Wherein, R ³ is a hydrogen atom or a methyl group, X is a hydrogen atom or a fluorine atom, n ³ is an integer of 1 to 8, n ⁴ is 1 to
An integer of 30 is shown. ) 4. A copolymer aqueous solution or aqueous dispersion (A)
The coating composition according to any one of claims 1 to 3, wherein the monomer mixture used in the production of (i) contains 1 to 30% by weight of a monomer (f) having a carbonyl group. 5. An aqueous solution or aqueous dispersion of a copolymer (A).
Has at least two -NH- in one molecule as a crosslinking agent.
4. The coating composition according containing the hydrazine derivative having the NH ₂ containing group. 6. An epoxy-terminated siloxane polymer (g).
Has a number average molecular weight of 300 to 30,000. The coating composition according to any one of claims 1 to 5, wherein 7. The coating composition according to claim 1, wherein the acid compound (h) is a sulfuric acid or sulfonic acid compound. 8. The coating composition according to claim 7, wherein the acid compound (h) is methanesulfonic acid. 9. The composition according to claim 1, wherein the content of the reaction product (B) is 1 to 40 parts by weight in terms of solids with respect to 100 parts by weight of solids in the aqueous copolymer solution or aqueous dispersion (A). 8
The coating composition according to any one of the above.