JPH10265712A - Aqueous resin composition and water-based coating agent using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition, capable of retaining water and solvent resistances and excellent in weatherability and adhesion by using a polymerizable unsaturated monomer having ultraviolet absorptivity. SOLUTION: This composition is obtained by dissolving or dispersing a copolymer prepared by copolymerizing (A) a polymerizable unsaturated monomer, represented by formula I (R<1> to R<3> are each a halogen, an alkoxy or hydroxy) and having a hydrolyzable silyl group (e.g. vinyltrichlorosilane) with (B) a polymerizable unsaturated monomer having ultraviolet absorptivity [preferably the monomer represented by formula II (X<1> is a 1-8C hydrocarbon; R<14> is a 1-8C hydrocarbon; R<15> is a 1-6C alkylene; R<16> is methyl) and formula III (Y is O; R<17> is a 1-8C hydrocarbon) and (C) a polymerizable unsaturated monomer other than the components A and B (e.g. an acrylic or a methacrylic monomer) in water. The amounts of the components A and B contained in the whole polymerizable unsaturated monomers are 0.5-50 wt.% component A and 0.1-10 wt.% component B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to undercoating of various materials such as wood materials, plastics, papers, and metals.
The present invention relates to an aqueous resin composition used for an aqueous coating agent applied to an overcoat, a clear coat, a lining, and the like, and an aqueous coating agent using the same.

[0002]

2. Description of the Related Art In recent years, in the field of coating agents, the transition from organic solvent-based coating agents to water-based coating agents has been rapidly progressing from the viewpoint of consideration for environmental problems and the like. Initially, the water-based coating agent had no crosslinkable functional group unlike the organic solvent-based coating agent, so the water resistance, solvent resistance, adhesion and weather resistance of the coating film were inferior to the organic solvent-based coating agent. Had disadvantages. Therefore, as a water-based coating agent having a crosslinkable functional group, a water-based coating agent using a resin composition obtained by emulsifying a resin having an alkoxysilyl group, which is a kind of hydrolyzable silyl group, has been proposed (for example, Japanese Unexamined Patent Publication No. Hei. 2161
No. 0). The use of this water-based resin composition has made it possible to obtain a water-based coating agent having improved water resistance and solvent resistance, but the adhesion and weather resistance have not been sufficient.

A method for improving the weather resistance of a water-based coating agent by blending additives such as a hindered amine type light stabilizer and a benzotriazole type ultraviolet absorber into a resin composition obtained by emulsifying a resin having an alkoxysilyl group is also known. However, simply blending these light stabilizers and ultraviolet absorbers physically causes a problem that the light stabilizers and ultraviolet absorbers may bleed out after the formation of the coating film. If the light stabilizer or the UV absorber causes bleed-out, not only the expected weather resistance cannot be obtained due to the disappearance thereof, but also the bleed-out substance may cause the interlayer between the coating film and the coating material to be coated with the material to be coated. It may intervene between them and hinder the adhesion of the coating film. In addition, when the light stabilizer or the ultraviolet absorber bleeds out, minute void defects are generated in the coating film to the extent that the light stabilizers and the ultraviolet absorbers disappear, and water and an organic solvent enter from the void defects to improve the water resistance of the coating film and the like. The solvent resistance is reduced.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and has been made in view of the excellent water resistance and solvent resistance of an aqueous coating agent containing a resin having a hydrolyzable silyl group such as an alkoxysilyl group. An object of the present invention is to improve the weather resistance and adhesion while maintaining the properties.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above-mentioned object, and have found that a water-based resin composition having a hydrolyzable silyl group is simply physically contained in a water-based resin composition. By using a polymerizable unsaturated monomer having an ultraviolet absorbing ability as a polymerization component of the resin, it is possible to improve weather resistance and adhesion while maintaining water resistance and solvent resistance. Find out what you can do,
The present invention has been completed.

That is, the present invention provides (a) a polymerizable unsaturated monomer having a hydrolyzable silyl group, (b) a polymerizable unsaturated monomer having an ultraviolet absorbing ability, and (c) the above (a) and An aqueous resin composition obtained by dissolving or dispersing a copolymer obtained by copolymerizing a polymerizable unsaturated monomer other than (b) in water ((Claim 1). A water-based coating agent using the water-based resin composition (claim 7).

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The features of the present invention will be described below in detail.

First, a first feature of the present invention resides in that a polymerizable unsaturated monomer having a hydrolyzable silyl group is used as one of the polymerizable components of the resin. Thereby, the hydrolyzable silyl group acts as a crosslinkable functional group at the time of forming the coating film, and it is possible to improve the water resistance and the solvent resistance of the coating film.

The polymerizable unsaturated monomer having a hydrolyzable silyl group includes, for example, a polymerizable unsaturated monomer having a silyl group represented by the following general formula (3).

[0010]

Embedded image

(Wherein R ¹ , R ² and R ³ are the same or different and are each a halogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an acyloxy group, a hydroxyl group, an amino group, an amino group Represents an oxy group or an alkylthio group, provided that at least one of R ^{1 to} R ³ is
One is a halogen atom, an alkoxy group or a hydroxyl group. The hydrolyzable silyl group usually has at least one of R ^{1 to} R ³ having a halogen atom, an alkoxy group and a hydroxyl group.

The halogen atom of the silyl group represented by the formula (3) includes, for example, fluorine, chlorine, bromine, iodine and the like, and is usually a chlorine atom.

The alkyl group includes, for example, C, methyl, ethyl, propyl, butyl, pentyl, hexyl and the like.
_It includes a _1-10 alkyl group and the like. The aryl group includes, for example, a C _6-10 aryl group such as a phenyl group, and the like,
The aralkyl group includes, for example, a C _7-10 aralkyl group such as a benzyl group.

Examples of the alkoxy group include C _1-16 alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, pentyloxy, hexyloxy, octyloxy, decyloxy, dodecyloxy and the like. Is included. Preferred alkoxy groups are C _1-4 alkoxy groups, especially methoxy groups and ethoxy groups. The alkoxy group also includes, for example, an alkoxy-alkoxy group such as a methoxyethoxy group.

The aryloxy group includes, for example, a C _6-10 aryloxy group such as a phenoxy group. Acyloxy groups include, for example, C _2-6 acyloxy groups such as acetyloxy, propionyloxy and butyryloxy groups.

The amino group includes, for example, an amino group which may have a substituent such as a dimethylamino group. The aminooxy group has a substituent such as a dimethylaminooxy group. And an optionally substituted aminooxy group. The alkylthio group includes, for example, a C _1-6 alkylthio group such as a methylthio and ethylthio group.

As the polymerizable unsaturated monomer having a hydrolyzable silyl group, for example, the following general formulas (4) to (15)
The compound represented by is included.

[0018]

Embedded image

(Wherein R ⁴ is a C _1-10 alkyl group, C _6-10
An aryl group or a C _7-10 aralkyl group is shown, and R ⁵ is a hydrogen atom or a methyl group. X represents a fluorine, chlorine, bromine or iodine atom. a shows the integer of 0-2. Examples of such compounds include vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinylmethylphenylchlorosilane, isopropenyltrichlorosilane, isopropenylmethyldichlorosilane, isopropenyldimethylchlorosilane, and isopropenylmethylphenylchlorosilane. Is mentioned.

[0020]

Embedded image

(Wherein R ⁴ is a C _1-10 alkyl group, C _6-10
An aryl group or a C _7-10 aralkyl group is shown, and R ⁵ is a hydrogen atom or a methyl group. X represents a fluorine, chlorine, bromine or iodine atom. a represents an integer of 0 to 2;
Indicates an integer of 12. Examples of such compounds include allyltrichlorosilane, allylmethyldichlorosilane, allyldimethylchlorosilane and the like.

[0022]

Embedded image

(Wherein R ⁴ is a C _1-10 alkyl group, C _6-10
An aryl group or a C _7-10 aralkyl group is shown, and R ⁵ is a hydrogen atom or a methyl group. X represents a fluorine, chlorine, bromine or iodine atom. a represents an integer of 0 to 2;
Indicates an integer of 12. Examples of such a compound include 2- (meth) acryloxyethyltrichlorosilane, 2- (meth) acryloxypropyltrichlorosilane, 2- (meth) acryloxyethylmethyldichlorosilane, and 3- (meth) acrylic. Roxypropylmethyldichlorosilane, 2- (meth)
Acryloxyethyl dimethylchlorosilane, 3- (meth) acryloxypropyldimethylchlorosilane and the like can be mentioned.

[0024]

Embedded image

(Wherein R ⁴ is a C _1-10 alkyl group, C _6-10
An aryl group or a C _7-10 aralkyl group, R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents a C _1-16 alkoxy group. a shows the integer of 0-2. Examples of such a compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinyltri (hexyloxy) silane, vinyltri (octyloxy) silane, vinyltri (decyloxy) silane, and vinyltri (dodecyloxy) Silane, vinyldimethoxymethylsilane, vinyldiethoxymethylsilane, vinylmethoxydimethylsilane, vinylethoxydimethylsilane, vinylbutoxydimethylsilane, vinyldiphenylethoxysilane, isopropenyltrimethoxysilane, isopropenyltriethoxysilane, isopropenyltributoxysilane , Isopropenyltri (hexyloxy) silane, isopropenyltri (octyloxy) silane, isopropenyltri (decyloxy) sila Isopropenyl tri (dodecyloxy) silane, isopropenyl dimethoxymethyl silane,
Isopropenyldiethoxymethylsilane, isopropenylmethoxydimethylsilane, isopropenylethoxydimethylsilane, isopropenylbutoxydimethylsilane, vinyltris (2-methoxyethoxy) silane, and the like.

[0026]

Embedded image

(Wherein R ⁴ is a C _1-10 alkyl group, C _6-10
An aryl group or a C _7-10 aralkyl group, R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents a C _1-16 alkoxy group, R ⁷ represents a C _1-12 alkylene group or a phenylene group. a shows the integer of 0-2. Examples of such compounds include allyltrimethoxysilane, vinyldecyltrimethoxysilane, vinyloctyltrimethoxysilane, vinylphenyltrimethoxysilane, vinylphenyldimethoxymethylsilane, vinylphenylmethoxydimethylsilane, and isopropenylphenyltrimethoxy. Examples thereof include silane, isopropenylphenyldimethoxymethylsilane, and isopropenylphenylmethoxydimethylsilane.

[0028]

Embedded image

(Wherein R ⁴ is a C _1-10 alkyl group, C _6-10
An aryl group or a C _7-10 aralkyl group, R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents a C _1-16 alkoxy group. a represents an integer of 0 to 2; n represents an integer of 1 to 12; Examples of such a compound include 2- (meth) acryloxyethyltrimethoxysilane, 2- (meth) acryloxyethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, and 3- (meth) ) Acryloxypropyltriethoxysilane, 3- (meth)
Acryloxypropylmethyldimethoxysilane, 3-
(Meth) acryloxypropyldiethoxymethylsilane, 3- (meth) acryloxypropyltris (2-methoxyethoxy) silane, and the like.

[0030]

Embedded image

(Wherein R ⁴ is a C _1-10 alkyl group, C _6-10
An aryl group or a C _7-10 aralkyl group, R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents a C _1-16 alkoxy group. a represents an integer of 0 to 2; n represents an integer of 1 to 12; Examples of such compounds include 3- (allyloxycarbonyl-o-phenylene-carboxy) propyltrimethoxysilane, 3- (allyloxycarbonyl-
o-phenylene-carboxy) propyldimethoxymethylsilane, 3- (allyloxycarbonyl-o-phenylene-carboxy) propylmethoxydimethylsilane,
3- (isopropenylmethyleneoxycarbonyl-o-
Phenylene-carboxy) propyltrimethoxysilane, 3- (isopropenylmethyleneoxycarbonyl-
o-phenylene-carboxy) propyldimethoxymethylsilane, 3- (isopropenylmethyleneoxycarbonyl-o-phenylene-carboxy) propylmethoxydimethylsilane, and the like.

[0032]

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Such compounds include, for example, 3-
(Vinylphenylamino) propyltrimethoxysilane, 3- (vinylphenylamino) propyltriethoxysilane, 3- (vinylbenzylamino) propyltrimethoxysilane, 3- (vinylbenzylamino) propyltriethoxysilane and the like are exemplified. .

[0034]

Embedded image

(Wherein R ⁴ is a C _1-10 alkyl group, C _6-10
An aryl group or a C _7-10 aralkyl group, R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents a C _1-16 alkoxy group. a shows the integer of 0-2. Examples of such a compound include 3- [vinylphenylenemethylene (ethylenediamino)] propyltrimethoxysilane, 3- [isopropenylphenylenemethylene (ethylenediamino)] propyltrimethoxysilane, and the like.

[0036]

Embedded image

(Wherein R ⁴ is a C _1-10 alkyl group, C _6-10
An aryl group or a C _7-10 aralkyl group, R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents a C _1-16 alkoxy group. a represents an integer of 0 to 2; n represents an integer of 1 to 12; Examples of such compounds include 2- (vinyloxy) ethyltrimethoxysilane and 3- (vinyloxy)
Examples thereof include propyltrimethoxysilane, 4- (vinyloxy) butyltriethoxysilane, and 2- (isopropenyloxy) ethyltrimethoxysilane.

[0038]

Embedded image

(Wherein R ⁴ is a C _1-10 alkyl group, C _6-10
An aryl group or a C _7-10 aralkyl group, R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents a C _1-16 alkoxy group, R ⁹ is -CH ₂ O-or -CH ₂ OCO- Show.
a represents an integer of 0 to 2; n represents an integer of 1 to 12; Examples of such compounds include 3- (allyloxy) propyltrimethoxysilane, 10- (allyloxycarbonyl) decyltrimethoxysilane, 3- (isopropenylmethyleneoxy) propyltrimethoxysilane, and 10- (isopropenyl). Methyleneoxycarbonyl) decyltrimethoxysilane.

[0040]

Embedded image

(Wherein R ⁴ is a C _1-10 alkyl group, C _6-10
An aryl group or a C _7-10 aralkyl group, R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents a C _1-16 alkoxy group. a represents an integer of 0 to 2, n represents an integer of 1 to 12, and m represents an integer of 1 to 12. Examples of such a compound include 3-[(meth) acryloxyethyleneoxy] propyltrimethoxysilane, 3-[(meth) acryloxyethyleneoxy] propyldimethoxymethylsilane, and the like.

The polymerizable unsaturated monomer having a hydrolyzable silyl group is, for example, divinyldimethoxysilane,
Divinyl group-containing compounds such as divinyldiethoxysilane and divinyldi (β-methoxyethoxy) silane may be used. The polymerizable unsaturated monomers having a hydrolyzable silyl group can be used alone or in combination of two or more. Preferred silyl group-containing monomers include, for example, ease of handling, economy and suppression of side reactions, for example,
A vinyl monomer containing an alkoxysilyl group is exemplified.

A second feature of the present invention resides in that a polymerizable unsaturated monomer having an ultraviolet absorbing ability is used as one of the polymerization components of the resin. By using the polymerizable unsaturated monomer having the ultraviolet absorbing ability as described above, it becomes possible to improve the ultraviolet absorbing ability of the coating film and to enhance the weather resistance.
Moreover, since the polymerizable unsaturated monomer having an ultraviolet absorbing ability is one of the polymerization components constituting the resin, a light stabilizer or an ultraviolet absorber as a physical additive is simply blended into the resin composition. As in the case, the light stabilizer and the ultraviolet absorber do not bleed out. Therefore, weather resistance can be maintained for a long time, and water and solvent do not enter due to void defects due to bleed-out, so that water resistance and solvent resistance are not impaired. Furthermore, since the bleed-out substance does not intervene between layers of the coating film or between the coating film and the material to be coated, thereby preventing the adhesion of the coating film, the adhesion of the coating film can be improved. .

Examples of the polymerizable unsaturated monomer having an ultraviolet absorbing ability include a polymerizable unsaturated monomer represented by the following general formula (1):

[0045]

Embedded image

Wherein X ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group, and R14 represents a hydrogen atom or 1 carbon atom. To 8 represent a hydrocarbon group, R15 represents a linear or branched alkylene group having 1 to 6 carbon atoms,
R16 represents a hydrogen atom or a methyl group. ) And a polymerizable unsaturated monomer represented by the following general formula (2)

[0047]

Embedded image

(Where Y is an oxygen atom, —OCH ₂ CH ₂ O—
Or -OCH ₂ CH (CH ₃₎ O- are shown, R16 is a hydrogen atom or a methyl group, R17 is a hydrogen atom, a hydrogen group,
And a hydrocarbon group having 1 to 8 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. 1) selected from the group consisting of
Species or two or more types of polymerizable unsaturated monomers are exemplified.

Examples of the polymerizable unsaturated monomer represented by the general formula (1) include 2- [2′-hydroxy-5 ′
-(Methacryloyloxyethyl) phenyl] benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] benzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxypropyl) phenyl] Benzotriazole, 2-
[2′-hydroxy-5 ′-(methacryloyloxyhexyl) phenyl] benzotriazole, 2-[[2 ′
-Hydroxy-3'-t-butyl-5 '-(methacryloyloxyethyl) phenyl] benzotriazole, 2
-[2'-hydroxy-5'-t-butyl-3 '-(methacryloyloxyethyl) phenyl] benzotriazole, 2-[[2'-hydroxy-5'-(methacryloyloxyethyl) phenyl] -5-chloro Benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-methoxybenzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxyethyl) phenyl] -5-cyano Benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-t-butylbenzotriazole, 2- [2'-hydroxy-5'
-(Methacryloyloxyethyl) phenyl] -5-nitrobenzotriazole and the like.

The polymerizable unsaturated monomer represented by the general formula (2) includes, for example, 2-hydroxy-4-methacryloxybenzophenone, 2-hydroxy-4-
Acryloxybenzophenone, 2-hydroxy-4-
(2-methacryloyloxy) ethoxybenzophenone, 2-hydroxy-4- (2-methyl-2-methacryloyloxy) ethoxybenzophenone, 2,2′-dihydroxy-4- (2-methacryloyloxy) ethoxybenzophenone, 2-hydroxy- 4- (2-methacryloyloxy) ethoxy-4'-methoxybenzophenone, 4'-t-butyl-2-hydroxy-4- (2-
(Methacryloyloxy) ethoxybenzophenone and the like.

Among the polymerizable unsaturated monomers represented by the general formulas (1) and (2), the polymerizable unsaturated monomer represented by the general formula (1) is particularly useful in improving weather resistance. Is preferred. Therefore, it is preferable to include at least the polymerizable unsaturated monomer represented by the general formula (1) as a copolymer component of the aqueous resin composition of the present invention.

The water-based resin composition for a coating agent of the present invention comprises, in addition to the above-mentioned polymerizable unsaturated monomer having a hydrolyzable silyl group and the polymerizable unsaturated monomer having an ultraviolet absorbing ability, other polymerizable monomers. The unsaturated unsaturated monomer (hereinafter also referred to as a third polymerizable unsaturated monomer) is copolymerized. The type of the third polymerizable unsaturated monomer to be copolymerized is appropriately selected from various known polymerizable unsaturated monomers according to the application to which the resin composition is applied.

Examples of such a third polymerizable unsaturated monomer include (meth) acrylic monomers, aromatic vinyls, unsaturated carboxylic acids, vinyl esters, halogen-containing vinyls, and vinyl ethers. (Eg, vinyl ethyl ether, etc.), vinyl ketones (eg, methyl vinyl ketone, etc.), vinyl heterocyclic compounds (eg, N-vinyl compounds such as N-vinyl pyrrolidone, N-vinyl imidazole, vinyl pyridine, etc.), olefins Examples include monomers (eg, ethylene, propylene, etc.), allyl compounds (eg, allyl esters such as allyl acetate, etc.). The third polymerizable unsaturated monomer can be used alone or in combination of two or more.

The (meth) acrylic monomer of the third polymerizable unsaturated monomer includes, for example, (meth) acrylate,
(Meth) acrylamides, (meth) acrylonitrile and the like are included.

The (meth) acrylate includes, for example, alkyl (meth) acrylate [for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, Isobutyl (meth) acrylate, t-butyl (meth) acrylate,
Hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
C _1-18 alkyl (meth) acrylates such as lauryl (meth) acrylate, etc.], cycloalkyl (meth)
Acrylates [eg, cyclohexyl (meth) acrylate etc.], aryl (meth) acrylates [eg [phenyl (meth) acrylate etc.], aralkyl (meth) acrylates [eg benzyl (meth) acrylate etc.], hydroxyalkyl (meth) Acrylates [eg, hydroxy-C such as 2-hydroxyethyl, 2-hydroxypropyl ((meth) acrylate);
_2-4 alkyl (meth) acrylate, etc.], glycidyl (meth) acrylate, dialkylamino-alkyl (meth) acrylate [for example, 2- (dimethylamino) ethyl (meth) acrylate, 2- (diethylamino) ethyl (meth) acrylate Di C _1-4 alkylamino-C _2-4 alkyl (meth) acrylate, etc.]
And so on.

(Meth) acrylamides include, for example,
(Meth) acrylamide, hydroxyalkyl (meth)
Acrylamide [for example, N-hydroxy-C _1-4 alkyl (meth) acrylamide such as N-methylol (meth) acrylamide], alkoxyalkyl (meth) acrylamide [for example N-methoxymethyl (meth) acrylamide or other N- C _1-4 alkoxy-C _1-4
Alkyl (meth) acrylamide, etc.], diacetone (meth) acrylamide, etc.

Preferred (meth) acrylic monomers include, for example, (meth) acrylates [eg, C _1-18 alkyl (meth) acrylate, hydroxy-C _2-4 alkyl (meth) acrylate, glycidyl (meth) acrylate Acrylate, di C _1-4 alkylamino-C _2-4 alkyl (meth) acrylate, etc.], and (meth) acrylamides.

Further preferred (meth) acrylic monomers include C _2-10 alkyl acrylate, C _1-6 alkyl methacrylate, hydroxy-C _2-3 alkyl (meth) acrylate, glycidyl (meth) acrylate,
Di C _1-3 alkylamino-C _2-3 alkyl (meth) acrylate and the like.

The unsaturated carboxylic acids include, for example, unsaturated monocarboxylic acids [eg, ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid] and unsaturated polycarboxylic acids [eg, maleic acid]. Acid, fumaric acid,
Ethylenically unsaturated polycarboxylic acids such as itaconic acid and its anhydrides (such as maleic anhydride) or esters (for example, monoalkyl esters of divalent carboxylic acids such as monomethyl maleate and monobutyl maleate)] And so on. Preferred unsaturated carboxylic acids include, for example, monocarboxylic acids such as (meth) acrylic acid, polycarboxylic acids such as maleic acid, and acid anhydrides or esters thereof.

The aromatic vinyls include, for example, styrene,
α-methylstyrene, vinyltoluene and the like are included, and styrene is often used.

The vinyl esters include, for example, vinyl acetate, vinyl propionate, vinyl versatate (Ve
oVa). Halogen-containing vinyls include, for example, vinyl chloride, vinylidene chloride, and the like.

Further, as other polymerizable unsaturated monomers, compounds having a silyl group represented by the following general formulas (16) to (18) may be used.

[0063]

Embedded image

(Wherein R ⁴ is a C _1-10 alkyl group, C _6-10
An aryl group or a C _7-10 aralkyl group, R ⁵ represents a hydrogen atom or a methyl group, R ¹⁰ and R ¹¹ are the same or different and a C _1-10 alkyl group. a shows the integer of 0-2. Examples of such a compound include vinyl bis (dimethylamino) methylsilane.

[0065]

Embedded image

(Wherein R ⁴ is a C _1-10 alkyl group, C _6-10
An aryl group or a C _7-10 aralkyl group is shown, R ⁵ is a hydrogen atom or a methyl group, and R ¹² is a C _2-6 acyl group. a shows the integer of 0-2. Examples of such compounds include vinyl tri (acetyloxy) silane, vinyl di (acetyloxy) methyl silane, and the like.

[0067]

Embedded image

(Wherein R ⁴ is a C _1-10 alkyl group, C _6-10
An aryl group or a C _7-10 aralkyl group, R ⁵ represents a hydrogen atom or a methyl group, R ¹³ represents a C _6-10 aryloxy group. a shows the integer of 0-2. As such a compound, for example, vinyltriphenoxysilane and the like can be mentioned.

As such a third polymerizable unsaturated monomer, a hard monomer [for example, a glass transition temperature of 80 to 120 such as methyl (meth) acrylate, styrene or the like] is usually used.
° C. (in particular 90 to 105 ° C.) and the monomer component] to form a degree of homopolymer, soft monomer [e.g., glass transition temperature -85, such as acrylic acid C _2-10 alkyl ester
Monomer component that forms a homopolymer at about 10 ° C. (particularly −85 ° C. to −20 ° C.)]. On the other hand, when a monomer component having an ionic functional group such as a carboxyl group or an amino group [for example, dialkylamino-alkyl (meth) acrylate or the like] is used as the third polymerizable unsaturated monomer, an emulsifier is used. An aqueous resin composition can be obtained without using it.

When a hard monomer, a soft monomer and an ionic group-containing monomer are used as the third polymerizable unsaturated monomer as described above, the mixing ratio is not particularly limited. % By weight (e.g. 15-85% by weight, preferably 20-80% by weight, more preferably 25-75% by weight, especially 30-7% by weight)
0% by weight), 10 to 90% by weight of a soft monomer (for example, 15 to 85% by weight, preferably 20 to 80% by weight,
More preferably 25 to 75% by weight, especially 30 to 70% by weight, and 0 to 80% by weight of the ionic group-containing monomer (for example, 0 to 70% by weight, preferably 0 to 60% by weight, more preferably 0 to 50% by weight). % By weight, especially 0 to 40% by weight)
It can be.

As described above, the aqueous resin composition of the present invention comprises a polymerizable unsaturated monomer having a hydrolyzable silyl group, a polymerizable unsaturated monomer having an ultraviolet absorbing ability, and a third polymerizable unsaturated monomer. A copolymer obtained by copolymerizing monomers is used. When each of these polymerizable unsaturated monomers is copolymerized, the ratio of the polymerizable unsaturated monomer having a hydrolyzable silyl group to the total polymerizable unsaturated monomer is from 0.5% by weight to 50% by weight. %,
In particular, 0.5 to 20.0% by weight is preferable. If the proportion of the polymerizable unsaturated monomer having a hydrolyzable silyl group in the total polymerizable unsaturated monomer is less than the above range, the water resistance, solvent resistance and adhesion of the cured coating film deteriorate. In some cases. Conversely, if this range exceeds the above range, there may be a problem that the polymerization stability and storage stability of the aqueous resin composition decrease.

The ratio of the polymerizable unsaturated monomer having an ultraviolet absorbing ability to the total polymerizable unsaturated monomer is from 0.1% by weight to 10% by weight, especially from 0.5% by weight to 10.0% by weight. % By weight is preferred. When the ratio of the polymerizable unsaturated monomer having an ultraviolet absorbing ability to the total polymerizable unsaturated monomer is less than the above range, a problem may occur that the weather resistance of the cured coating film is deteriorated. . Conversely, if this range exceeds the above range, there may be a problem that the storage stability of the aqueous resin composition is lowered or the color tone of the cured coating film is affected.

A third feature of the present invention is that the resin composition containing the polymer is aqueous. The aqueous resin composition containing a polymer may be an aqueous solution or an aqueous emulsion (aqueous polymer emulsion). Such an aqueous resin composition is an aqueous resin composition formed without using a special cross-linking resin such as a cross-linked product of an acrylic silicone oligomer containing a hydrolyzable alkoxysilyl group. Is high. In addition, by using this water-based resin composition, a coating agent which has a low risk of air pollution, poisoning, fire and the like and has good workability can be obtained.

The average particle size of the polymer particles in the aqueous emulsion is within a range that does not impair the dispersion stability, adhesion, etc., for example, 0.01 to 2 μm, preferably 0.01 to 2 μm.
To 1 μm, more preferably 0.01 to 0.5 μm, and still more preferably about 0.01 to 0.3 μm.

The method for preparing the aqueous solution or emulsion of the polymer is not particularly limited, and may be a conventional method, for example, (a) having a polymerizable unsaturated monomer having a hydrolyzable silyl group and having an ultraviolet absorbing ability. With the polymerizable unsaturated monomer, a third polymerizable unsaturated monomer including a polymerizable unsaturated monomer having an ionic functional group such as a carboxyl group or an amino group is mixed and copolymerized, This polymer is converted into an alkali (eg, an alkylamine such as triethylamine, a cyclic amine such as morpholine, an alkanolamine such as triethanolamine, pyridine, ammonia, etc.) or an acid [eg, an inorganic acid (eg, hydrochloric acid, sulfuric acid, etc.), Dissolving or dispersing using an organic acid (for example, carboxylic acid such as acetic acid and propionic acid, sulfonic acid, etc.), (b) emulsifying the polymer Etc. can be employed more soluble or method for emulsifying and dispersing, and (c) emulsion polymerization.

In the method (a) or (b), the polymer may be adjusted by solution polymerization, or may be adjusted by emulsion polymerization, suspension polymerization, bulk polymerization, or the like. The polymerization may be of a batch type or a continuous type.

In the solution polymerization, an organic solvent (for example, alcohol (for example, ethanol, isopropanol, n-butanol, etc.), an aromatic hydrocarbon (for example, benzene,
Toluene, xylene, etc.), aliphatic hydrocarbons (for example,
Pentane, hexane, heptane, etc.), alicyclic hydrocarbons (eg, cyclohexane, etc.), esters (eg,
Ethyl acetate, n-butyl acetate, etc.), ketones (for example,
The polymerization can be carried out in the presence of acetone, methyl ethyl ketone, etc.), ethers (eg, diethyl ether, dioxane, tetrahydrofuran, etc.). The organic solvents may be used alone or in combination of two or more. As the organic solvent, usually, alcohols such as isopropanol, aromatic hydrocarbons such as toluene, ketones such as methyl ethyl ketone, and the like are used.

The amount of the organic solvent used is not particularly limited. For example, the amount of the organic solvent relative to the total amount of the polymerizable unsaturated monomers is (0.1 / 1 to 5/1) by weight, and preferably (0/1). .5
/ 1 to 2/1).

In the solution polymerization, the polymerization may be started by irradiation with an electron beam or ultraviolet rays, but the polymerization is often started using a polymerization initiator.

Examples of the polymerization initiator include, for example, azo compounds [eg, azobisisobutyronitrile, 2,2-azobis (2,4-dimethylvaleronitrile), azobiscyanovaleric acid, 2,2-azobis (2- Amidinopropane) hydrochloride, 2,2-azobis (2-amidinopropane) acetate, etc.], inorganic peroxides (for example, persulfates such as potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide), organic Peroxides [e.g., benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide, di (2-ethoxyethyl) peroxydicarbonate] and redox catalysts [e.g., sulfites or bisulfites (e.g.,
A catalyst comprising a combination of a reducing agent such as an alkali metal salt or an ammonium salt), L-ascorbic acid or erythorbic acid and an oxidizing agent such as a persulfate (eg, an alkali metal salt or an ammonium salt) or a peroxide; System]. The polymerization initiators can be used alone or in combination of two or more.

The amount of the polymerization initiator used is, for example, 0.001 to 20% by weight based on the total weight of the polymerizable unsaturated monomer,
Preferably 0.01 to 10% by weight (for example, 0.1 to 1%)
0% by weight).

The reaction temperature in the solution polymerization is, for example, 5
The temperature is 0 to 150 ° C, preferably about 70 to 130 ° C.
The reaction time is, for example, about 1 to 10 hours, preferably about 2 to 7 hours. The end point of the polymerization can be confirmed by disappearance of double bond absorption (1648 cm ^-1 ) in the infrared absorption spectrum or reduction of unreacted monomer by using gas chromatography.

In emulsifying the polymer, an emulsifier such as an anionic surfactant such as an alkyl sulfate, an alkylaryl sulfonate, an alkyl phosphate or a fatty acid salt; an alkylamine salt; an alkyl quaternary ammonium salt; Nonionic surfactants such as polyoxyethylene alkylaryl ether, polyoxyethylene alkyl ether, or bruronic type, carboxylate type (amino acid type, betaine type, etc.) or sulfonate type An amphoteric surfactant such as can be used. Note that the pH of the emulsion may be adjusted with a pH adjuster that is generally used.

When the polymer contains a cationic group such as an amino group, an imide group or a cation-forming group,
When an acid is used, hydrophilicity is improved, and the polymer can be easily dissolved or emulsified. Such acids include, for example, inorganic acids (eg, hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, etc.) and organic acids [eg, saturated aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid; oxalic acid, adipic acid Unsaturated aliphatic monocarboxylic acids such as (meth) acrylic acid; unsaturated aliphatic polycarboxylic acids such as maleic acid and itaconic acid; aliphatic oxycarboxylic acids such as lactic acid and citric acid Etc.].

When the polymer has an acidic group such as a carboxyl group, the use of a base can easily dissolve or emulsify the polymer. Such bases include, for example, organic bases (eg, alkylamines such as triethylamine, cyclic amines such as morpholine, alkanolamines such as triethanolamine, pyridine, etc.), and inorganic bases (eg, ammonia, alkali metal hydroxides) Such)
And so on.

The amount of the acid used can be selected, for example, from the range of about 0.3 / 1 to 1.5 / 1 (molar ratio) of the base / acid group based on the total moles of the acid groups.

The emulsification of the polymer obtained by the solution polymerization is as follows:
It can be carried out in the presence or absence of an organic solvent. When dissolving or emulsifying and dispersing a polymer in the presence of an organic solvent,
As the organic solvent, a water-soluble organic solvent (for example, an alcohol such as isopropanol) is often used. When the polymer is emulsified in the presence of an organic solvent, the organic solvent may be removed after the emulsification by evaporation or the like, and the emulsion may contain an organic solvent. When the organic solvent is removed before emulsifying the polymer, a low-boiling organic solvent (for example, a ketone such as methyl ethyl ketone) is often used.

When the polymer obtained by the solution polymerization is emulsified in the presence of an organic solvent, an additive (for example, an emulsifier, a pH adjuster, an acid, etc.) is added to an organic solution containing the polymer, and then added to water. Can be added to emulsify. In this case, it is preferable that water is gradually added by dropping or the like. The temperature at the time of emulsification is preferably low, and for example, can be selected from the range of about 70 ° C. or less (eg, 5 to 70 ° C.), preferably about 50 ° C. or less (eg, 10 to 50 ° C.).

The removal of the organic solvent after emulsification by adding water is carried out, for example, at a temperature of 80 ° C. or lower (eg, about 5 to 80 ° C.) at normal pressure or reduced pressure (eg, 0.0001 to 1 atm). Degree) in many cases.

The emulsion polymerization of the polymerizable unsaturated monomer is carried out by
It can be carried out according to a conventional emulsion polymerization method, for example,
Monomer batch charging method (for example, a method of batch charging and polymerizing a polymerizable unsaturated monomer in an aqueous medium), a monomer addition method (polymerizable unsaturated monomer in an aqueous medium, (A method of adding and polymerizing). The polymerizable unsaturated monomer may be used as a pre-emulsified emulsion. In preparing this emulsion, the emulsion may be emulsified using a polymerizable emulsifier as a copolymerization component, or may be emulsified using an emulsifier.

Examples of the polymerization initiator used in the emulsion polymerization include inorganic peroxides (for example, persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate, hydrogen peroxide and the like) among the polymerization initiators in the solution polymerization. ) Can be used, and may constitute a water-soluble redox-type polymerization initiator system.

Examples of the polymerizable emulsifier include, for example, various conventional polymerizable emulsifiers (for example, a quaternary ammonium salt containing a (meth) allyl group or a (meth) acryl group as a polymerizable group, and an emulsifying functional group). A cationic group such as a tertiary amine salt, an amino group or an imide group, an anionic group such as a sulfonate or a carboxylate, or a nonionic group such as an ethylene oxide group].
The amount of the polymerizable emulsifier used is, for example, 0.1 to 20% by weight, preferably 0.5 to 10% by weight based on the total amount of the monomers.
You can choose from a range of degrees.

Examples of the emulsifier that can be used in emulsion polymerization include emulsifiers that can be used in emulsifying the polymer obtained by the solution polymerization. Further, for stabilization of emulsion polymerization, etc., protective colloid agent (for example, partially saponified polyvinyl alcohol, carboxymethyl cellulose,
Methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, etc.). The pH of the emulsion may be adjusted.

The conditions such as the temperature in the emulsion polymerization may be the same as those in the solution polymerization.

In solution polymerization or emulsion polymerization, a chain transfer agent, for example, alcohols such as catechol, thiols, and mercaptans (for example, n-laurylmercaptan, n-dodecyl) are used to adjust the molecular weight of the polymer. Mercaptan, t-dodecyl mercaptan, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, etc.) may be used.

In the aqueous resin composition, if necessary, for example,
Fluororesin, silicone resin, organic sulfonate compound,
Lubricants such as organic phosphate compounds and organic carboxylate compounds, antioxidants, ultraviolet absorbers, stabilizers such as heat stabilizers, radical scavengers, quenchers, antistatic agents, plasticizers,
Additives such as thickeners and defoamers may be added.

[0097]

The present invention will be described below in detail with reference to examples.

Example 1 219 parts by weight of isopropyl alcohol was placed in a 2 liter reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a nitrogen inlet tube and a thermometer, and azobisisobutyronitrile as a catalyst was stirred with stirring. 0.62 parts by weight was added and dissolved, and the mixture was heated to 80 degrees Celsius. 4.94 parts by weight of 3-methacryloxypropyltrimethoxysilane (trade name: A-174, manufactured by Nippon Unicar Co., Ltd.) as a polymerizable unsaturated monomer having a hydrolyzable silyl group, and polymerization having an ultraviolet absorbing ability [2'-Hydroxy-5 '-(methacryloyloxyethyl) phenyl] as the unsaturated monomer
Benzotriazole (trade name RU manufactured by Otsuka Chemical Co., Ltd.
VA-93) is 1.25 parts by weight, methyl methacrylate is 135.7 parts by weight, and n-butyl acrylate is 98.
A copolymer component consisting of 7 parts by weight and 7.39 parts by weight of acrylic acid was mixed and dropped into the reaction vessel over about 4 hours using a dropping funnel. After completion of the dropwise addition, 1.25 parts by weight of azobisisobutyronitrile as an additional catalyst was dissolved in 25 parts by weight of isopropyl alcohol and dropped into the reaction vessel, and the reaction was maintained for another 2 hours. After completion of the polymerization, 6.95 parts by weight of 25% aqueous ammonia was added into the reaction vessel while stirring was continued, and 705 parts by weight of water was dropped into the reaction vessel over about 2 hours to emulsify. After the emulsification, isopropyl alcohol was evaporated using a rotary evaporator to obtain an aqueous resin composition for a coating agent of Example 1. The solid content of this aqueous resin composition is 35% by weight.
Met. The proportion of the polymerizable unsaturated monomer having a hydrolyzable silyl group in the copolymer component of the aqueous resin composition was 2.0% by weight, and the amount of the polymerizable unsaturated monomer having an ultraviolet absorbing ability was 2.0% by weight. The body percentage is 0.5% by weight.

Example 2 As a polymerizable unsaturated monomer having an ultraviolet absorbing ability in a copolymer component, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] benzotriazole was used instead of the above-mentioned 2- [2'-hydroxy-5'-(methacryloyloxyethyl) phenyl] benzotriazole. An aqueous resin composition for a coating agent of Example 2 was obtained in the same manner as in Example 1 except that 1.25 parts by weight of 2-hydroxy-4- (methacryloyloxy) ethoxybenzophenone was used. The proportion of the polymerizable unsaturated monomer having a hydrolyzable silyl group in the copolymer component of the aqueous resin composition was 2.0% by weight, and the ratio of the polymerizable unsaturated monomer having an ultraviolet absorbing ability was 2.0% by weight. The proportion is 0.5% by weight.

Example 3 The amount of 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] benzotriazole (RUVA-93 (trade name) manufactured by Otsuka Chemical Co., Ltd.) used was 2.49 parts by weight. A water-based resin composition for a coating agent of Example 3 was obtained in the same manner as in Example 1 except for the above. The proportion of the polymerizable unsaturated monomer having a hydrolyzable silyl group in the copolymer component of the aqueous resin composition was 2.0% by weight, and the ratio of the polymerizable unsaturated monomer having an ultraviolet absorbing ability was 2.0% by weight. The proportion is 1.0% by weight.

Example 4 As a copolymer component, 3-methacryloxypropyltrimethoxysilane (trade name A manufactured by Nippon Unicar KK)
-174) 4.94 parts by weight, 2- [2'-hydroxy-
5 ′-(methacryloyloxyethyl) phenyl] benzotriazole (trade name R manufactured by Otsuka Chemical Co., Ltd.
UVA-93) The same procedures as in Example 1 were carried out except that 1.25 parts by weight, 124.0 parts by weight of methyl methacrylate, 86.8 parts by weight of n-butyl acrylate and 7.44 parts by weight of acrylic acid were used. Thus, an aqueous resin composition for coating agent No. 4 was obtained. The proportion of the polymerizable unsaturated monomer having a hydrolyzable silyl group in the copolymer component of the aqueous resin composition was 2.0% by weight, and the ratio of the polymerizable unsaturated monomer having an ultraviolet absorbing ability was 2.0% by weight. The proportion is 10.0% by weight.

Example 5 3-methacryloxypropyltrimethoxysilane was used as a copolymer component (trade name A manufactured by Nippon Unicar KK).
-174) 1.25 parts by weight, 2- [2'-hydroxy-
5 ′-(methacryloyloxyethyl) phenyl] benzotriazole (trade name R manufactured by Otsuka Chemical Co., Ltd.
(UVA-93) 1.25 parts by weight, 138.9 parts by weight of methyl methacrylate, 99.2 parts by weight of n-butyl acrylate and 7.44 parts by weight of acrylic acid, except that Example 1 was used. Thus, an aqueous resin composition for coating agent No. 5 was obtained. The proportion of the polymerizable unsaturated monomer having a hydrolyzable silyl group in the copolymerized component of the aqueous resin composition is 0.5% by weight, and the ratio of the polymerizable unsaturated monomer having an ultraviolet absorbing ability is 0.5% by weight. The proportion is 0.5% by weight.

Example 6 3-methacryloxypropyltrimethoxysilane was used as a copolymer component (trade name A manufactured by Nippon Unicar KK).
-174) 49.6 parts by weight, 2- [2'-hydroxy-
5 ′-(methacryloyloxyethyl) phenyl] benzotriazole (trade name R manufactured by Otsuka Chemical Co., Ltd.
UVA-93) The same procedure as in Example 1 was carried out except that 1.25 parts by weight, 115.3 parts by weight of methyl methacrylate, 74.4 parts by weight of n-butyl acrylate and 7.44 parts by weight of acrylic acid were used. Thus, an aqueous resin composition for coating agent No. 6 was obtained. The proportion of the polymerizable unsaturated monomer having a hydrolyzable silyl group in the copolymerizable component of the aqueous resin composition was 20.0% by weight, and the ratio of the polymerizable unsaturated monomer having an ultraviolet absorbing ability was 20.0% by weight. The proportion is 0.5% by weight.

Example 7 4.04 parts by weight of 3-methacryloxypropyltrimethoxysilane (trade name A-174 manufactured by Nippon Unicar Co., Ltd.) as a copolymer component, 2- [2'-hydroxy-5 ' -(Methacryloyloxyethyl) phenyl] benzotriazole (trade name: RUVA-93 manufactured by Otsuka Chemical Co., Ltd.), 2.04 parts by weight, methyl methacrylate 111.1 parts by weight, n-butyl acrylate 80.8
Weight part and 6.06 parts by weight of acrylic acid were mixed, and 4.67 parts by weight of sodium alkyl allyl sulfosuccinate (trade name: Eleminol JS-2 manufactured by Sanyo Chemical Co., Ltd.) was dissolved in 58.47 parts by weight of deionized water. It was pre-emulsified by dropping into an aqueous solution.

On the other hand, a stirrer, a reflux condenser, a dropping funnel,
1. 157 parts by weight of deionized water was placed in a 2 liter reaction vessel equipped with a nitrogen inlet tube and a thermometer, and sodium alkyl allyl sulfosuccinate (trade name Eleminor JS-2 manufactured by Sanyo Chemical Co., Ltd.) was stirred while stirring. 34 parts by weight were added for dissolution, and 0.77 parts by weight of ammonium persulfate was further added for dissolution. After the reaction vessel was heated to 60 degrees Celsius, the pre-emulsion and 53 parts by weight of a 0.68% by weight aqueous sodium thiosulfate solution were dropped into the reaction vessel over about 4 hours using a dropping funnel. After dropping,
The reaction was maintained for another 2 hours to obtain an aqueous resin composition of Example 7. The solid content of this aqueous resin composition was 39% by weight. The proportion of the polymerizable unsaturated monomer having a hydrolyzable silyl group in the copolymer component of the aqueous resin composition was 2.0% by weight, and the amount of the polymerizable unsaturated monomer having an ultraviolet absorbing ability was 2.0% by weight. The body percentage is 1.0% by weight.

Comparative Example 1 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] benzotriazole (RUVA-9 manufactured by Otsuka Chemical Co., Ltd.
3) 1.25 parts by weight, methyl methacrylate 135.7
A water-based resin composition for a coating agent of Comparative Example 1 was obtained in the same manner as in Example 1, except that 98.7 parts by weight of n-butyl acrylate and 7.39 parts by weight of acrylic acid were used. The proportion of the polymerizable unsaturated monomer having an ultraviolet absorbing ability in the copolymer component of the aqueous resin composition was 0.5% by weight, and the copolymerizable component of the aqueous resin composition contained a hydrolyzable monomer. No polymerizable unsaturated monomer having a silyl group is included.

Comparative Example 2 As a copolymer component, 3-methacryloxypropyltrimethoxysilane (trade name A manufactured by Nippon Unicar KK)
-174) 4.94 parts by weight, methyl methacrylate 13
5.7 parts by weight, 98.7 parts by weight of n-butyl acrylate and 7.39 parts by weight of acrylic acid were mixed, and 2- (2′-hydroxy-3 ′,
5'-di-t-butylphenyl) benzotriazole (trade name TINUVIN32 manufactured by Ciba-Geigy Corporation)
0) An aqueous resin composition for a coating agent of Comparative Example 2 was obtained in the same manner as in Example 1 except that 1.25 parts by weight was used. The proportion of the polymerizable unsaturated monomer having a hydrolyzable silyl group in the copolymer component of the aqueous resin composition was 2.0% by weight, and the copolymer component of the aqueous resin composition contained ultraviolet rays. It does not contain any polymerizable unsaturated monomers having absorption capacity. The aqueous resin composition contains 0.5 parts by weight of the ultraviolet absorbing additive based on 100 parts by weight of the copolymer component.

Comparative Example 3 As a copolymer component, 3-methacryloxypropyltrimethoxysilane (trade name A manufactured by Nippon Unicar KK)
-174) 4.94 parts by weight, methyl methacrylate 13
5.7 parts by weight, 98.7 parts by weight of n-butyl acrylate and 7.39 parts by weight of acrylic acid were mixed, and 2,4-dihydroxybenzophenone (a product of Tokyo Chemical Industry Co., Ltd.) as an ultraviolet absorbing additive was added thereto. Name D0573) 1.
An aqueous resin composition for a coating agent of Comparative Example 3 was obtained in the same manner as in Example 1 except that 25 parts by weight was used. The proportion of the polymerizable unsaturated monomer having a hydrolyzable silyl group in the copolymerized component of the aqueous resin composition is 2.
0% by weight, and the copolymerizable component of this aqueous resin composition does not contain a polymerizable unsaturated monomer having an ultraviolet absorbing ability. The aqueous resin composition contains 0.5 parts by weight of the ultraviolet absorbing additive based on 100 parts by weight of the copolymer component.

Comparative Example 4 As a copolymer component, 3-methacryloxypropyltrimethoxysilane (trade name A manufactured by Nippon Unicar KK)
-174) 4.94 parts by weight, methyl methacrylate 13
An aqueous resin composition for a coating agent of Comparative Example 4 was obtained in the same manner as in Example 1 except that 5.7 parts by weight, 98.7 parts by weight of n-butyl acrylate and 7.39 parts by weight of acrylic acid were used. . The proportion of the polymerizable unsaturated monomer having a hydrolyzable silyl group in the copolymer component of the aqueous resin composition was 2.0% by weight, and the copolymer component of the aqueous resin composition contained ultraviolet rays. It does not contain any polymerizable unsaturated monomers having absorption capacity. Further, this water-based resin composition does not contain an ultraviolet absorbing additive.

The aqueous resin compositions of Examples 1 to 7 and Comparative Examples 1 to 4 were subjected to the formulation shown in Table 1 below to obtain aqueous coating agents.

[0111]

[Table 1]

Experimental Examples The aqueous resin compositions of Examples 1 to 7 and Comparative Examples 1 to 4 were subjected to a water resistance test, a solvent resistance test and an adhesion test. The aqueous coating agents obtained from the aqueous resin compositions of Examples 1 to 7 and Comparative Examples 1 to 4 were subjected to a weather resistance test. Each test method is as follows.

Water resistance test The aqueous resin composition adjusted to a solid content of 20% by weight was prepared as 1
The composition was applied to an acrylic plate with a bar coater No. 2 and cured and dried at 105 ° C. for 5 minutes. Thereafter, the acrylic plate was immersed in a water bath at 20 degrees Celsius for 7 days, and changes in the coating film were visually evaluated.も の indicates no change in the coating film, 塗膜 indicates that the coating film was slightly whitened, and x indicates that the coating film dissolved and disappeared.
And

Solvent resistance test A coating film was formed on an acrylic plate in the same manner as in the water resistance test described above, and a rubbing test was performed on the coating film with a cotton swab dipped in acetone until the coating film was dissolved. The number of times was recorded.

The adhesion test was carried out with the aqueous resin composition adjusted to a solid content of 20% by weight. 1
The composition was applied to a polyethylene terephthalate plate using a bar coater No. 2 and cured and dried at 105 ° C. for 5 minutes.
Thereafter, the coating film on the polyethylene terephthalate plate was subjected to a cross-cut peeling test using cellophane tape, and the number of remaining cross-cuts among 100 cross-cuts was visually counted.

[0116] Weather resistance test The composition was applied to an aluminum plate with a bar coater No. 12 and cured and dried at 105 ° C. for 5 minutes. The test piece was subjected to a 1500 hour acceleration test using a QUV accelerated weathering tester, and the gloss retention was quantified using a gloss meter. Note that the peak wavelength of the amount of ultraviolet light in this tester is 310 nm, which is almost equal to that of ultraviolet light included in natural light.

The results of these tests are shown in Tables 2 and 3 below.

[0118]

[Table 2]

[0119]

[Table 3]

From Tables 2 and 3, it can be seen from Example 1 that a polymerizable unsaturated monomer having a hydrolyzable silyl group was used as a copolymer component.
It can be seen that the water-based resin composition of No. 7 is superior to the water-based resin composition of Comparative Example 1 in which the water-based resin composition was not used as a copolymer component and the solvent resistance was excellent. This is because a cross-linking reaction occurs during the formation of the coating film due to the action of the hydrolyzable silyl group.

Further, the aqueous coating agent comprising the aqueous resin composition of Examples 1 to 7 using a polymerizable unsaturated monomer having an ultraviolet absorbing ability as a copolymer component is an ultraviolet absorbing agent (polymerizable unsaturated monomer). It can be seen that the weather resistance is superior to that of the water-based coating agent comprising the water-based resin composition of Comparative Example 4 which does not contain the (body and additives).

Further, the aqueous coating agent comprising the aqueous resin composition of Examples 1 to 7 using a polymerizable unsaturated monomer having an ultraviolet absorbing ability as a copolymer component was obtained in Comparative Examples 2 and 3 containing an ultraviolet absorbing additive. It turns out that it is more excellent in weather resistance than the aqueous coating agent which consists of an aqueous resin composition of No. 3. This is because the UV-absorbing additive bleeds out in the water-based coating agent comprising the water-based resin compositions of Comparative Examples 2 and 3, and the UV-absorbing effect is impaired. Further, it can be seen that the aqueous resin compositions of Examples 1 to 7 are more excellent in water resistance than the aqueous resin compositions of Comparative Examples 2 and 3. This is because in the water-based resin compositions of Comparative Examples 2 and 3, water penetrates into fine void defects caused by bleed-out of the ultraviolet absorbing additive. Examples 1 to 7
It can be seen that the aqueous resin composition of Comparative Example 2 is more excellent in adhesion than the aqueous resin compositions of Comparative Examples 2 and 3. This is because the bleed-out ultraviolet absorbing additive is interposed between the polyethylene terephthalate plate and the coating film and impairs the adhesion between the two.

From Table 2, it can be seen that the water resistance, the solvent resistance, the adhesion and the weather resistance are improved by any of the solution polymerization (Examples 1 to 6) and the emulsion polymerization (Example 7). It can be seen that an excellent aqueous resin composition or an aqueous coating agent can be obtained.

Further, comparing the water-based coating agents containing the water-based resin compositions of Example 1 and Example 2, the polymerizable unsaturated monomer having the ultraviolet absorbing ability used in Example 2 was used. Compared with a certain 2-hydroxy-4- (methacryloyloxy) ethoxybenzophenone (the chemical structure of which is represented by the general formula (2)), a polymerizable unsaturated monomer having an ultraviolet absorbing ability used in Example 1 is used. 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] benzotriazole (the chemical structure of which is represented by the general formula (1)), which is a compound, has a greater effect of improving weather resistance. Recognize. This is 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl]
It is considered that benzotriazole is more excellent in the ability to absorb ultraviolet light having a wavelength of 300 to 370 nm, which is particularly contained in natural light in the ultraviolet region.

[0125]

As described above, according to the present invention,
While maintaining the advantages of a water-based coating that is less likely to cause air pollution, poisoning, and fire, and has good workability, it also improves the water, solvent, adhesion, and weather resistance, which are disadvantages of water-based coatings. be able to. Thus, an aqueous resin composition excellent in all and an aqueous coating agent using the same have not been obtained so far.

Claims (7)

[Claims] 1. A polymerizable unsaturated monomer having a hydrolyzable silyl group, (b) a polymerizable unsaturated monomer having an ultraviolet absorbing ability, and (c) the above (a) and (b) An aqueous resin composition obtained by dissolving or dispersing a copolymer obtained by copolymerizing a polymerizable unsaturated monomer other than the above in water. 2. The proportion of (b) the polymerizable unsaturated monomer having an ultraviolet absorbing ability in the polymerizable unsaturated monomer constituting the copolymer is 0.1% by weight to 10% by weight. The aqueous resin composition according to claim 1, which is: 3. The proportion of (a) the polymerizable unsaturated monomer having a hydrolyzable silyl group in the polymerizable unsaturated monomer constituting the copolymer is from 0.5% by weight to 50% by weight. The water-based resin composition according to claim 1, which is in weight%. 4. The proportion of (b) a polymerizable unsaturated monomer having an ultraviolet absorbing ability in the polymerizable unsaturated monomer constituting the copolymer is 0.1% by weight to 10% by weight. The aqueous resin composition according to claim 1, wherein (a) the proportion of the polymerizable unsaturated monomer having a hydrolyzable silyl group occupies 0.5% by weight to 50% by weight. 5. The polymerizable unsaturated monomer having the ultraviolet absorbing ability (b) is a polymerizable unsaturated monomer represented by the following general formula (1). (Wherein X ¹ is a hydrogen atom, a halogen atom, a carbon number of 1 to 8)
R14 represents a hydrogen atom or a carbon atom having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group.
To R8, R15 represents a linear or branched alkylene group having 1 to 6 carbon atoms, and R16 represents a hydrogen atom or a methyl group. ) And a polymerizable unsaturated monomer represented by the following general formula (2): (Wherein Y is an oxygen atom, —OCH ₂ CH ₂ O— or —OCH
₂ CH (CH ₃₎ O- are shown, R16 is a hydrogen atom or a methyl group, R17 is a hydrogen atom, hydrocarbon group, a hydrocarbon group or an alkoxy group having 1 to 4 carbon atoms from 1 to 8 carbon atoms. 5) The aqueous resin composition according to any one of claims 1 to 4, which is one or more polymerizable unsaturated monomers selected from the group consisting of: 6. The method according to claim 1, wherein the (b) polymerizable unsaturated monomer having an ultraviolet absorbing ability contains at least the polymerizable unsaturated monomer represented by the general formula (1). An aqueous resin composition according to any one of the above. 7. An aqueous coating agent using the aqueous resin composition according to any one of claims 1 to 6.