JPH083278A - Curable resin composition - Google Patents

Abstract

PURPOSE:To produce a liquid resin applicable without using a solvent. CONSTITUTION:A curable resin composition comprising a copolymer (i) obtained by copolymerizing 35-98wt.% styrene monomer represented by the formula CH2=C(R<1>)-phi-X-R<2>, 2-50wt.% epoxidized vinyl monomer, and 0-20wt.% other polymerizable vinyl compound and a hardener (ii) having per molecule two or more functional groups bondable to the epoxy groups of the copolymer (i). In the formula, R<1> is hydrogen or CH3; R<2> is a 5-22C alkyl or (CnH<2n>O)mR<3> (wherein (n) is an integer of 1-3, (m) is an integer of 4-25, and R<3> is hydrogen or a 1-4C alkyl); phi is an optionally substituted phenylene group; and X is O, COO, or R<4>O [wherein R<4> is CH2, CH2CH2, O-CO-R<5>-CO, CH2O-CO-R<5>-CO, or CH2CH2O-CO-R<5>-CO(R<5> is a direct bond or a 1-7C optionally branched alkylene group)].

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition which can be coated or molded without using a solvent, and is then treated with heat to give a solid cured product. INDUSTRIAL APPLICABILITY The resin of the present invention is used as a solvent-free liquid resin for coating materials such as paints, adhesives, pressure-sensitive adhesives and inks, as well as for fillers, molding materials and surface modification materials.

[0002]

2. Description of the Related Art Conventionally, coating materials such as paints and printing inks,
Resin solutions containing organic solvents have been used for adhesives, adhesives, fillers, and molding materials. These resin solutions scatter a large amount of organic solvents in the painting, filling and curing / drying steps. With increasing interest in the global environment and working environment, restrictions on the use of such resin solutions are being imposed. One of the methods is to use an aqueous solution or powder of resin, or a hot melt material,
The aqueous solution of the resin contains some organic solvent from the viewpoint of improving the coating property, and it is hard to say that the odor in the working environment is removed. Also, along with the incineration process of the released organic solvent,
Requires investment in wastewater treatment. In a painting and filling factory equipped with a large-scale exhaust gas treatment facility, the release of organic solvents into the atmosphere can be suppressed, but in a small factory without such equipment,
There is a problem that wastewater cannot be treated even if it can be treated with an organic solvent. In addition, in the case of coating or filling powder or hot melt, it is necessary to introduce new equipment because the method is significantly different from the conventional painting and filling equipment.

In order to solve the above problems, high solidification of the resin solution and improvement of the aqueous solution of the resin have been carried out. Due to such efforts, the usage amount of the resin solution will become more prominent in the future. Conceivable. However, as a fundamental solution, there is a strong demand for the development of a solventless liquid resin which is free from problems such as pollution, safety and hygiene, ignition and explosion, can be widely applied, and is easy to apply and fill. Further, these solventless liquid resins need to be formed into a coating film or a molded product that is cured by a conventional drying device. Such a solventless liquid resin is disclosed in JP-A-57-171. This technique uses a liquid resin based on an acrylic monomer, but since the resulting resin is an oligomer and contains a residual monomer in the composition, further improvement is desired.
In terms of physical properties, it is known that it is difficult to control the physical properties of the coating film after curing in the case of coatings composed of resins in the oligomer domain (Soichi Muroi, "1992 Adhesion and Painting Study Group Course"). Proceedings, p4, 1993),
It is desired to increase the molecular weight while maintaining low viscosity.

[0004]

DISCLOSURE OF THE INVENTION The present invention does not contaminate the working environment of the coating process with the organic solvent that scatters and does not discharge the organic solvent into the atmosphere, and thus does not require special exhaust gas treatment equipment. Moreover, the coating that has been used conventionally,
The present invention provides a liquid resin which can be coated and filled by a filling method, for example, a roll coater or a knife coater, and which does not disperse the solvent even if a conventional heating and drying is performed and becomes a hard film or a molded product.

[0005]

Means for Solving the Problems As a result of extensive studies on the solution of the above problems, the present inventor found that a resin composition comprising a specific styrene monomer and a vinyl monomer having an epoxy group has a high molecular weight. However, it was found that a resin composition which can be coated and filled by a conventional coating and filling method and which reacts with a cross-linking agent having at least two functional groups capable of binding to an epoxy group to be cured becomes a resin composition. It was

That is, the present invention provides 35 to 98% by weight of a styrene monomer (A) represented by the following general formula, 2 to 50% by weight of a vinyl monomer (B) having an epoxy group, and other polymerizations. Resin (i) obtained by copolymerizing 0 to 20% by weight of a polymerizable vinyl compound (C), and a curing agent having two or more functional groups capable of binding to an epoxy group of the copolymer (i) in one molecule ( ii) is related to the curable resin composition. General ^{_{formula: CH 2 = C (R 1}} ) -φ-X-R 2 ( wherein, R ¹ represents a hydrogen atom or CH _3, R ² is 5 carbon atoms
22 represents an alkyl group of 22 or (C _n H _2n O) _m R ³ . Here, n is an integer of 1 to 3, m is an integer of 4 to 25, and R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. φ is a phenylene group which may have a substituent, X is —O—,
-COO- or -R represents a ⁴ O-. Here, R ⁴ is −
_{CH 2 -, - CH 2 CH} 2 -, - O-CO-R 5 -CO-,
^{_{-CH 2 O-CO-R 5}} -CO-, CH 2 CH 2 O-CO-
R ⁵ —CO— (However, R ⁵ is a direct bond or has 1 to 1 carbon atoms.
7 represents an optionally branched alkylene group. ) Represents. Further, in the present invention, the copolymer (i) has a viscosity of 500 to 3
It is a liquid resin of 0000 cps (50 ° C.).
The curable resin composition described above.

Styrene monomer (A) used in the present invention
Is a compound in which an alkyl group or a poly (alkyleneoxy) group is bonded via a bonding group X to a styrene compound that may have a substituent such as an alkyl group as represented by the above general formula. . The number of carbon atoms in the alkyl group is 5 or more 2
It is preferable that the number of repeating units of alkyleneoxy group is 2 or less, or 4 or more and 25 or less.

Styrene monomer (A) used in the present invention
As, for example, vinylphenyl pentyl ether, vinylphenyl hexyl ether, vinylphenyl heptyl ether, vinylphenyl octyl ether,
Vinyl phenyl nonyl ether, vinyl phenyl decyl ether, vinyl phenyl undecyl ether,
Vinyl phenyl dodecyl ether, vinyl phenyl
Tridecyl ether, vinyl phenyl tetradecyl ether, vinyl phenyl pentadecyl ether, vinyl phenyl hexadecyl ether, vinyl phenyl
Heptadecyl ether, vinyl phenyl octadecyl ether, vinyl phenyl nonadecyl ether, vinyl phenyl eicosyl ether, vinyl phenyl hen eicosyl ether, vinyl phenyl docosyl ether, vinyl phenyl methyl butyl ether, vinyl phenyl methyl pentyl ether, vinyl phenyl methyl hexyl ether , Vinyl phenyl methyl heptyl ether, vinyl phenyl methyl octyl ether, vinyl phenyl methyl nonyl ether, vinyl phenyl methyl decyl ether, vinyl phenyl methyl undecyl ether, vinyl phenyl methyl dodecyl ether, vinyl phenyl methyl tridecyl ether, vinyl phenyl methyl tetradecyl Ether, vinyl phenylmethyl pentadecyl ether , Vinylphenylmethyl hexadecyl ether, vinylphenylmethyl heptadecyl ether, vinylphenylmethyl octadecyl ether, vinylphenylmethyl nonadecyl ether, vinylphenylmethyl eicosyl ether, vinylphenylmethyl heneicosyl ether, vinylphenylmethyl docosyl ether, etc. A styrene compound having a long-chain alkyl group,

Isopropenylphenylmethyl butyl ether, isopropenylphenylmethyl pentyl ether, isopropenylphenylmethyl hexyl ether, isopropenylphenylmethyl heptyl ether, isopropenylphenylmethyl octyl ether, isopropenylphenylmethyl nonyl ether,
Isopropenyl phenyl methyl decyl ether, isopropenyl phenyl methyl undecyl ether, isopropenyl phenyl methyl dodecyl ether, isopropenyl phenyl methyl tridecyl ether, isopropenyl phenyl methyl tetradecyl ether, isopropenyl phenyl methyl pentadecyl ether, isopropenyl phenyl methyl Hexadecyl ether, isopropenylphenylmethyl heptadecyl ether,
Cumene compounds with long-chain alkyl groups such as isopropenylphenylmethyl octadecyl ether, isopropenylphenylmethyl nonadecyl ether, isopropenylphenylmethyl eicosyl ether, isopropenylphenylmethyl heneicosyl ether, isopropenylphenylmethyl docosyl ether,

Hexyl 4-vinylbenzoate, octyl 4-vinylbenzoate, nonyl 4-vinylbenzoate,
Decyl 4-vinylbenzoate, dodecyl 4-vinylbenzoate, tetradecyl 4-vinylbenzoate, hexadecyl 4-vinylbenzoate, octadecyl 4-vinylbenzoate, eicosyl 4-vinylbenzoate, docosyl 4-vinylbenzoate, 4 -Isopropenylbenzoic acid
Hexyl, Octyl 4-isopropenyl benzoate, 4
-Nonyl isopropenyl benzoate, decyl 4-isopropenyl benzoate, dodecyl 4-isopropenyl benzoate, tetradecyl 4-isopropenyl benzoate,
4-isopropenyl benzoic acid hexadecyl, 4-isopropenyl benzoic acid octadecyl, 4-isopropenyl benzoic acid eicosyl, 4-isopropenyl benzoic acid docosyl and the like vinyl benzoic acid ester or isopropenyl benzoic acid ester having a long chain alkyl group, Examples include mono-long-chain alkyl esters of dicarboxylic acids such as vinyl phenyl nonyl succinate, vinyl phenyl methyl decyl hexahydrophthalate, and vinyl phenyl ethyl dodecyl terephthalate. As these alkyl groups, either straight-chain alkyl groups or branched alkyl groups can be used.

Further, tetra (oxyethylene) vinyl phenyl ether, methyl tetra (oxyethylene)
Vinyl phenyl ether, ethyl tetra (oxyethylene) vinyl phenyl ether, propyl tetra (oxyethylene) vinyl phenyl ether, n-butyl tetra (oxyethylene) vinyl phenyl ether, n-
Pentyl tetra (oxyethylene) vinyl phenyl ether, tetra (oxypropylene) vinyl phenyl ether, methyl tetra (oxypropylene) vinyl phenyl ether, ethyl tetra (oxypropylene)
Vinyl phenyl ether, propoxytetra (oxypropylene) vinyl phenyl ether, n-butyl tetra (oxypropylene) vinyl phenyl ether,
n-Pentoxytetra (oxypropylene) vinyl phenyl ether, poly (oxyethylene) vinyl phenyl ether, methyl poly (oxyethylene) vinyl phenyl ether, ethyl poly (oxyethylene) vinyl phenyl ether, poly (oxypropylene) vinyl phenyl ether, methyl poly (Oxypropylene) vinyl phenyl ether, ethyl poly (oxypropylene) vinyl phenyl ether, poly (oxyethylene) vinyl benzyl ether, methyl poly (oxyethylene) vinyl benzyl ether, ethyl poly (oxyethylene) vinyl benzyl ether, poly (oxypropylene) vinyl Benzyl ether, methyl poly (oxypropylene) vinyl Benzyl ether, ethyl poly (oxypropylene) vinyl Benzyl ether, poly (oxyethylene) vinylphenyl ethyl ether, methyl poly (oxyethylene) vinylphenyl ethyl ether, ethyl poly (oxyethylene)
Styrene compounds having a long chain polyalkyleneoxy group such as vinyl phenyl ethyl ether, poly (oxypropylene) vinyl phenyl ethyl ether, methyl poly (oxy propylene) vinyl phenyl ethyl ether, ethyl poly (oxy propylene) vinyl phenyl ethyl ether,

Poly (oxyethylene) isopropenyl phenyl ether, methyl poly (oxyethylene) isopropenyl phenyl ether, ethyl poly (oxyethylene) isopropenyl phenyl ether, poly (oxypropylene) isopropenyl phenyl ether,
Methyl poly (oxypropylene) isopropenyl phenyl ether, ethyl poly (oxypropylene) isopropenyl phenyl ether, poly (oxyethylene)
Polyalkyleneoxy groups such as isopropenyl benzyl ether, methyl poly (oxyethylene) isopropenyl benzyl ether, ethyl poly (oxyethylene) isopropenyl benzyl ether, poly (oxypropylene) isopropenyl benzyl ether, methyl poly (oxypropylene) isopropenyl benzyl ether A cumene compound having

Mono-polyalkylene glycol ester of dicarboxylic acid such as vinylphenyl succinate poly (oxyethylene), vinylphenylmethyl methyl hexa (hydroethylenephthalate) poly (oxyethylene), vinylphenylethyl ethyl terephthalate poly (oxyethylene), 4-vinylbenzoic acid. Acid poly (oxyethylene), 4-vinylbenzoic acid ethyl poly (oxyethylene), 4-isopropenylbenzoic acid methyl poly (oxypropylene), 4-isopropenylbenzoic acid ethyl poly (oxypropylene) and other vinyls having a polyalkyleneoxy group Examples thereof include benzoic acid ester and isopropenyl benzoic acid ester. You may use 2 or more types of these. In addition, a phenylene group of φ in the general formula is usually a mixture of a p-phenylene group and an o-phenylene group.

Examples of the epoxy group-containing vinyl monomer (B) used in the present invention include glycidyl (meth) acrylate, glycidyl cinnamate, allyl glycidyl ether, vinylcyclohexene monoepoxide, and 1,3-butadiene. Examples include monoepoxide. You may use 2 or more types of these.

The other polymerizable vinyl compound (C) used in the present invention can be used for improving the water resistance and hardness of the coating film. Specifically, aliphatic vinyl carboxylates such as vinyl acetate, aliphatic allyl carboxylates such as allyl acetate, allyl ethers such as allyl phenyl ether, alkyl (meth) acrylates such as methyl acrylate and ethyl methacrylate, styrene. , (Meth) acrylonitrile, (meth) acrylamide and the like. You may use 2 or more types of these.

The amount of the styrene monomer (A) used is 35 to 98% by weight, preferably 5% by weight, based on the whole copolymer (i).
0 to 95% by weight, and when the monomer (A) in the copolymer (i) is less than 35% by weight, the copolymer (i)
However, if it exceeds 98% by weight, a hard cured product cannot be obtained, which is not preferable. The amount of the epoxy group-containing vinyl monomer (B) used is 2 to 50% by weight, preferably 5 to 50% by weight, based on the whole copolymer (i).
35% by weight, and the component (B) in the copolymer (i) is 2
If it is less than 50% by weight, it becomes difficult to obtain a hard cured product. On the other hand, if it is more than 50% by weight, the viscosity of the liquid resin becomes high and coating becomes difficult, which is not preferable.

The liquid resin of the present invention has a number average molecular weight (in terms of polystyrene) of 5,000 to 100,000 measured by GPC method (gel permeation chromatograph) by adjusting the blending amount of the initiator. ,Preferably,
It is synthesized in the range of 8,000 to 60,000. When the number average molecular weight is less than 5,000, it is difficult to isolate the resin component from the polymerization solution, and the hardness,
The mechanical properties of the cured product such as flexibility may deteriorate, solvent resistance,
It is not preferable because boiling water resistance is lowered, and when the number average molecular weight is more than 100,000, the resin cannot maintain a coatable viscosity, which is not preferable.

The copolymer (i) used in the present invention can be produced by a solution method or a dispersion method of radical polymerization using a known radical polymerization initiator. Examples of the solvent used include ethyl acetate, methyl ethyl ketone, toluene, benzene, dioxane, tetrahydrofuran, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert.
-Butanol, methyl cellosolve, butyl cellosolve,
Examples thereof include methyl carbitol, ethyl carbitol, methyl cellosolve acetate, ethyl cellosolve acetate, diacetone alcohol and mixed solutions thereof. The radical polymerization initiator is not particularly limited, but examples thereof include peroxides such as benzoyl peroxide, t-butyl peroxide, cumene hydroperoxide, lauroyl peroxide, azobisisobutyronitrile, azobiscyclohexanenitrile. And the like, and persulfate initiators such as potassium persulfate and ammonium persulfate can be used. The content of such radical polymerization initiator is preferably 0.01 to 5% by weight, more preferably 0.1 to 3% by weight, based on the total amount of the monomers.

The viscosity of the obtained copolymer (i) is 500 to 3 at 50 ° C. measured by a rotary vibration viscometer.
It is preferably 10,000 cps, more preferably 800 to 20,000 cps.

Further, the copolymer (i) used in the present invention
Examples of the curing agent (ii) having two or more functional groups capable of binding to the epoxy group in one molecule include oxalic acid, malonic acid, succinic acid, glutaric acid, hexanedioic acid, citric acid, maleic acid, Aliphatic dicarboxylic acids such as methyl nadic acid and their anhydrides, ethylene glycol, diethylene glycol, glycerin, erythritol, arabitol, xylitol, sorbitol, dulcitol,
Polyhydric alcohols or polyhydric phenol compounds such as mannitol, catechol, resorcin, hydroquinone, guaiacol, hexylresorcin, pyrogallol, trihydroxybenzene, phloroglysin, dimethylolphenol, trimethylolpropane, or their alkoxy modified products, hexa Melamine compounds having an alkylol group or an alkoxy group such as methylolated melamine, hexamethoxymethylated melamine, and hexabutoxymethylated melamine, amino resins such as cyanuric acid, ammelide, melamine, benzoguanamine, diethanolamine, triethanolamine, and diaminopyridine. Compounds,

Tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, 1,5-naphthalene diisocyanate, lysine diisocyanate, hydrogenated 4,4'-diphenylmethane. Diisocyanates such as diisocyanate and hydrogenated tolylene diisocyanate, or isocyanate-end adducts of these with glycols or diamines, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, polyvalent isocyanate such as coronele L, glycine, Amino acids such as alanine and their lactams, citric acid, 12-hydroxystearic acid, 6-hydroxy Such as hydroxycarboxylic acids and lactones, such as lanthanum acid. You may use 2 or more types of these.

The composition amount of the curing agent (ii) is determined by the ratio of the epoxy group equivalent in the copolymer (i) and the functional group equivalent in the curing agent (ii). 0.01 to 10 chemical equivalents, preferably 0.1 to 5 chemical equivalents, relative to 1 equivalent of the epoxy group Copolymer (i)
When the functional group equivalent in the curing agent (ii) is less than 0.01 chemical equivalent to 1 equivalent of the epoxy group, a hard cured product cannot be obtained. On the contrary, when it is more than 10 chemical equivalents, unreacted. The curing agent (ii) is not preferable because it causes poor curing.

The resin composition of the present invention can be used as a substantially solvent-free paint or molding material. However, in order to improve the fluidity of the resin, a small amount of water, an organic solvent or the like may be added within 5% by weight of the resin composition. In addition, titanium white, colorants such as various pigments,
A lubricant or the like may be added. When the resin composition of the present invention is subjected to heat treatment or the like after coating or molding, the resin composition has an epoxy group-derived vinyl monomer (B) -derived epoxy group and a curing agent (ii) -derived functional group. , Addition reaction occurs and can be cured.

A curing catalyst generally used for improving the curing characteristics of the curable liquid resin composition of the present invention can be used. Examples of typical curing catalysts include pyridines such as pyridine, 4-dimethylaminopyridine, and 4-pyrrolidinopyridine, triethylamine, N, N.
Tertiary amines such as dimethylaniline, N, N-dimethylbenzylamine, N, N, N ′, N′-tetramethyl-1,3-butanediamine,

Organometallic compounds or organic complexes of metals such as diethylzinc, tetra (n-butoxy) titanium, dibutyltin dilaurate, dibutyltin di (2-ethylhexoate), sulfuric acid, zinc chloride, sodium hydroxide. Inorganic substances such as. The amount of such a curing catalyst added is preferably 0.01 to 1% by weight, and more preferably 0.02 to 0.5% by weight, based on the curable liquid resin composition. The heat treatment is preferably heating between 30 ° C and 250 ° C. The heat source is not particularly limited, but generally a heat circulation type oven or a heating roll is preferably used.

[0026]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. (Synthesis Example 1) 19 g of 1-dodecanol and 8 g of sodium hydride were stirred at room temperature in a tetrahydrofuran solvent. Then, 15 g of chloromethylstyrene (mixture of o-form and p-form) and 0.1 g of hydroquinone were added dropwise and refluxed for 10 hours to synthesize dodecyl vinylphenyl methyl ether.

(Synthesis Example 2) 17 g of 1-decanol and 20 g of thionyl chloride were stirred at room temperature in a tetrahydrofuran solvent. Then, after thionyl chloride was distilled off, 17 g of sodium 4-vinylbenzoate and 0.1 g of hydroquinone were added.
Was added dropwise and refluxed for 10 hours to synthesize decyl vinyl benzoate.

(Synthesis Example 3) 55 g of polyethylene glycol monomethyl ether (average molecular weight 550, manufactured by Aldrich) and 8 g of sodium hydride were stirred at room temperature in a tetrahydrofuran solvent. Then, 15 g of chloromethylstyrene (mixture of o-form and p-form) and 0.1 g of hydroquinone were added dropwise, and the mixture was refluxed for 10 hours to synthesize methyl poly (oxyethylene) vinylphenyl methyl ether.

(Synthesis Example 4) 75 g of polyethylene glycol monomethyl ether (average molecular weight 750, manufactured by Aldrich) and 70 g of thionyl chloride were stirred at room temperature in a tetrahydrofuran solvent. Thereafter, thionyl chloride was distilled off, 17 g of sodium 4-vinylbenzoate and 0.1 g of hydroquinone were added dropwise, and the mixture was refluxed for 10 hours to synthesize methyl poly (oxyethylene) vinylbenzoate.

(Synthesis Example 5) In a tetrahydrofuran solvent, 35 g of polyethylene glycol monomethyl ether (average molecular weight 350, manufactured by Aldrich) and 8 g of sodium hydride were stirred at room temperature. Then, 15 g of chloromethylstyrene (mixture of o-form and p-form) and 0.1 g of hydroquinone were added dropwise, and the mixture was refluxed for 10 hours to synthesize methyl poly (oxyethylene) vinylphenyl methyl ether.

(Examples 1 to 10 and Comparative Examples 1 and 2) The styrene monomer (A) synthesized in Synthesis Examples 1 to 5 and the vinyl monomer having an epoxy group (B) shown in Table 1 were used. ) Was copolymerized at the compounding ratio shown in Table 1. The copolymerization was carried out by using azobisisobutyronitrile as an initiator and refluxing it in hexane in Synthesis Examples 6 to 9 and in isopropanol solvent in Synthesis Examples 10 to 15 for 10 hours to obtain a resin. Each resin was precipitated and purified in petroleum ether. The obtained copolymer was analyzed by gel permeation chromatography (SC-8020, manufactured by Tosoh Corp.) using a number average molecular weight in terms of styrene and a rotational vibration viscometer (VM-100, manufactured by Yamaichi Denki Co., Ltd.). Viscosity measurements at 50 ° C were measured. The measurement results of the number average molecular weight and the viscosity (50 ° C.) are shown in Table 1.

Table 1 ──────────────────────────────────── Synthesis Example Styrene Having an epoxy group (A ) :( B) Monomer (A) vinyl unit at a number average of 50 ° C Weight ratio Molecular weight Viscosity cps Body (B) (× 10 ⁴ ) ──────────────── ───────────────────── 6 Synthesis Example 1 GMA Note 1) 90:10 1.0 8500 7 Synthesis Example 1 AGE Note 2) 95: 5 1.2 9500 8 Synthesis Example 2 GMA 85:15 1.3 11000 9 Synthesis example 2 AGE 95: 5 0.9 7000 10 Synthesis example 3 GMA 80:20 1.0 2000 11 Synthesis example 3 AGE 95: 5 1.1 2000 12 Synthesis example 4 GMA 70:30 1.3 3000 13 Synthesis example 4 AGE 95: 5 1.2 2300 14 Synthesis Example 5 GMA 90:10 0.8 1500 15 Synthesis Example 5 AGE 95: 5 1.2 2200 ──────────────────────── ───────────── Note 1) GMA: Grease Le methacrylate Note 2) AGE: allyl glycidyl ether

With respect to 1 equivalent of the epoxy group in the copolymer (i), the equivalent amount of the functional group of the curing agent (ii) was added as shown in Table 2, and dimethylbenzylamine was added to the total amount of 0. Pencil hardness after heating at 200 ° C for 20 minutes when 5% by weight is added (0.5 ° C on an aluminum plate on a hot plate at 50 ° C).
Coating with a mill applicator) is shown in Table 2. In Table 2, HMDI
Is hexamethylene diisocyanate, IPDI is isophorone diisocyanate, Coronate L is toluylene diisocyanate-modified trimethylolpropane manufactured by Nippon Polyurethane Industry Co., Ltd., and CY350 is methanol-modified melamine manufactured by Cyanamid. In Example 4, cobalt naphthenate was used instead of dimethylbenzylamine.

Table 2 ──────────────────────────────────── Examples and copolymers Curing agents Curing Agent (ii) Chemical equivalent of Comparative Example (i) (ii) after heating Pencil hardness ────────────────────────────── ─────── Example 1 Synthesis Example 6 HMDI 1.0 H Example 2 Synthesis Example 7 IPDI 1.0 H Example 3 Synthesis Example 8 Coronate L 1.0 3H Example 4 Synthesis Example 9 CY350 1.0 3H Example 5 Synthesis Example 10 Ethylene glycol 1.0 H Example 6 Synthetic example 11 Triethanolamine 1.0 2H Example 7 Synthetic example 12 Pyromellitic anhydride 1.0 3H Example 8 Synthetic example 13 Succinic anhydride 1.0 H Example 9 Synthetic example 14 Maleic anhydride 1.0 H Example 10 Synthetic Example 15 Terephthalic Anhydride 1.0 H Comparative Example 1 Synthetic Example 6--Softer than 9B Comparative Example 2 Synthetic Example 10--Softer than 9B ──────── ────────────────────────────

According to the present invention, a compatibilizer, an interface modifier,
A curable liquid comb resin used as a liquid resin for adhesives, medical materials, metal chelating agents, solvent-free paints, adhesives, and pressure-sensitive adhesives is simply provided.

Claims (2)

[Claims] 1. A styrene monomer (A) represented by the following general formula (35) to 98% by weight, a vinyl monomer (B) having an epoxy group (2) to 50% by weight, and other polymerizable vinyl compounds ( C) A copolymer (i) obtained by copolymerizing 0 to 20% by weight, and a curing agent (i) having two or more functional groups capable of binding to the epoxy group of the copolymer (i) in one molecule.
A curable resin composition comprising i). General ^{_{formula: CH 2 = C (R 1}} ) -φ-X-R 2 ( wherein, R ¹ represents a hydrogen atom or CH _3, R ² is 5 carbon atoms
22 represents an alkyl group of 22 or (C _n H _2n O) _m R ³ . Here, n is an integer of 1 to 3, m is an integer of 4 to 25, and R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. φ is a phenylene group which may have a substituent, X is —O—,
-COO- or -R represents a ⁴ O-. Here, R ⁴ is −
_{CH 2 -, - CH 2 CH} 2 -, - O-CO-R 5 -CO-,
^{_{-CH 2 O-CO-R 5}} -CO-, CH 2 CH 2 O-CO-
R ⁵ —CO— (However, R ⁵ is a direct bond or has 1 to 1 carbon atoms.
7 represents an optionally branched alkylene group. ) Represents. ) 2. The copolymer (i) has a viscosity of 500 to 30,0.
The curable resin composition according to claim 1, which is a liquid resin of 00 cps (50 ° C).