JP2000063614A - Resin composition and cured substance using this resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a one-pack type resin compsn. available for a wide range of uses in the fields, from a variety of coatings down, inks, adhesives, sealing agents, etc. SOLUTION: This resin compsn. contains (A) a polymer obtained by copolymerizing a monomer compsn. contg. (a) an ethylenically unsatd. monomer having two carboxylic acid groups in the mol. and (b) an ethylenicaly unsatd. monomer having at least one hydroxyl group in the molecule, (B) a compd. having one or more epoxy groups in the molecule, and (C) an onium salt selected from quaternary ammonium salts and quaternary phosphonium salts.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel and useful resin composition. INDUSTRIAL APPLICABILITY The resin composition of the present invention can be used in a wide variety of applications such as various paints, inks, adhesives, and sealing agents.

[0002]

2. Description of the Related Art For various paints, it is desired to make a one-pack type because of the ease of handling, etc., but in a one-pack type thermosetting paint, it is necessary to satisfy both the thermosetting property and the storage stability over time. It has become a challenge. As one of the paints that solves the above-mentioned problems and is provided with water resistance and acid resistance, a one-pack paint containing a half ester group, a hydroxyl group and an epoxy group as a curing component is disclosed in JP-A-2-45577 and JP-A-3-287650.
It is disclosed in the publication. However, in these paints, the complicated operation of obtaining a half ester group-containing compound by reacting an alcohol after copolymerizing an unsaturated monomer having an acid anhydride group such as maleic anhydride is required. Has been done. Further, since the reactivity of the acid anhydride group is high, there has been a problem that other monomer components and a polymerization solvent for copolymerizing the acid anhydride group-containing monomer are limited.

[0003]

Therefore, the present inventors
As a result of intensive studies to solve the above problems, it can be easily prepared with any composition, excellent storage stability over time,
Furthermore, we succeeded in synthesizing a resin composition in which a coating film formed by heat curing can exhibit good coating material physical properties such as adhesion to substrates and water resistance.

[0004]

The first invention is (A)
Ethylenic unsaturated containing (a) an ethylenically unsaturated monomer having two carboxylic acid groups in the molecule, and (b) an ethylenically unsaturated monomer having at least one hydroxyl group in the molecule A polymer obtained by copolymerizing a monomer composition, (B) a compound having one or more epoxy groups in the molecule, and (C) a quaternary ammonium salt,
A resin composition containing an onium salt selected from quaternary phosphonium salts. The second invention is
(A) The first ethylenically unsaturated monomer having two carboxylic acid groups in the molecule is itaconic acid
A resin composition according to the invention.

The third invention is characterized in that (C) the onium salt selected from the quaternary ammonium salt and the quaternary phosphonium salt is a tetraalkylammonium hydroxide having an alkyl group selected from 1 to 4 carbon atoms. The resin composition according to the first or second invention. 4th invention WHEREIN: Among the ethylenically unsaturated monomers, (a) 1 to 1 is the ethylenically unsaturated monomer which has two carboxylic acid groups in a molecule.
50% by weight, (b) 1 to 70% by weight of an ethylenically unsaturated monomer having at least one hydroxyl group in the molecule, and (A) an ethylenically unsaturated monomer composition is copolymerized. 1 to 100 parts by weight of a compound having one or more epoxy groups in the molecule, and (C) a quaternary ammonium salt or a quaternary phosphonium salt, relative to 100 parts by weight of the resulting polymer. First to third, wherein the amount of the onium salt is 0.1 to 20 parts by weight.
A resin composition according to any one of the inventions.

The fifth invention is a cured product using the resin composition according to any one of the first to fourth inventions.

[0007]

DETAILED DESCRIPTION OF THE INVENTION Although the detailed mechanism of the present invention is unknown, an onium salt selected from a quaternary ammonium salt and a quaternary phosphonium salt has a good catalytic activity for the reaction between a dibasic acid group and a hydroxyl group. The present invention has been found to have the following. The ethylenically unsaturated monomer having two carboxylic acid groups in the molecule (a) used in the present invention is not particularly limited, and examples thereof include itaconic acid, maleic acid, fumaric acid, glutaconic acid, Tetrahydrophthalic acid, a mixture thereof and the like,
Itaconic acid is particularly preferable. (A) The ethylenically unsaturated monomer having two carboxylic acid groups in the molecule is preferably 1 to 50% by weight in the ethylenically unsaturated monomer. If it is less than 1% by weight, it is difficult to sufficiently obtain the expected physical properties of the cured coating film.

The (b) ethylenically unsaturated monomer having at least one hydroxyl group in the molecule is not particularly limited, and examples thereof include 2-hydroxyethyl (meth) acrylate and 3-hydroxypropyl (meth). Acrylate, 2-hydroxypropyl (meth) acrylate,
4-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, glycerin (meth) acrylate, polyethylene glycol mono (meth) acrylate (n = 2 to 50), polycaprolactone Examples thereof include modified hydroxyethyl (meth) acrylate (n = 1 to 6), epoxy (meth) acrylate, hydroxyl group-terminated urethane (meth) acrylate, and a mixture thereof.
(B) The ethylenically unsaturated monomer having at least one hydroxyl group in the molecule is 1 in the ethylenically unsaturated monomer.
˜70 wt% is preferred. If it is less than 1% by weight, it is difficult to sufficiently obtain the expected physical properties of the cured coating film. The ethylenically unsaturated monomer composition may contain other ethylenically unsaturated monomers depending on the desired physical properties of the coating film. Other ethylenically unsaturated monomers are not particularly limited and examples thereof include (meth) acrylic acid, alkyl (meth) acrylate, styrene, vinyltoluene, (meth) acrylonitrile, vinyl acetate and the like. . The polymerization of the ethylenically unsaturated monomer composition is carried out in the presence of an initiator under an inert gas flow of 50.
It is carried out at ˜150 ° C. for 2 to 10 hours. If necessary, it may be carried out in the presence of a solvent. As the initiator, benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, diisopropyl peroxycarbonate, di t-butyl peroxide, organic peroxides such as t-butyl peroxybenzoate, 2,2 ′ Examples include azo compounds such as azobisisobutyronitrile. The initiator is preferably used in an amount of 1 to 20 parts by weight based on 100 parts by weight of the ethylenically unsaturated monomer composition. (B) The compound having one or more epoxy groups in the molecule is not particularly limited,
Examples include butyl glycidyl ether, phenyl glycidyl ether, biphenol diglycidyl ether type epoxy resin, bisphenol A diglycidyl ether type epoxy resin, bisphenol S diglycidyl ether type epoxy resin, bisphenol F diglycidyl ether type epoxy resin, hexahydrobisphenol A Diglycidyl ether type epoxy resin, polyethylene glycol diglycidyl ether (n = 1 to 50), polypropylene glycol diglycidyl ether (n = 1 to 5)
0), polytetraethylene glycol diglycidyl ether (n = 1 to 50), glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, neopentyl glycol diglycidyl ether, cresol novolac type epoxy resin and other glycidyl ether compounds; phthalic acid Glycidyl ester compounds such as diglycidyl ester, glycidyl amine compounds such as tetraglycidyl diaminodiphenylmethane, tetraglycidyl metaxylenediamine; glycidyl compounds such as triglycidyl isocyanurate; 3,4-epoxy-6-
Aliphatic epoxy compounds such as methylcyclohexylmethylcarboxylate; Copolymerizing ethylenically unsaturated monomers having at least one epoxy group in the molecule such as glycidyl (meth) acrylate with other ethylenically unsaturated monomers Examples of the resin obtained by such a method include compounds obtained by oxidizing a compound having an unsaturated double bond such as epoxidized polybutadiene. (B) 1 in the molecule
The compound having one or more epoxy groups is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the polymer obtained by copolymerizing the (A) ethylenically unsaturated monomer composition. If the amount is less than 1 part by weight or more than 100 parts by weight, it is difficult to obtain the desired physical properties of the cured coating film.

The (C) onium salt selected from quaternary ammonium salts and quaternary phosphonium salts is not particularly limited, and examples thereof include tetramethyl and tetraethyl as substituents bonded to nitrogen or phosphorus atoms. ,
Tetrapropyl, tetrabutyl, tetrahexyl, tetraoctyl, tetradecyl, tetrahexadecyl, trimethylethyl, trimethyloctyl, trimethyldodecyl, trimethyldecyl, trimethyldodecyl, trimethylcetyl, trimethylbenzyl, trimethyl2-hydroxyethylammonium, triethylhexyl, triethylbenzyl , Dimethylethylcetyl, dimethylethylhexadecyl, dimethylbenzylcetyl, dimethylhexadecylbenzyl, dimethyldidecyl, dimethyldidodecyl, dimethyldihexadecyl, dimethyldilauryl,
As a counter anion of quaternary salt such as dimethyldioctadecyl, dimethyldistearyl, dimethyldiallyl,
Examples thereof include chloride, bromide, iodide, hydroxide, acetate, p-toluenesulfonate, hydrogen sulfate, phosphate, sulfate and the like. In particular, tetraalkylammonium hydroxide having an alkyl group selected from 1 to 4 carbon atoms is preferable. The onium salt (C) selected from the quaternary ammonium salt and the quaternary phosphonium salt is 0.1 parts by weight with respect to 100 parts by weight of a polymer obtained by copolymerizing the (A) ethylenically unsaturated monomer composition. It is preferably about 20 parts by weight. If it is less than 0.1 part by weight, it is difficult to obtain the expected cured coating properties sufficiently, and if it exceeds 20 parts by weight, the onium salt remaining in the coating deteriorates the coating properties such as water resistance. Is likely to occur and is not preferable. The resin composition of the present invention can be used by containing an organic solvent, if necessary.

Further, although the resin composition of the present invention can be used alone, it can be used by containing other resin components if necessary. For example, acrylic resin, polyester resin, urethane resin and the like can be mentioned, and it is preferably used in an amount of 5 to 95% by weight based on the total solid content. Further, these resin compositions include dyes for coloring and the like, pigments, various additives for improving the physical properties of the cured product, such as fillers, leveling agents, curing agents, flame retardants, and thickeners, if necessary. Agents, lubricity imparting agents and the like can be contained. INDUSTRIAL APPLICABILITY The resin composition of the present invention can be suitably used for a wide variety of applications such as various paints, inks, adhesives, and sealing agents. The coating method is not particularly limited, and examples thereof include brush coating, coating with a roll coater, bar coater, applicator, etc., electrodeposition coating, spray coating, dipping and the like. Further, after coating, it is easily cured by heating and exhibits excellent coating film physical properties. The curing temperature is not particularly limited, but 100 ° C or higher is desirable.

[0011]

EXAMPLES The present invention will be specifically described below with reference to examples. In the following, all "parts" represent parts by weight. A production example of a resin solution will be described before the examples. Production Example 1 Temperature control regulator in a separable 4-neck flask,
Butyl cellosolve 100 with cooling tube and stirring device
Parts, the temperature was raised to about 90 ° C., and the inside of the reaction vessel was replaced with nitrogen, then 40 parts of styrene, 40 parts of ethyl acrylate, 20 parts of glycidyl methacrylate, organic peroxide (“Perbutyl O” manufactured by NOF CORPORATION). ) 5 parts was added dropwise over 2 hours. After the dropping was completed, the reaction was continued for another 3 hours to obtain a resin solution (B1) having a solid content of 50%.

Example 1 A separable 4-neck flask was equipped with a temperature control regulator,
Butyl cellosolve 100 with cooling tube and stirring device
Parts were charged, the temperature was raised to about 90 ° C., and the inside of the reaction vessel was replaced with nitrogen. Then, 2 parts of itaconic acid, 2 parts of 2-hydroxyethyl methacrylate, 70 parts of styrene, 26 parts of ethyl acrylate, organic peroxide ( 5 parts of "Perbutyl O" manufactured by NOF CORPORATION was added dropwise over 2 hours. After the dropping was completed, the reaction was continued for another 3 hours to obtain a resin solution (A
1) was obtained. To 100 parts of the obtained resin solution (A1), 1 part of trimethylolpropane triglycidyl ether and 1 part of tetramethylammonium hydroxide were added with sufficient stirring to obtain a resin composition.

Example 2 A separable 4-neck flask was equipped with a temperature control regulator,
Butyl cellosolve 100 with cooling tube and stirring device
Then, the temperature in the reaction vessel was replaced with nitrogen, and then 45 parts of itaconic acid, 20 parts of 2-hydroxyethyl methacrylate, 30 parts of styrene, 5 parts of ethyl acrylate, and organic peroxide ( 5 parts of "Perbutyl O" manufactured by NOF CORPORATION was added dropwise over 2 hours. After the dropping is completed,
The reaction was continued for another 3 hours, and the resin solution (A
2) was obtained. 50 parts of the resin solution (A2) thus obtained, 50 parts of the epoxy group-containing resin solution (B1) obtained in Production Example 1,
Tetramethylammonium hydroxide 0.1 part was added with sufficient stirring to obtain a resin composition.

Example 3 A separable 4-neck flask was equipped with a temperature control regulator,
Butyl cellosolve 100 with cooling tube and stirring device
Parts, the temperature was raised to about 90 ° C. and the inside of the reaction vessel was replaced with nitrogen, then 10 parts of itaconic acid, 65 parts of 4-hydroxybutyl acrylate, 25 parts of styrene, organic peroxide (manufactured by NOF Corporation) 5 parts of perbutyl O ") was added dropwise over 2 hours. After the dropping was completed, the reaction was continued for another 3 hours to obtain a resin solution (A3) having a solid content of 50%. Epicoat 828 (bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd.) 12.5 on 100 parts of the obtained resin solution (A3)
Parts and 6.5 parts of tetrabutylammonium hydroxide were added with sufficient stirring to obtain a resin composition.

Comparative Example 1 To 100 parts of the resin solution (A1) obtained in Example 1, 1 part of trimethylolpropane triglycidyl ether was added with sufficient stirring to obtain a resin composition. Comparative Example 2 To 100 parts of the resin solution (A1) obtained in Example 1, 1 part of trimethylolpropane triglycidyl ether and 1 part of p-toluenesulfonic acid were added with sufficient stirring to obtain a resin composition. Comparative Example 3 To 100 parts of the resin solution (A2) obtained in Example 2, 0.1 part of tetramethylammonium hydroxide was added with sufficient stirring to obtain a resin composition.

Comparative Example 4 A separable four-necked flask was equipped with a temperature control regulator,
Butyl cellosolve 100 with cooling tube and stirring device
Was charged, the temperature was raised to about 90 ° C., and the inside of the reaction vessel was replaced with nitrogen. Then, 0.5 part of itaconic acid, 0.5 part of 2-hydroxyethyl methacrylate, 50 parts of styrene, 49 parts of ethyl acrylate, organic 5 parts of peroxide (“Perbutyl O” manufactured by NOF CORPORATION) was added dropwise over 2 hours. After the dropping was completed, the reaction was continued for another 3 hours to obtain a resin solution having a solid content of 50%. To 100 parts of the obtained resin solution, 1 part of trimethylolpropane triglycidyl ether and 0.02 part of tetramethylammonium hydroxide were added with sufficient stirring to obtain a resin composition.

Comparative Example 5 A separable four-necked flask was equipped with a temperature control regulator,
Butyl cellosolve 100 with cooling tube and stirring device
Parts, the temperature was raised to about 90 ° C. and the inside of the reaction vessel was replaced with nitrogen, then 70 parts of itaconic acid, 20 parts of 2-hydroxyethyl methacrylate, 10 parts of styrene, organic peroxide (manufactured by NOF CORPORATION). 5 parts of perbutyl O ") was added dropwise over 2 hours. After the dropping is completed, the reaction is continued for another 3 hours,
A resin solution having a solid content of 50% was obtained. Resin solution 10 obtained
To 0 part, 1 part of trimethylolpropane triglycidyl ether and 15 parts of tetramethylammonium hydroxide were added with sufficient stirring to obtain a resin composition.

The changes in viscosity of the resin compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 5 after storage at room temperature for 3 months were evaluated. Further, these resin compositions were applied to a tin-free steel plate by a wire bar coater so that the dry coating film thickness was about 10 μm, and dried at 160 ° C. for 10 minutes. The results of evaluation of alkali resistance are shown in Table 1.

[0019]

[Table 1]

(Note 1) A cross-cut cellophane tape peeling test was performed by the ratio of the number of squares left without peeling. (Note 2) The state of the coating film after being immersed in boiling water for 30 minutes was visually evaluated. (Note 3) About 0.05 of 0.1N sodium hydroxide aqueous solution
Droplets of ml were dropped on the coating film, and changes in the coating film after 24 hours were visually evaluated.

[0021]

The resin composition thus obtained has excellent storage stability over time and has good substrate adhesion, water resistance, chemical resistance and the like in its cured coating film, and for various paints and inks. ,
As a binder for adhesives and sealing agents,
It can be used for a wide range of applications and has been found to be extremely useful.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 63/00 C08L 63/00 C (72) Inventor Yufumi Mashita 2-33 Kyobashi, Chuo-ku, Tokyo Toyo Inki Manufacturing Co., Ltd. F term (reference) 4J002 BG071 BH021 CD012 CD022 CD052 CD102 CD112 CD132 CD142 CD162 CD191 CH051 EL026 EL036 EN137 EW177 FD142 FD146 FD157 GH01 GJ00

Claims (5)

[Claims] 1. (A) (a) an ethylenically unsaturated monomer having two carboxylic acid groups in the molecule, and (b) an ethylenically unsaturated monomer having at least one hydroxyl group in the molecule. A polymer obtained by copolymerizing an ethylenically unsaturated monomer composition containing and, (B) a compound having one or more epoxy groups in the molecule, and (C) 4
A resin composition comprising an onium salt selected from a quaternary ammonium salt and a quaternary phosphonium salt. 2. The resin composition according to claim 1, wherein the (a) ethylenically unsaturated monomer having two carboxylic acid groups in the molecule is itaconic acid. 3. An onium salt selected from (C) quaternary ammonium salt and quaternary phosphonium salt is a tetraalkylammonium hydroxide having an alkyl group selected from 1 to 4 carbon atoms. 1 or 2
The resin composition described. 4. In the ethylenically unsaturated monomer, 1 to 50% by weight of (a) an ethylenically unsaturated monomer having two carboxylic acid groups in the molecule, and (b) at least one in the molecule. 1 to 70% by weight of the ethylenically unsaturated monomer having a hydroxyl group, and (A) based on 100 parts by weight of a polymer obtained by copolymerizing the ethylenically unsaturated monomer composition. , (B) 1 to 100 parts by weight of a compound having one or more epoxy groups in the molecule, and (C) 0.1 to 20 parts by weight of an onium salt selected from a quaternary ammonium salt and a quaternary phosphonium salt. It exists, The resin composition in any one of Claims 1-3. 5. A cured product using the resin composition according to claim 1.