JP2000063615A - Resin composition and cured substance using the same - 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 molecules and (b) an ethylenically unsatd. monomer having at least one hydroxyl group in the molecule, and (B) 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 resin composition comprising a polymer obtained by copolymerizing a monomer composition and (B) an onium salt selected from a quaternary ammonium salt and a quaternary phosphonium salt. A second invention is the resin composition according to the first invention, characterized in that (a) the ethylenically unsaturated monomer having two carboxylic acid groups in the molecule is itaconic acid.

The third invention is characterized in that the onium salt (B) 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. 0.1 to 20 parts by weight of the onium salt selected from (B) quaternary ammonium salt and quaternary phosphonium salt, relative to 100 parts by weight of the resulting polymer. A resin composition according to any one of the inventions.

A fifth aspect of the invention is that the ethylenically unsaturated monomer composition contains (c) 1 to 50% by weight of an ethylenically unsaturated monomer having at least one epoxy group in the molecule. The resin composition according to any one of the first to fourth aspects of the invention. A sixth 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 and tetrahydro. Examples thereof include phthalic acid and a mixture thereof, with itaconic acid being 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. 1% by weight
If it is less than 50% by weight, it is difficult to sufficiently obtain the expected physical properties of the cured coating film.

(B) The 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), modified with polycaprolactone Examples thereof include hydroxyethyl (methacrylate (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 to 70 in the ethylenically unsaturated monomer.
Weight percent 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.

Further, it contains (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. By containing (c) an ethylenically unsaturated monomer having at least one epoxy group in the molecule in the ethylenically unsaturated monomer composition, the physical properties such as water resistance of the resulting cured coating film can be improved. It is possible to further improve. (C) The ethylenically unsaturated monomer having at least one epoxy group in the molecule is not particularly limited, and examples thereof include glycidyl (meth) acrylate and 3,4-epoxycyclohexanylmethyl (meth).
Examples thereof include acrylate, 3,4-epoxycyclohexanylmethyl group-containing lactone-modified methacrylic acid ester (manufactured by Daicel Chemical Industries, Cyclomer), and allyl glycidyl ether. (C) The ethylenically unsaturated monomer having at least one epoxy group in the molecule is preferably 1 to 50% by weight in the ethylenically unsaturated monomer. 1
If it is less than 50% by weight, it is difficult to sufficiently obtain the expected physical properties of the cured coating film, and if it exceeds 50% by weight, the viscosity of the resin is increased, which is not preferable.

The above-mentioned 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. . Polymerization of the ethylenically unsaturated monomer composition is carried out in the presence of an initiator under an inert gas stream at 50 to 150 ° C. for 2 to 10 hours. If necessary, it may be carried out in the presence of a solvent.

As the initiator, organic peroxides such as benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, diisopropyl peroxycarbonate, dit-butyl peroxide and t-butyl peroxybenzoate, 2 , 2'-azobisisobutyronitrile and other azo compounds. 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 onium salt selected from the quaternary ammonium salt and the quaternary phosphonium salt is not particularly limited, and examples thereof include tetramethyl, tetraethyl and tetrapropyl as the substituent bonded to the nitrogen or phosphorus atom. , Tetrabutyl, tetrahexyl, tetraoctyl, tetradecyl, tetrahexadecyl, trimethylethyl, trimethyloctyl, trimethyldodecyl, trimethyldecyl, trimethyldodecyl, trimethylcetyl, trimethylbenzyl, trimethyl2-hydroxyethylammonium, triethylhexyl, triethylbenzyl, dimethyl Ethyl cetyl, dimethyl ethyl hexadecyl, dimethyl benzyl cetyl, dimethyl hexadecyl benzyl,
Dimethyldidecyl, dimethyldidodecyl, dimethyldihexadecyl, dimethyldilauryl, dimethyldioctadecyl, dimethyldistearyl, dimethyldiallyl, etc., 4
As counter anions of primary salts, chloride, bromide, iodide, hydroxide, acetate, p
-Toluene sulfonate, 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 (B) quaternary ammonium salt and the onium salt selected from the quaternary phosphonium salt are 0.1 parts by weight per 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. Furthermore, the resin composition of the present invention can be used alone, but 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.

The resin composition of the present invention is used for various paints,
It can be suitably used for a wide range of applications such as inks, adhesives and sealing agents. The coating method is not particularly limited, and as an example, brush coating,
Examples include 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.

[0014]

EXAMPLES The present invention will be specifically described below with reference to examples. In the following, all "parts" represent parts by weight. Example 1 A separable four-necked 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 10 parts of itaconic acid, 20 parts of 2-hydroxyethyl methacrylate, 50 parts of styrene, 20 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 (A1) having a solid content of 50%. To 100 parts of the obtained resin solution (A1), 1 part of tetramethylammonium hydroxide was added with sufficient stirring to obtain a resin composition.

Example 2 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 atmosphere in the reaction vessel was replaced with nitrogen.
5 parts of organic 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 (A2) having a solid content of 50%. To 100 parts of the obtained resin solution (A2), 1 part of tetrabutylammonium bromide 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 atmosphere in the reaction vessel was replaced with nitrogen. 5 parts of organic 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 (A3) having a solid content of 50%. To 100 parts of the obtained resin solution (A3), 0.1 part of tetramethylammonium hydroxide was added with sufficient stirring to obtain a resin composition.

Example 4 A separable four-necked flask was equipped with a temperature control regulator,
Butyl cellosolve 100 with cooling tube and stirring device
20 parts of itaconic acid, 20 parts of 2-hydroxyethyl methacrylate, and 15 parts of ethyl acrylate were added from a dropping pipe after the contents were charged, the temperature was raised to about 90 ° C. and the inside of the reaction vessel was replaced with nitrogen.
Parts, 45 parts of glycidyl methacrylate, and 5 parts of organic peroxide (“Perbutyl O” manufactured by NOF CORPORATION) were added dropwise over 2 hours. After the dropping was completed, the reaction was continued for another 3 hours to obtain a resin solution (A4) having a solid content of 50%. To 100 parts of the obtained resin solution (A4), 6.5 parts of tetraethylammonium hydroxide was added with sufficient stirring to obtain a resin composition.

Comparative Example 1 The resin solution (A1) obtained in Example 1 was used as it was as a resin composition. Comparative Example 2 The resin solution (A2) obtained in Example 2 was used as it was as a resin composition. Comparative Example 3 To 100 parts of the resin solution (A1) obtained in Example 1, 1 part of p-toluenesulfonic acid was added with sufficient stirring to obtain a resin composition.

Comparative Example 4 To 100 parts of the resin solution (A2) obtained in Example 2, 1 part of p-toluenesulfonic acid was added with sufficient stirring to obtain a resin composition. Comparative Example 5 A separable 4-necked flask 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, 0.02 part of tetramethylammonium hydroxide was added with sufficient stirring to obtain a resin composition.

Comparative Example 6 A separable 4-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
15 parts of tetramethylammonium hydroxide was added to 0 parts with sufficient stirring to obtain a resin composition. The change in viscosity of the resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 6 after storage at room temperature for 3 months was 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.

[0021]

[Table 1]

(Note 1) In the cross-cut cellophane tape peeling test, the number of squares left without peeling was evaluated. (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.

[0023]

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 has been found that it can be used in a wide range of applications and is extremely useful in industry.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // C09D 133/14 C09D 133/14 135/00 135/00 C09J 133/14 C09J 133/14 135/00 135/00 (72) Inventor Yukifumi Mashita 2-3-13 Kyobashi, Chuo-ku, Tokyo Toyo Inki Manufacturing Co., Ltd. F-term (reference) 4J002 BE041 BG071 BH021 CD191 CH011 EN136 EV266 EW176 GH01 GJ01 GJ02 4J038 CG061 CG071 CG141 CH121 EA011 GA03 GA06 JB11 JC29 4J040 DF061 DG001 DN061 GA05 GA07 HC01 HD21 JB02 LA05 LA06 LA07

Claims (6)

[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. And (B) a polymer obtained by copolymerizing an ethylenically unsaturated monomer composition containing
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 (B) a quaternary ammonium salt and a 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. The resin composition according to any one of claims 1 to 3, wherein the onium salt selected from (B) quaternary ammonium salt and quaternary phosphonium salt is 0.1 to 20 parts by weight. 5. An ethylenically unsaturated monomer composition containing (c)
The resin composition according to any one of claims 1 to 4, which contains 1 to 50% by weight of an ethylenically unsaturated monomer having at least one epoxy group in the molecule. 6. A cured product using the resin composition according to claim 1.