JP4193677B2 - Self-crosslinking resin, production method, resin composition and application - Google Patents

Description

  The present invention relates to a self-crosslinking resin having an oxetane group and a heat latent carboxyl group in the same molecule, a method for producing the same, a resin composition, a cured product obtained by curing the self-crosslinking resin or the resin composition, and a cured product. It relates to the use of things.

Self-crosslinking resins having an epoxy group and a carboxyl group in the same molecule are widely used as a means for curing a paint film. For example, a self-crosslinkable resin prepared by polymerizing a monomer component mainly composed of a glycidyl group-containing polymerizable unsaturated monomer and a carboxyl group-containing polymerizable unsaturated monomer has been proposed. (Patent Document 1)
However, in this method, the functional groups of the two unsaturated monomers react with each other at the time of blending the components or during polymerization, so that gelation or partial polymerization occurs. There is a problem that the variation of the size becomes large.
Resins having self-crosslinking properties have been developed in which oxetane groups with lower reactivity are introduced instead of epoxy groups (Patent Documents 2 and 3). However, the problem of gelation and polymerization has not been solved at all.
As a method for solving these problems, a self-crosslinkable resin obtained by ring-opening half-ester reaction of a cyclic acid anhydride with the hydroxyl group of a compound having a hydroxyl group and an epoxy group in the same molecule, or an epoxy group and a cyclic acid anhydride A self-crosslinkable resin in which an alcohol component is subjected to a ring-opening half ester reaction with the cyclic acid anhydride group of a compound having a group in the same molecule has been proposed. (Patent Document 4)
However, even in these methods, the reaction between the carboxyl group generated by the ring-opening half-esterification reaction and the epoxy group proceeds, resulting in problems such as gelation and polymerization. For this reason, there is a demand for a material that is excellent in stability in a compounding system, can be cured by heat alone without a catalyst, and exhibits excellent physical properties chemically and physically when the resin composition is cured.

JP-A-63-135465 JP-A-9-221602 JP 2002-322268 A JP 7-126345 A

A first object of the present invention is to provide a self-crosslinking resin having an oxetane group and a heat latent carboxyl group in the same molecule.
A second object of the present invention is to provide a method for producing the self-crosslinkable resin without gelation or partial polymerization.
Furthermore, the third object of the present invention is to provide a thermosetting composition using the self-crosslinking resin.
The fourth object of the present invention is to provide a cured product obtained by curing the self-crosslinkable resin or resin composition and a use.

  As a result of intensive studies to develop the self-crosslinking resin, the present inventors have added a cyclic acid anhydride group to the hydroxyl group of a compound having at least one hydroxyl group and one oxetane group per molecule. A specific self-crosslinkable resin obtained by esterification and further reacting a generated vinyl group with a monovinyl (thio) ether compound can achieve its purpose, and the present invention has been completed. It was.

That is, the present invention includes the following [1] to [11].
[1] Using a hydroxyoxetane compound having at least one hydroxyl group and an oxetane group in one molecule and a compound having at least one cyclic acid anhydride group in one molecule, the hydroxyl group and the cyclic acid anhydride group Is a self-crosslinkable resin obtained by carrying out a half-esterification reaction to obtain a compound having a carboxyl group and an oxetane group, and further subjecting the carboxyl group of the compound to a monovinyl (thio) ether compound.
[2] The self-crosslinking resin according to the above [1] represented by the following formula (1).

[Wherein, m, n is an integer from 1 to 6, R is 2-12 monovalent organic group having 1 to 50 carbon atoms, ^{A 1} is a group represented by the following formula (2) or (3) A ² represents a linear or branched alkyl group having 1 to 20 carbon atoms. ]

(In the formula, R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, R ⁴ is an organic group having 1 to 18 carbon atoms, and Y ¹ is an oxygen atom or a sulfur atom.)

(Wherein R ⁵ and R ⁶ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, R ⁷ is a divalent organic group having 1 to 18 carbon atoms, and R ⁸ is a divalent carbon group having 1 to 18 carbon atoms. An organic group, Y ² is an oxygen atom or a sulfur atom, and forms a heterocycle having Y ² as a hetero atom.)

[3] A method for producing a self-crosslinkable resin, characterized by performing the following step I and step II.
Step I: a step of subjecting a hydroxyl oxetane compound having at least one hydroxyl group and an oxetane group in a molecule as a raw material to a half esterification reaction of the hydroxyl group with a compound having at least one cyclic acid anhydride group per molecule .
Step II: Further, a step of adding a monovinyl (thio) ether compound to the generated carboxyl group.
[4] The method for producing a self-crosslinking resin according to [3], wherein a base catalyst is used as a catalyst in the reaction.
[5] A thermosetting composition containing the self-crosslinking resin according to the above [1] or [2] and a catalyst.
[6] The thermosetting composition according to [5], wherein the catalyst is a thermolatent catalyst that exhibits activity during heat curing.

[7] The thermosetting composition according to the above [5] or [6], wherein the catalyst is a compound derived from an aluminum complex.
[8] Any one of [5] to [7] above, further comprising a compound having one or more reactive functional groups capable of forming a chemical bond with a carboxyl group by heating in one molecule. The thermosetting composition as described.
[9] The thermosetting composition according to [8], wherein the reactive functional group is an epoxy group or an oxetane group.
[10] A cured resin obtained by curing the self-crosslinking resin according to [1] or [2] or the thermosetting composition according to any of [5] to [9].
[11] An electronic component obtained by curing the self-crosslinking resin according to [1] or [2] or the thermosetting resin composition according to any one of [5] to [9].

  According to the present invention, there is provided a self-crosslinkable resin that is excellent in solubility in various organic solvents and resins, does not require a curing agent, and can be cured by heating alone. Moreover, the thermosetting resin composition which is excellent also in storage stability is provided by mix | blending the thermosetting resin of this invention. Furthermore, by curing the self-crosslinking resin and the thermosetting resin composition of the present invention, a cured resin product excellent in chemical performance and physical performance, and an electronic component utilizing these performances are provided.

Hereinafter, the present invention will be described in detail.
The self-crosslinkable resin (A) of the present invention comprises a hydroxyoxetane compound (a1) having at least one hydroxyl group and an oxetane group in one molecule, and a compound having one or more cyclic acid anhydride groups in one molecule ( Using a2), the hydroxyl group and the cyclic acid anhydride group are half-esterified to obtain a compound (a12) having a carboxyl group and an oxetane group, and further, the carboxyl group of the compound (a12) and monovinyl It can be obtained by addition reaction of (thio) ether compound (a3).
The self-crosslinking resin (A) of the present invention is more preferably represented by the following formula (1).

(Wherein, m, n is an integer from 1 to 6, R is 2-12 monovalent organic group having 1 to 50 carbon atoms, ^{A 1} is represented by the following formula (2) or (3) .A ² showing a group represents a linear or branched alkyl group having a carbon number of 1-20.
Specifically, R in the formula is a substituted or unsubstituted hydrocarbon group having 1 to 50 carbon atoms, a substituted or unsubstituted aromatic group, or the like. )

(In the formula, R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, R ⁴ is an organic group having 1 to 18 carbon atoms, and Y ¹ is an oxygen atom or a sulfur atom.)

(Wherein R ⁵ and R ⁶ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, R ⁷ is a divalent organic group having 1 to 18 carbon atoms, and R ⁸ is a divalent carbon group having 1 to 18 carbon atoms. An organic group, Y ² is an oxygen atom or a sulfur atom, and forms a heterocycle having Y ² as a hetero atom.)

In the formula (2), R ¹ , R ² and R ³ are each a hydrogen atom or a saturated hydrocarbon group having 1 to 18 carbon atoms, an unsaturated hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. R ⁴ is an organic group such as a saturated hydrocarbon group having 1 to 18 carbon atoms, an unsaturated hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group, and these organic groups May have an appropriate substituent, and Y ¹ is an oxygen atom or a sulfur atom.
In Formula (3), R ⁵ and R ⁶ are each an organic atom such as a hydrogen atom or a saturated hydrocarbon group having 1 to 18 carbon atoms, an unsaturated hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. Group, these organic groups may have an appropriate substituent, R ⁷ is a divalent organic group having 1 to 18 carbon atoms, R ⁸ is a divalent organic group having 1 to 18 carbon atoms, Y ² is an oxygen atom or a sulfur atom, form a heterocyclic structure which comprises Y ² as the hetero atom.

  In the present invention, the self-crosslinking property refers to a property having curable properties by itself without adding any other subcomponent. In the resin (A) of the present invention, a blocked carboxyl group that is a latent reactive group is converted to a carboxyl group by heating, and an addition reaction with an oxetane group in the same resin (A) The self-crosslinking property is shown.

The self-crosslinkable resin (A) of the present invention can be produced by the following method.
That is, as the reaction in Step I, the compound (a2) having one or more cyclic acid anhydride groups per molecule is opened on the hydroxyl group of the hydroxyoxetane compound (a1) having a hydroxyl group and an oxetane group in the same molecule. Half-esterification reaction is performed, and then, as a reaction of Step II, the compound obtained by the reaction of Step I described above is used as a starting material, and the newly generated carboxyl group is converted to a monovinyl (thio) ether compound (a3). Is added to obtain a self-crosslinkable resin (A) in which the carboxyl group is blocked.
The series of two-stage reactions may be performed sequentially, or may be continuously performed in the same reaction vessel without once recovering the intermediate reactant.

Next, the raw material used for manufacture of self-crosslinkable resin (A) is demonstrated.
Examples of the hydroxyoxetane compound (a1) having a hydroxyl group and an oxetane group in the same molecule include compounds represented by the following formula (4).

(Here, A ² is the same as described above and represents a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms.)

Specifically, 3-hydroxymethyl oxetane, 3-methyl-3-hydroxymethyl oxetane, 3-ethyl-3-hydroxymethyl oxetane, 3-propyl-3-hydroxymethyl oxetane, 3-butyl-3-hydroxymethyl oxetane 3-hexyl-3-hydroxymethyloxetane, 3-cyclohexyl-3-hydroxymethyloxetane, 3-phenyl-3-hydroxymethyloxetane, and the like. Among these hydroxyoxetane compounds (a1), 3-ethyl-3-hydroxymethyloxetane is preferable from the viewpoint of availability.
The said raw material (a1) can be used individually by 1 type or in mixture of 2 or more types.

Examples of the compound (a2) having one or more cyclic carboxylic acid anhydride groups in one molecule include the following compounds 1) and 2).
1) A compound having one cyclic carboxylic anhydride group in one molecule.
More specifically, aromatic carboxylic anhydrides such as phthalic anhydride, trimellitic anhydride, tetrabromophthalic anhydride, and tetrachlorophthalic anhydride; aliphatics such as succinic anhydride, maleic anhydride, and dodecenyl succinic anhydride Carboxylic anhydrides; alicyclic carboxylic anhydrides such as tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl nadic anhydride, hymic anhydride, chlorendic anhydride (trade name is anhydrous het acid) It is done.
2) A compound having two or more cyclic carboxylic anhydride groups in one molecule.
More specifically, pyromellitic anhydride 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, ethylene glycol bis (anhydrotrimellitate), Aromatic carboxylic acid anhydrides such as glycerol bisanhydro trimellitate monoacetate and diphenylsulfone tetracarboxylic dianhydride; anhydrides of aliphatic carboxylic acids such as butanetetracarboxylic dianhydride; hydrogenated trimellitic anhydride 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,4-dicarboxy-1,2,3,4 -Alicyclic carboxylic acid anhydrides such as tetrahydro-1-naphthalene succinic dianhydride.
The compound (a 2 ) having one or more cyclic acid anhydride groups in one molecule may have a functional group other than the cyclic carboxylic acid anhydride group. In step II, the group can react with the vinyl (thio) ether (a3) and function as a part of the latent active group of the self-crosslinkable resin (A) of the present invention. Specifically, for example, benzene polycarboxylic acid such as pyromellitic anhydride formed an anhydride; cycloalkane polycarboxylic acid such as cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride is anhydrous What formed the thing etc. can use it conveniently.
Among these cyclic acid anhydrides (a2), succinic anhydride, tetrahydrophthalic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 5- (2,5-Dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride is a point of availability and the solvent or resin of the resulting self-crosslinkable resin From the viewpoint of solubility in
The said raw material (a2) can be used individually by 1 type or in mixture of 2 or more types.

  Examples of the monovinyl (thio) ether compound (a3) include compounds represented by the following formula (5) or (6).

(Here, R ¹ , R ² , R ³ , R ⁴ , Y ¹ are the same as those in the formula (2), and R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms. R ⁴ is an organic group having 1 to 18 carbon atoms, and Y ¹ is an oxygen atom or a sulfur atom.)

(Wherein R ⁵ and R ⁶ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, R ⁷ is a divalent organic group having 1 to 18 carbon atoms, and R ⁸ is a divalent carbon group having 1 to 18 carbon atoms. An organic group, Y ² is an oxygen atom or a sulfur atom, and forms a heterocycle having Y ² as a hetero atom.)
Examples of the chain vinyl (thio) ether compound represented by the formula (5) include methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, t- Alkyl vinyl ethers such as amyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether; hydroxyethyl vinyl ether, 9-hydroxynonyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, cyclohexanedimethanol monovinyl ether, Hydroxybutyl vinyl ether, ethylene glycol monovinyl ether, hexanediol monovinyl Ethers, vinyl ethers containing hydroxyl groups such as diethylene glycol monovinyl ether; ethylene glycol butyl vinyl ether, alkylene glycol alkyl vinyl ethers such as triethylene glycol methyl vinyl ether; other vinyl ethers such as aminopropyl vinyl ether, diethylaminoethyl vinyl ether, propenyl ether propylene carbonate, etc. And the corresponding vinyl thioethers.

  Furthermore, specific examples of the cyclic vinyl (thio) ether compound represented by the formula (6) include 2,3-dihydrofuran, 3,4-dihydrofuran, and 2,3-dihydro-2H. -Pyran, 3,4-dihydro-2H-pyran, 3,4-dihydro-2-methoxy-2H-pyran, 3,4-dihydro-4,4-dimethyl-2H-pyran-2-one, 3,4 -Cyclic vinyl ether compounds such as -dihydro-2-ethoxy-2H-pyran, 3,4-dihydro-2H-pyran-2-carboxylic acid sodium, and cyclic vinyl thioether compounds corresponding to these.

Among the aliphatic vinyl ethers, aliphatic vinyl thioethers, cyclic vinyl ether compounds, and cyclic vinyl thioether compounds, the availability of the aliphatic vinyl ethers, and the compound (a12) having a carboxyl group and an oxetane group generated in Step I, Preferably mentioned from the point of the reactivity of.
The said raw material (a3) can be used individually by 1 type or in mixture of 2 or more types.

Next, the steps I and II will be described.
First, in the model I, the ring-opening half esterification reaction of the hydroxyl group of the hydroxyoxetane compound (a1) and the cyclic acid anhydride is, as a model, 1 mol of the cyclic acid anhydride group reacts with respect to 1 mol of the hydroxyl group. Thus, the cyclic acid anhydride group is opened to produce 1 mol of a free carboxyl group. This ring-opening half esterification reaction can be performed by a method known per se, for example, in a temperature range of room temperature to 200 ° C. in an organic solvent.

The ratio of the raw materials (a1) and (a2) used in the ring-opening half-esterification reaction in Step I can be arbitrarily selected according to the purpose, but usually the hydroxyl group 1 of the hydroxyoxetane compound (a1). The component (a2) is used so that the cyclic acid anhydride group is usually 0.2 to 2 mol, preferably 0.5 to 1.5 mol, more preferably 0.8 to 1.2 mol per mol. Is suitable.
In the ring-opening half esterification reaction in Step I, a catalyst such as an organic amine compound can be used to accelerate the reaction. Specifically, examples of such a catalyst include methylamine, ethylamine, butylamine, s-butylamine, t-butylamine, amylamine, octylamine, cyclohexylamine, vinylmethylamine, allylamine, ethoxymethylamine and the like. Primary amines; secondary amines such as dimethylamine, diethylamine, dipropylamine, diallylamine, dihexylamine, didodecylamine; tertiary amines such as trimethylamine, triethylamine, tripropylamine; ethanolamine, diethanolamine, triamine Alkanolamines such as ethanolamine; benzines such as phenylpropylamine, phenylethylamine, methoxybenzylamine, diethylbenzylamine, benzylamine, dimethylbenzylamine Aliphatic amines having a ring; morpholine derivatives such as morpholine and methylmorpholine; aniline derivatives such as t-butylaniline; aromatic amines such as dimethyltoluidine; 2-hydroxypyrimidine, 2-hydroxypyridine, 3-hydroxypyridine, Pyridine derivatives such as 4-hydroxypyridine; piperidine derivatives such as piperidine, methylpiperidine, benzylpiperidine; pyrrolidine derivatives such as methylpyrrolidine; pyrrole derivatives such as pyrrole; 2-hydroquinoline, 3-hydroquinoline, 4-hydroquinoline, 2 -Quinoline derivatives such as methylquinoline and 4-methyl-8-hydroquinoline; imidazole derivatives such as benzimidazole, methylimidazole and imidazole; tetramethylammonium hydroxide, tetraethylan Quaternary ammonium salts such as triphenylsulfonium hydroxide, and the like.
Further, organotin compounds such as dibutyltin laurate and butyltin oxyacetate can also be used as a catalyst for promoting the reaction.
The said catalyst can be used individually by 1 type or in mixture of 2 or more types.
The amount of the catalyst used is preferably 0.005 to 10 parts by weight, more preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the total amount of the compound (a1) and the compound (a2) as raw materials. 5 parts by weight.

Next, the reaction in Step II will be described.
This is a reaction for obtaining the self-crosslinking resin (A) of the present invention by adding the monovinyl (thio) ether compound (a3) to the intermediate raw material (a12) obtained in the above step I.
This addition reaction can be performed by a method known per se, for example, at a temperature of room temperature to 200 ° C.

The ratio of the raw materials (a12) and (a3) used in the addition reaction in Step II can be arbitrarily selected according to the purpose, but usually 1 mol of the carboxyl group formed by the ring-opening half esterified product (a12). It is appropriate to use the component (a3) so that the vinyl (thio) ether group is 0.2 to 2 mol, particularly 0.5 to 2 mol.

  In the blocking reaction in Step II, an acid catalyst can be used for the purpose of promoting the reaction. Examples of such an acid catalyst include acidic phosphoric acid esters represented by the following formula (7).

(In the formula, R ⁹ is an alkyl group having 3 to 10 carbon atoms, a cycloalkyl group or an aryl group, and h is 1 or 2.)
More specifically, primary alcohols such as n-propanol, n-butanol, n-hexanol, n-octanol, 2-ethylhexanol, and isopropanol, 2-butanol, 2-hexanol, 2-octanol, cyclo Examples thereof include phosphoric acid monoesters or phosphoric acid diesters of secondary alcohols such as hexanol.
The said catalyst can be used individually by 1 type or in mixture of 2 or more types.

The amount of the acid catalyst used is not particularly limited, but the total amount of the compound obtained by subjecting the hydroxyl group of the hydroxyoxetane compound to a ring-opening half esterification reaction with a cyclic acid anhydride and the monovinyl (thio) ether compound (a3) is 100 parts by weight. In contrast, 0.0005 to 5 parts by weight is usually preferable, and 0.001 to 1 part by weight is particularly preferable.
Although depending on the molecular weight of the self-crosslinkable resin to be synthesized, the application in which the resin is used, and the compounding system selected, the acid value of the resin usually obtained is 50 mgKOH / g or less. More preferably, the acid value of the resin is 30 mgKOH / g or less, and further preferably 5 mgKOH / g or less.
In particular, when the self-crosslinkable resin of the present invention is used for flux or solder paste, it is desirable that the acid value of the resin is better because it is more stable during storage.

In each of the reactions of the two steps, an organic solvent can be used for the purpose of making the reaction system uniform and facilitating the reaction. Examples of such organic solvents include benzene, toluene, xylene, ethylbenzene, aromatic petroleum naphtha, tetralin, turpentine oil, Solvesso # 100 (registered trademark of Exxon Chemical Co., Ltd.), Solvesso # 150 (Exxon Chemical Co., Ltd.) Aromatic hydrocarbons such as (registered trademark); ethers such as dioxane and tetrahydrofuran; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, amyl acetate, propylene glycol Esters and ether esters such as monomethyl ether and methoxybutyl acetate; acetone, methyl ethyl ketone, diisobutyl ketone, diethyl ketone, methyl propyl ketone, diisopropyl ketone, methylamylohexanone, isophorone, mesityl oxide , Ketones such as methyl isoamyl ketone, ethyl n-butyl ketone and ethyl amyl ketone; phosphate esters such as trimethyl phosphate, triethyl phosphate and tributyl phosphate; and aprotic polarities such as dimethyl sulfoxide and N, N-dimethylformamide Solvent: Triethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether acetate, ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, dipropylene glycol, diethylene glycol-2-ethylhexyl Ether, tetraethylene glycol dimethyl ether Glycol derivatives such as Le like.
More preferably, propylene glycol monomethyl ether acetate is used.
The said organic solvent can be used individually by 1 type or in combination of 2 or more types. Although the usage-amount of the said organic solvent is not specifically limited, It is 5-95 weight part normally with respect to 100 weight part of reaction raw materials in each reaction step, Preferably, it is 20-80 weight part.
In all the two-stage reactions, the same or different organic solvents can be used, and in the reaction in the subsequent step II, a method such as distilling off part or all of the solvent used in the previous stage. Or may be used as it is without being removed, or by further adding a solvent.

Furthermore, the self-crosslinkable resin (A) of the present invention provides a uniform and transparent cured film by heating and curing as a resin composition alone without adding other subcomponents.
In some cases, the above resin composition maintains good long-term storage stability and accelerates the curing reaction when cured in a short time at low temperatures, giving the cured product good chemical and physical performance. For this purpose, a thermal latent catalyst that exhibits activity during heat curing can be contained.
The thermal latent acid catalyst is preferably a compound that exhibits acid catalytic activity at a temperature of 60 ° C. or higher. When this heat-latent acid catalyst exhibits acid catalyst activity at a temperature of less than 60 ° C., the resulting composition may cause an undesirable situation such as thickening during storage or gelation. Specifically, a compound (i) obtained by neutralizing a protonic acid with a Lewis base, a compound (ii) obtained by neutralizing a Lewis acid with a Lewis base, a mixture (iii) of a Lewis acid and a trialkyl phosphate, sulfonic acid esters ( Preferable examples include iv), phosphate esters (v), onium compounds (vi), and compounds (vii) derived from aluminum complexes.

Examples of the compound (i) obtained by neutralizing the protonic acid with a Lewis base include halogenocarboxylic acids, sulfonic acids, sulfuric monoesters, phosphoric mono- and diesters, polyphosphoric esters, boric mono- and diesters, and the like. Various amines such as ammonia, monoethylamine, triethylamine, n-butylamine, cyclohexylamine, monoethanolamine, diethanolamine, triethanolamine, pyridine, piperidine, aniline, morpholine, or trialkylphosphine, triarylphosphine, trialkylphosphine. Phyto, compounds neutralized with triaryl phosphite, and Necurer 2500X, X-47-110, 3525, 5225 (trade name, King) commercially available as acid-base blocking catalysts Ndasutorizu Co., Ltd.) and the like. Examples of the compound (ii) obtained by neutralizing a Lewis acid with a Lewis base include compounds obtained by neutralizing a Lewis acid such as BF ₃ , FeCl ₃ , SnCl ₄ , AlCl ₃ , ZnCl ₂ with the above Lewis base. . Or the mixture (iii) of the said Lewis' acid and trialkyl phosphate is also mentioned. Examples of the sulfonic acid esters (iv) include those represented by the formula (8)

(Wherein, R ¹⁰ is a phenyl group in the formula, a substituted phenyl group, a naphthyl group, substituted naphthyl group or alkyl group, R ¹¹ is 3 carbon bonded with sulfonyloxy group through a primary carbon or secondary carbon 18 alkyl groups, alkenyl groups, aryl groups, alkaryl groups, alkanol groups, saturated cycloalkyl groups, hydroxycycloalkyl groups, unsaturated cycloalkenyl groups, or hydroxycycloalkenyl groups. It is done.
Specific examples of the compound include sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, and nonylnaphthalenesulfonic acid, and n-propanol, n-butanol, Primary alcohols such as n-hexanol and n-octanol or esterified products with secondary alcohols such as isopropanol, 2-butanol, 2-hexanol, 2-octanol and cyclohexanol, and Examples include β-hydroxyalkyl sulfonic acid esters obtained by reacting sulfonic acids with oxirane group-containing compounds.
Examples of the phosphate esters (v) include the acid catalyst that can be used in Step I, that is, the compound represented by the formula (7).

Examples of the onium compound (vi) include compounds represented by formulas (9) to (12).
[(R ¹² ) ₃ NR ¹³ ] ⁺ · X ⁻ (9)
[(R ¹⁴ ) ₃ PR ¹⁵ ] ⁺ · X ⁻ (10)
[(R ¹⁶ ) ₂ OR ¹⁷ ] ⁺ · X ⁻ (11)
[(R ¹⁸ ) ₂ SR ¹⁹ ] ⁺ · X ⁻ (12)
(A ^{R 12,} R ^{14, R 16} and ^{R 18} is an alkyl group having 1 to 12 carbon atoms, an alkenyl group, an aryl group, alkaryl group, alkanol group or a cycloalkyl group, wherein two ^{R 12} , R ¹⁴ , R ¹⁶ and R ¹⁸ may be bonded to each other to form a heterocycle having N, P, O or S as a hetero atom, and R ¹³ , R ¹⁵ , R ¹⁷ and R ¹⁹ are hydrogen atoms. , An alkyl group having 1 to 12 carbon atoms, an alkenyl group, an aryl group, an alkaryl group, and X ⁻ is SbF ₆ ⁻ , AsF ₆ ⁻ , PF ₆ ^— or BF ₄ ^— ). .

  More specifically, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium halide such as tetrabutylammonium iodide, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium halide such as tetrabutylphosphonium iodide, And tetraphenylphosphonium halides such as tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, and tetraphenylphosphonium iodide.

  Further, a compound (vii) derived from an aluminum complex can be used as a catalyst. Specific examples include metal soaps such as aluminum octylate, β-diketonate aluminum complexes, β-diketoesterate aluminum complexes, and o-carbonylphenolate aluminum complexes. Examples of the β-diketone used as the ligand of the aluminum complex include 1,3-diphenyl-1,3-propanedione, 1-phenyl-1,3-butanedione, 2,4-pentanedione, 3-phenyl- 2,4-pentanedione, 5-dimethyl-2,4-hexanedione, 5-phenyl-2,4-pentanedione, 2,6-dimethyl-3,5-heptanedione, 2,6-tetramethyl-3 , 5-pentanedione and the like.

  Examples of β-diketoesters include ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate, t-butyl acetoacetate, and ethyl benzoyl acetate. Examples of o-carbonylphenol include 2-hydroxy-benzaldehyde, 2 ′ -Hydroxy-acetophenone, methyl-2-hydroxybenzoate, phenyl-2-hydroxybenzoate and the like.

Furthermore, in order to increase the activity, an aluminum complex in which a silanol compound is further mixed with the above aluminum complex may be used. Such silanol compounds include triphenylsilanol, tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxy. Silane, phenyltriethoxysilane, diphenyldiethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, trifluoropropyltrimethoxysilane, heptadecatrifluorodecyltrimethoxysilane, triphenylmethoxysilane, And triphenylethoxysilane.
Of these catalysts, a compound derived from an aluminum complex is more preferable.

  In the resin composition of the present invention, one type of catalyst may be used, or two or more types may be combined, and the blending amount is usually based on 100 parts by weight of the self-crosslinking resin (A). It is selected in the range of 0.01 to 10 parts by weight. When the amount of the heat latent acid catalyst is less than 0.01% by weight, the catalytic effect is not sufficiently exerted, and when it exceeds 10% by weight, the finally obtained cured product is colored or the water resistance is lowered. This is not preferable.

The self-crosslinkable resin (A) of the present invention has at least one reactive functional group that forms a chemical bond with a carboxyl group by heating for the purpose of adjusting the mechanical properties and physical properties of the cured film, preferably 2 to 50. A compound (B) having one in one molecule can be blended.
The reactive functional group is not particularly limited as long as it has a property of reacting with a carboxyl group, and examples thereof include an epoxy group, an oxetane group, an oxazoline group, a silanol group, an alkoxysilane group, a hydroxyl group, and an amino group. Preferred examples include groups, imino groups, isocyanate groups, blocked isocyanate groups, cyclocarbonate groups, vinyl ether groups, vinyl thioether groups, aminomethylol groups, alkylated aminomethylol groups, acetal groups, and ketal groups. One type of these reactive functional groups may be contained in B component, and 2 or more types may be contained. More preferably, an epoxy group, an oxetane group, an oxazoline group, etc. are mentioned.

Specifically, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl Examples thereof include epoxy group-containing compounds such as homopolymers and copolymers such as methyl (meth) acrylate, and further, epoxy group-containing compounds such as polyglycidyl compounds obtained by reaction of polycarboxylic acids or polyols with epichlorohydrin. It is done. More preferably, a bisphenol A type epoxy resin and a bisphenol F type epoxy resin are mentioned.
Furthermore, the condensate of the compound represented by Formula (13) is mentioned.

^{_{(R 20) k -Si- (OR}} 21) 4-k ··· (13)

(In the formula, R ²⁰ and R ²¹ are each an alkyl group or aryl group having 1 to 18 carbon atoms, and k is 0, 1 or 2.)
Furthermore, homopolymers or copolymers of α, β-unsaturated silane compounds such as acryloyloxypropyltrimethoxysilane, methacryloyloxypropyltrimethoxysilane, methacryloyloxypropyltri-n-butoxysilane, and compounds of these compounds Silanol group and alkoxysilane group-containing compounds such as hydrolysis products; α, such as aliphatic polyols, phenols, polyalkyleneoxy glycols, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate Hydroxyl group-containing compounds such as homopolymers or copolymers of β-unsaturated compounds and ε-caprolactone adducts of these polyols; aliphatic and aromatic diamino compounds and polyamino compounds, and cyanoethyls of the polyols An amino group-containing compound such as a polyamino compound obtained by reducing a silylation reaction product; an imino group-containing compound such as an aliphatic or aromatic polyimino compound; p-phenylene diisocyanate, biphenyl diisocyanate, tolylene diisocyanate, 3,3 ′ -Dimethyl-4,4'-biphenylene diisocyanate, 1,4-tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexane-1,6-diisocyanate, methylene bis (phenyl isocyanate), lysine methyl ester diisocyanate, bis (Isocyanate ethyl) fumarate, isophorone diisocyanate, methyl cyclohexyl diisocyanate, 2-isocyanatoethyl-2,6-diisocyanate hexanoate and their Isuret and isocyanurate bodies, and further isocyanate group-containing compounds such as adduct compounds of these isocyanates with the polyols; phenols, lactams, active methylenes, alcohols, acid amides of the isocyanate group-containing compounds, Blocked isocyanate group-containing compounds such as imides, amines, imidazoles, ureas, imines, oximes and the like; 3- (meth) acryloyloxypropylene carbonate homopolymer or copolymer, the epoxy group A cyclocarbonate group-containing compound such as a polyvalent cyclocarbonate group-containing compound obtained by reacting the compound with carbon dioxide; a polyvalent vinyl obtained by reacting the polyvalent hydroxyl group-containing compound with a halogenated alkyl vinyl ether. Ether compounds, polyvinyl ether compounds obtained by reaction of hydroxyalkyl vinyl ethers with polyvalent carboxyl group-containing compounds and polyisocyanate compounds, copolymers of vinyloxyalkyl (meth) acrylates with α, β-unsaturated compounds Vinyl ether compounds such as vinyl thioether compounds and vinyl thioether compound-containing compounds such as melamine formaldehyde resins, glycolyl formaldehyde resins, urea formaldehyde resins, aminomethylol groups and alkylated aminomethylol groups containing α, β -An aminomethylol group or alkylated aminomethylol group-containing compound such as a homopolymer or copolymer of an unsaturated compound; a polyvalent ketone, a polyvalent aldehyde compound, the polyvalent vinyl ether A polyacetal compound obtained by reaction of a compound and the like with an alcohol or an ortho acid ester, a condensate of these with a polyol compound, and further, the vinyloxyalkyl (meth) acrylate with an alcohol or an ortho acid ester. Examples include acetal group and ketal group-containing compounds such as homopolymers or copolymers of adducts.

Examples of the compound containing an oxazoline group include 1,2-bis (2-oxazolin-2-yl) ethane, 1,4-bis (2-oxazolin-2-yl) butane, and 1,6-bis (2 -Oxazolin-2-yl) hexane, 1,8-bis (2-oxazolin-2-yl) octane, 1,4-bis (2-oxazolin-2-yl) cyclohexane, 1,2-bis (2-oxazoline) -2-yl) benzene, 1,3-bis (2-oxazolin-2-yl) benzene, 1,4-bis (2-oxazolin-2-yl) benzene, 1,2-bis (5-methyl-2) -Oxazolin-2-yl) benzene, 1,3-bis (5-methyl-2-oxazolin-2-yl) benzene, 1,4-bis (4,4-dimethyl-2-oxazolin-2-yl) benzene Etc. It is below.
As a commercial item of the compound containing the above oxazoline group, for example, Nippon Shoku Kagaku Co., Ltd., a product name “1-5 mol% of 2-ethyl-2-oxazoline copolymerized with an acrylic monomer” There are "Epocross K-1000" and "Epocross K-2000" series (number average molecular weight 70,000 to 80,000) and the like, which can be preferably used.

  Examples of the compound containing an oxetane group include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, di [1-ethyl (3 -Oxetanyl)] methyl ether, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, oxetanylsilsesquioxane, 1,4-bis [(1-ethyl -3-Oxetanyl) methoxy] benzene, 1,3-bis [(1-ethyl-3-oxetanyl) methoxy] benzene, 4,4′-bis [(3-ethyl-3-oxetanyl) methoxy] biphenyl, phenol novolak And oxetane.

As the compound of component B, in addition to the compound having one kind of reactive functional group, a compound having two or more kinds of the reactive functional group may be used. Moreover, the compound of B component may be mix | blended individually by 1 type, and may be mix | blended in combination of 2 or more type. However, in this case, a combination showing an active action when the respective functional groups are combined is not preferable because storage stability is impaired.
Examples of such an unfavorable combination include a combination of a functional group selected from an epoxy group, an isocyanate group, a vinyl ether group, a vinyl thioether, a cyclocarbonate group and a silanol group with an amino group or an imino group, and an isocyanate. -A combination of a thio group or a vinyl ether group and a hydroxyl group.

The thermosetting composition of the present invention is a thermoplastic resin, a solvent, a coloring pigment, a filler, an elastomer, a solvent, an ultraviolet absorber, an antioxidant, a flow control agent, as necessary, as long as the effects of the present invention are not impaired. Etc. can be blended.
Specific examples of the thermoplastic resin used in the thermosetting composition of the present invention include polyester resins, acrylic resins, vinyl chloride resins, and polyvinyl ether resins.
It does not specifically limit as a solvent used for the thermosetting composition of this invention. It can be used by appropriately selecting from ordinary general-purpose solvents. Specifically, for example, the same solvent as that used in the reaction during the production of the self-crosslinkable resin (A) can be used. The amount added is approximately 0 to 50% by weight.

  The thermosetting composition of the present invention is manufactured by blending various components including the self-crosslinking resin (A) as a main component in a lump or sequentially, and a blade-type stirrer, a desolver, a kneader, a ball mill blender. Using a roll disperser, mixing may be performed by a normal method. The mixing temperature is preferably 10 to 30 ° C. in order to avoid condensation and volatilization of the solvent, although it depends on the blending components.

The thermosetting composition of this invention can obtain a preferable resin cured material by thermosetting. There is no restriction | limiting in particular in the apparatus used for hardening, Hardening apparatuses, such as a closed-type hardening furnace and a tunnel furnace which can be continuously hardened, are employable. The heating source is not particularly limited and can be performed by a method such as hot air circulation, infrared heating, high-frequency heating or the like.
The temperature and time required for curing vary depending on the temperature at which the free carboxyl group is regenerated from the blocked carboxyl group in the self-crosslinkable resin (A), the type of catalyst, etc., but usually in the range of 50 to 250 ° C. Then, curing is completed by heating for about 2 minutes to 10 hours. A more preferable reaction temperature and time is a temperature in the range of 80 to 200 ° C., and heating for about 10 minutes to 2 hours.

  The self-crosslinkable resin (A) of the present invention has a self-crosslinkability that regenerates a free carboxyl group under heating and forms a chemical bond with an oxetane group. In addition to this reaction, an addition reaction can be caused to the oxetane group as a so-called active ester based on an intramolecular polarization structure. In this case, since no desorption reaction is involved in the crosslinking reaction, it is possible to contribute to the reduction of emission of volatile organic substances.

  The thermosetting composition of the present invention includes a color filter, an IC circuit, and a color filter mounted on a color liquid crystal display device, a color video camera, etc. as an electronic component application in addition to general-purpose applications such as paints, inks, adhesives, and molded products. It can be used for a photosensitive resist related to the manufacture of a photomask, a thermosetting flux for soldering when mounting components on a mounting substrate, and a solder paste containing the flux.

EXAMPLES Next, although an Example demonstrates this invention in detail, this invention is not restrict | limited to these.
Next, the measurement method and evaluation method used are shown.
1. <IR measurement conditions>
Model: JASCO Corporation, FT / IR-600
Cells; liquid film method decomposed with potassium bromide; ^{4 cm -1}
Number of integrations: 32 times2. <Measurement conditions for ¹ H-NMR>
Model: Nippon Bruker Co., Ltd., 400 MHz Advance 400
Number of integrations: 16 times Solvent; CDCl ₃ , TMS standard 3. <Measurement conditions for ¹³ C-NMR>
Model: Nippon Bruker Co., Ltd., 400 MHz Advance 400
Accumulation count: 1024 times Solvent; CDCl ₃ , TMS standard 4. <Viscosity measurement>
Model: Toki Sangyo Co., Ltd., EHD viscometer Measurement temperature: 25 ° C
5. <Measurement of acid value>
It measured according to the method of JISK0070-3 (1992).

Example 1; Production of self-crosslinkable resin (a-1) <Step I>
To a 200 ml four-necked flask equipped with a thermometer, reflux condenser, and stirrer was added 25.6 grams of 3-ethyl-3-hydroxymethyloxetane, 5- (2,5-dioxotetrahydro-3-furanyl). -3-Methyl-3-cyclohexene-1,2-dicarboxylic anhydride 24.2 grams, 28.1 grams of propylene glycol monomethyl ether acetate (PMA) were charged, the temperature was raised to 140 ° C., and the same temperature The reaction was continued for 2 hours while maintaining the above, and the reaction was terminated when the reaction rate reached 98% by measuring the acid value of the sampled reaction solution.
<Process II>
Thereafter, the temperature in the system was lowered to 100 ° C., and 22.1 g of n-butyl vinyl ether was added dropwise at a constant rate over 30 minutes. The reaction was continued for 2 hours at the same temperature, and the reaction was terminated when the acid value of the mixture became 5 mgKOH / g or less. After allowing to cool, the product was transferred to a separatory funnel, washed with alkali with 100 g of a 10% by weight aqueous sodium hydrogen carbonate solution, and washed repeatedly with 200 g of deionized water until the pH of the washing solution was 7 or less. Next, after drying the organic layer with magnesium sulfate, it was concentrated under reduced pressure at a bath temperature of 35 ° C., and the residue was further dried with a vacuum pump to obtain 65.3 g of a self-crosslinkable resin (a-1). Table 1 shows the analysis results such as the charged composition, reaction conditions, and viscosity.

Examples 2 and 3; Production of Self-Crosslinking Resin (a-2, a-3) The reaction was conducted in the same manner as in Example 1 except that the charged composition and conditions were changed as shown in Table 1, and further purification was performed. As a result, pale yellow self-crosslinking resins (a-2, a-3) were obtained. Table 1 shows the results of the analysis of the charged composition, reaction conditions, viscosity, etc., as in Example 1.

The components and abbreviations in Table 1 indicate the following.
* 1) Epicron B-4400 (5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, Dainippon Ink & Chemicals, Inc. ) Product name
* 2) Ricacid TDA-100 (3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, trade name, manufactured by Shin Nippon Rika Co., Ltd.)
* 3) Aron oxetane OXT-101 (3-ethyl-3-hydroxymethyloxetane, manufactured by Toa Gosei Co., Ltd., trade name)
* 4) PMA (propylene glycol monomethyl ether acetate)

The structures of the self-crosslinkable resins obtained in Examples 1 to 3 were confirmed by infrared absorption spectrum measurement (IR spectrum), ¹ H-NMR, and ¹³ C-NMR. The structures of the compounds of Examples 1 to 3 are shown in the following formulas (14) to (16). Further, FIG. 1 shows a chart of the IR spectrum of the self-crosslinkable resin (a-1) obtained in Example 1, FIG. 2 shows a ¹ H-NMR chart, and FIG. 3 shows a ¹³ C-NMR chart.

Than 1, absorption derived from a carbonyl of the carboxylic acid derivatives have been observed in 1736 cm ^-1, further, it was confirmed that the broad absorption around 2500～3500Cm ^-1 derived from a carboxyl group is lost.
From FIG. 2, a peak attributed to the hemiacetal structure was observed in the vicinity of 5.9 ppm, and a peak attributed to the oxetane structure was observed in the vicinity of 4.4 ppm.
3. From FIG. 3, a peak attributed to the carbonyl carbon of the ester structure was observed at around 171 ppm, a peak of methine carbon based on the hemiacetal structure was observed at around 100 ppm, and a peak attributed to the oxetane structure was observed at around 78 ppm.
From the above analysis results, it was confirmed that the obtained self-crosslinking resin (a-1) had the structure of the formula (14).

Examples 4-9
Thermosetting compositions were produced using the self-crosslinking resins (a-1 to 3) obtained in Examples 1 to 3. The composition is shown in Table 2. Using the obtained thermosetting resin, a cured product was obtained by the following method.
<Method for measuring physical properties of cured film>
Preparation of the test piece was performed on a anodized brush-polished aluminum plate using the resin composition of Examples 4 to 9 described in Table 2 with a bar coater so that the dry film thickness was 50 μm. After prebaking at 80 ° C. for 30 minutes, the test piece was prepared by curing at 180 ° C. for 60 minutes.

Using the test piece of the cured film prepared by the above method, performance evaluation was performed by the following test method.
(1) Acid resistance-1
2 ml of 40% by weight sulfuric acid was placed on the test piece on a spot and allowed to stand at 20 ° C. for 48 hours, and then the abnormality of the cured film was visually determined.
(2) Acid resistance-2
2 ml of 40 wt% sulfuric acid was placed on the test piece on a spot, heated at 60 ° C. for 30 minutes, and then the abnormality of the cured film was visually determined.
(3) Acid resistance-3
The test piece was immersed in 0.1 N sulfuric acid and kept at 60 ° C. for 24 hours, and then the abnormality of the cured film was visually determined.
(4) Impact resistance Using an impact deformation tester [JIS K-5400 (1979) 613.3 B method], a test piece is placed in a shooting mold having a radius of 6.35 mm, and a 500 g weight is dropped from a height of 40 cm. The damage of the cured film at the time of making was judged visually.
(5) Knoop hardness It measured at 20 degreeC with the M-type micro hardness tester by Shimadzu Corporation. The larger the value, the harder it is.
(6) Acetone extract The remaining test piece weight (%) after extracting the test piece in acetone solvent for 3 hours was determined.
(7) Xylene wiping property The test piece was rubbed strongly with gauze moistened with mixed xylene (JIS K 2435 product), and the surface of the test piece after 10 reciprocations was visually judged.
(8) Tensile strength, elastic modulus Measured using an autograph AGS-H manufactured by Shimadzu Corporation.
(9) Cured film Tg (° C)
Using TMA (Seiko Instruments TMA / SS150), the temperature at which the elongation of the cured product suddenly changes when the temperature is raised at 10 ° C./min is defined as a cured film Tg (° C.).
(10) Storage stability test 10 g of the composition shown in Table 2 was hermetically stored at 50 ° C., and the state after storage for 30 days was visually observed.
These results are shown in Table 2.

The components and abbreviations in Table 2 indicate the following.
* 1) 60 wt% toluene solution of aluminum complex in which acetylacetonate aluminum complex and triphenylsilanol were reacted in equimolar ratio * 2) 80% of zinc complex in which zinc octylate and triethanolamine were reacted in equimolar ratio Weight% cyclohexanone solution,
* 3) Made by Japan Epoxy Resin Co., Ltd., bisphenol A type epoxy resin,
In Examples 4 to 9, cured films having excellent transparency were obtained.

Comparative Example 1
To 2000 g of a 50% xylene solution of acrylic resin (weight average molecular weight by GPC of 40000) consisting of 2 mol / kg of glycidyl methacrylate, 2 mol / kg of 2-hydroxyethyl methacrylate and the remainder n-butyl methacrylate, 296 g of phthalic anhydride and dibutyl 0.5 g of tin dilaurate was blended and an acid anhydride group ring-opening reaction was carried out at 50 ° C. for 8 hours to obtain a 50% xylene solution product of self-crosslinkable resin (b). The acid value of the resin was 85 mgKOH / g and the weight average molecular weight was 45,000.
Using this self-crosslinking resin (b), the same tests and evaluations as in Examples 4 to 9 were performed. The results are shown in Table 2.

Comparative Example 2
Using a xylol 50% solution (self-crosslinkable resin (c)) of an acrylic resin consisting of 2 mol / kg of glycidyl methacrylate, 2 mol / kg of methacrylic acid and the rest n-butyl methacrylate, the same as in Examples 4 to 9 Tested and evaluated. The results are shown in Table 2. The acid value of the self-crosslinking resin (c) was 112 mgKOH / g, and the weight average molecular weight was 43,000.
Using this self-crosslinking resin (c), the same tests and evaluations as in Examples 4 to 9 were performed. The results are shown in Table 2.

  From the results of Examples 4 to 9, the resin composition using the self-crosslinkable resin of the present invention was very excellent in storage stability, cured alone, and excellent in mechanical and physical properties, uniform. It turns out to give a transparent cured product. In particular, it can be seen that the acid resistance and tensile strength are excellent. Furthermore, from the results of Examples 1 to 3, the self-crosslinking resin of the present invention can be stably produced by the method for producing a self-crosslinking resin of the present invention without causing gelation or partial polymerization. It was shown that there is.

1 is an infrared absorption spectrum chart of the self-crosslinkable resin obtained in Example 1. FIG. FIG. 2 is a ¹ H-NMR chart of the self-crosslinkable resin obtained in Example 1. FIG. 3 is a ¹³ C-NMR chart of the self-crosslinkable resin obtained in Example 1.

Claims (8)

Using a hydroxyoxetane compound having at least one hydroxyl group and an oxetane group in one molecule and a compound having at least one cyclic acid anhydride group in one molecule, the hydroxyl group and the cyclic acid anhydride group are half-esterified. To obtain a compound having a carboxyl group and an oxetane group, and further, an addition reaction between the carboxyl group of the compound and a monovinyl (thio) ether compound, and represented by the following formula (1) Crosslinkable resin.

[Wherein, m, n is an integer from 1 to 6, R is 2-12 monovalent organic group having 1 to 50 carbon atoms, ^{A 1} is a group represented by the following formula (2) or (3) Indicates. A ² represents a linear or branched alkyl group having 1 to 20 carbon atoms. ]

(In the formula, R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, R ⁴ is an organic group having 1 to 18 carbon atoms, and Y ¹ is an oxygen atom or a sulfur atom.)

(Wherein R ⁵ and R ⁶ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, R ⁷ is a divalent organic group having 1 to 18 carbon atoms, and R ⁸ is a divalent carbon group having 1 to 18 carbon atoms. An organic group, Y ² is an oxygen atom or a sulfur atom, and forms a heterocycle having Y ² as a hetero atom.) The method for producing a self-crosslinking resin according to claim 1, wherein the following step I and step II are performed.
Step I: a step of subjecting a hydroxyl oxetane compound having at least one hydroxyl group and an oxetane group in a molecule as a raw material to a half esterification reaction of the hydroxyl group with a compound having at least one cyclic acid anhydride group per molecule .
Step II: Further, a step of adding a monovinyl (thio) ether compound to the generated carboxyl group. The method for producing a self-crosslinkable resin according to claim 2, wherein a base catalyst is used as a catalyst in the reaction of the step I. A thermosetting composition comprising the self-crosslinking resin according to claim 1 and a catalyst. The thermosetting composition according to claim 4, wherein the catalyst is a thermolatent catalyst that exhibits activity during heat curing. The thermosetting composition according to claim 4 or 5, wherein the catalyst is a compound derived from an aluminum complex. The thermosetting agent according to any one of claims 4 to 6, further comprising a compound having at least one reactive functional group capable of forming a chemical bond with a carboxyl group by heating in one molecule. Composition. The thermosetting composition according to claim 7, wherein the reactive functional group is an epoxy group or an oxetane group.

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