KR950000991B1 - Resin composition - Google Patents

Abstract

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Description

Heat resistant resin composition

The present invention relates to a heat resistant resin composition. In more detail, the present invention enables the production of cured products having excellent secondary moldability, such as curability and processability, satisfactory stability even at high temperature, and satisfactory mechanical strength, and the occurrence of cracking due to thermal expansion and shrinkage during curing. It is related with the heat resistant resin composition which does not allow generation.

As resin which has high stability at high temperature, various heat resistant resins represented by polyimide resin and polyamideimide resin are illustrated. However, since these heat-resistant resins have high melting point, they require high temperature and high pressure during molding, and must be left for a long time under high pressure and high temperature to cure, and must be dissolved in a specific high boiling point solvent to be used at high temperature under pressure or major. There is an important problem in secondary moldability, such as requiring a step of removing the solvent by leaving it for a long time. Therefore, it is extremely difficult to produce large secondary molded articles from these heat resistant resins, or to continuously produce secondary molded articles into these resins by pultrusion molding or extrusion molding.

Examples of resins excellent in secondary moldability such as curability and processability include polyhydric phenol type epoxy resins such as bisphenol type epoxy resins or noblock type epoxy resins and radical polymerization such as epoxy (meth) acrylates or unsaturated polyesters derived from (meth) acrylic acid. Mold resins are known in the art. In general, these resins are widely used in the form of vinyl ester resins or unsaturated polyester resins in which radical polymerizable crosslinking agents such as styrene are incorporated. However, these resins are not sufficiently satisfactory in thermal stability at high temperatures. This defect in thermal stability is a serious obstacle to the development of resins. In this situation, the demand for the development of a resin having excellent thermal stability has dominated the industrial field.

Therefore, it is an object of the present invention to provide a novel heat resistant resin composition.

It is another object of the present invention to produce a cured product having excellent secondary molding aptitude such as curability and processability, satisfactory high temperature stability and mechanical strength, and heat resistance that does not allow cracking due to thermal expansion and contraction during curing. It is to provide a resin composition.

The above object is (A) 30 to 95% by weight of at least one unsaturated ester compound compound selected from the group consisting of an unsaturated ester compound represented by the following general formula (I) and an unsaturated ester compound represented by the following general formula (II), At least one (meth) acryloyl group based on 70 to 5% by weight of (B) a polymerizable crosslinking agent and (C) 100 parts by weight of a vinyl ester resin consisting of (A) an unsaturated ester compound and (B) a polymerizable crosslinking agent Is achieved by a heat resistant resin composition containing 0.5 to 15 parts by weight of butadiene-acrylonitrile copolymer having in its molecular unit.

[Wherein R ¹ and R ⁵ are each

(Wherein R ³ and R ⁴ each represent a hydrogen atom or a methyl group)

And one kind selected from the group consisting of hydrogen atoms, at least one R ¹ and R ⁵ is

로 이루어진 군에서 선택된 이가 유기기를 나타내고, n이 1내지 10의 정수인 경우에는Wherein R ³ and R ⁴ each represent a hydrogen atom or a methyl group, and R ² and R ⁶ each represent an atom or organic selected from the group consisting of a hydrogen atom, a halogen atom, a methoxy group and an alkyl group of 1 to 5 carbon atoms Group, m and n each represent 0 or an integer of 1 to 10, and X represents a case where n is 0

When the divalent selected from the group consisting of represents an organic group, n is an integer of 1 to 10

및 -CH₂-로 이루어진 군에서 선택된 이가 유기기를 나타낸다.]

And -CH ₂ -represents a divalent organic group selected from the group consisting of.]

Generally, resins are used to produce castings formed from resins only by high temperature curing, or to produce castings formed of composite materials by resin transfer molding, which is relatively easy to form products having a relatively low reinforcement content and lacking the distribution unity of the reinforcement. Using the composition, the resulting molded product will have cracks in portions of high resin content due to regional differences in the volume shrinkage or thermal expansion coefficients induced during curing. Even in such a case, by using the resin composition of the present invention, a product having excellent strength and appearance without cracking can be obtained.

As used herein, the (I) unsaturated ester compound or (II) unsaturated ester compound from which the (A) unsaturated ester compound is selected therefrom is represented by the general formula (I) or (II) described above. An unsaturated ester compound can be manufactured, for example by one of the following methods.

The first production method comprises (a) an aromatic polyamine represented by the following general formula (III) or (b) an aromatic diamine represented by the following general formula (IV) having an epoxy group and a radical polymerizable unsaturated bond in its molecular unit, It reacts with the compound (c) represented by Formula (V), It is characterized by the above-mentioned.

[Wherein, R ² and R ⁶ each represent an atom or an organic group selected from the group consisting of a hydrogen atom, a halogen atom, a methoxy group and an alkyl group of 1 to 5 carbon atoms, and m and n are each an integer of 0 or 1 to 10, respectively X represents n is 0,

로 이루어진 군에서 선택된 이가 유기기를 나타내고, n이 1내지 10의 정수인 경우에는

When the divalent selected from the group consisting of represents an organic group, n is an integer of 1 to 10

및 -CH₂-로 이루어진 군에서 선택된 이가 유기기를 나타내고, R³및 R⁴는 각각 수소원자 또는 메틸기를 나타낸다.]

And a divalent organic group selected from the group consisting of -CH _2- , and R ³ and R ⁴ each represent a hydrogen atom or a methyl group.]

(a) The aromatic polyamine is represented by the above general formula (III), neutralizing the aniline derivative using hydrochloric acid to prepare a hydrochloride aniline derivative solution, and the formaldehyde and hydrochloride aniline derivative solutions are not fractions of formaldehyde. It can manufacture by making it react at the ratio which falls in the range of 0.25-1.0 mol per mole. Examples of aniline derivatives include aniline, p (m- or o-) chloroaniline p- (m- or o-) toluidine, p- (m- or o-) ethylaniline, p- (m- or o-) iso Propylaniline, p- (m- or o-) n-propylaniline and p- (m- or o-) methoxyaniline. These aniline derivatives may be used alone or in combination in the form of a mixture of two or more. Poly (phenylenemethylene) polyamines obtained by the reaction of aniline with formaldehyde are now commercially produced as raw materials of polyurethanes. For example, a commercially available product (product of Mitsui-Toatsu Chemicals Inc.) sold under the codes of MDA-220 and MDA-150 may be used as (a) aromatic polyamine in unmodified form.

(b) Aromatic diamine is represented by the said general formula (IV). Examples of this aromatic diamine include 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenyl ether , 4,4'-diaminodiphenyl ether, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 1,3-bis (4-amino Phenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] Propane, bis [4- (4-aminophenoxy) phenyl] sulfone, 1- (p-aminobenzoyl) -4- (p-aminobenzyl) benzene, 1- (p-aminobenzoyl) -4- (m- Aminobenzyl) benzene, 1- (m-aminobenzoyl) -4- (p-aminobenzyl) benzene, 1- (m-aminobenzoyl) -4- (m-aminobenzyl) benzene, 1,4-bis (m -Aminobenzoyl) benzene, 1,4-bis (p-aminobenzoyl) benzene, 1,3-bis (m-aminobenzyl) benzene, 4,4'-bis (m-aminobenzoyl) dipanyl methane, 4, 4'-bis (p-aminobenzoyl) diphenyl methane and 4,4'-bis (m-aminobenzyl ) Diphenylmethane and the above compounds having an aromatic hydrogen substituted by a halogen atom, a methoxy group or an alkyl group of 1 to 5 carbon atoms. These aromatic diamines may be used alone or in combination in the form of a mixture of two or more.

(c) The compound is represented by the above general formula (V) and contains an epoxy group and a radical polymerizable unsaturated bond. Examples of this compound include glycidyl methacrylate, glycidyl acrylate, 2-methylglycidyl methacrylate and 2-methylglycidyl acrylate. These compounds may be used alone or in combination in the form of a mixture of two or more.

Ring-open addition reactions of (c) compounds to (a) aromatic polyamines or (b) aromatic diamines to produce (I) unsaturated ester compounds or (II) unsaturated ester compounds, for example, (c) compounds and (a (C) the fraction of the compound (c) per equivalent of hydrogen atoms directly bonded to the aromatic polyamine or (b) the aromatic diamine to (a) the aromatic diamine or (b) the nitrogen atom contained in the aromatic diamine, preferably from 0.2 to 1.5 equivalents. Is mixed at a rate such that it is in a range of 0.3 to 1.0, and the resulting mixture is heated at a temperature in the range of 30 to 150 ° C., preferably 50 to 130 ° C., in an inert solvent or in the absence of a solvent, preferably in the presence of air. This can be done by inducing a reaction under the following conditions. In order to prevent the reaction mixture from gelling by a polymerization reaction, for example, at least one kind selected from the group consisting of hydroquinones such as methylhydroquinone and vhydroquinone and benzoquinones such as p-benzoquinone and p-toluquinone It is preferable to use a polymerization inhibitor in the reaction system.

In the reaction, a ring-opening addition catalyst may be used to shorten the reaction time. Ring-opening addition reaction catalysts that can be used in the reaction include, for example, water; Alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol; Phenols such as phenol and t-butyl caterol; Organic acids such as salicylic acid, citric acid and malic acid; Organic acid salts such as zinc salicylate and tin octylate; And boron trifluoride-monoethanolamine complexes.

Toluene, xylene, or dimethylformamide can be used as the inert solvent. Ethyl alcohol or acetic acid already provided as catalyst can be used simultaneously as the reaction medium. The solvent must be removed from the reaction product at the end of the reaction. Therefore, it is advantageous to use this polymerizable crosslinker as a solvent in the reaction, especially when a polymerizable crosslinker which is liquid at room temperature is additionally used in the final composition.

The second production method is (a) aromatic polyamine represented by general formula (III) or (b) aromatic represented by general formula (III) of (d) epihalohydrin represented by general formula (VI) After chemical addition reaction to diamine to prepare N-halohydrin as an intermediate, dehydrohalogenation of the N-halohydrin with alkali is used to give it a glycidyl group to give an epoxy compound (hereinafter referred to as "epoxy compound). (e) ", and (e) further ring-open chemical addition reaction of acrylic acid and / or methacrylic acid to the epoxy compound.

[In formula, R <^3> represents a hydrogen atom or a methyl group, and Y represents a halogen atom.]

(d) Epihalohydrin is a compound represented by the above general formula. Examples of epihalohydrin are epichlorohydrin, epibromohydrin, epiiodohydrin, β-methyl epichlorohydrin, β-methyl epibromohydrin and β-methyl epiiodohydrin.

Production of (e) epoxy compound by reaction of (a) aromatic polyamine or (b) aromatic diamine and (d) epihalohydrin. For example, hydrogen atom 1 directly bonded to the nitrogen atom of (d) epihalohydrin and (a) aromatic polyamine or (b) aromatic or (b) aromatic diamine (a) aromatic polyamine or (b) aromatic diamine Equivalent (d) Mix at a rate such that the fraction of epihalohydrin is in the range of 1 to 5 equivalents, preferably 2 to 3 sugars, and the resulting mixture is mixed for 5 to 30 hours at a temperature in the range of 40 to 100 ° C. , Preferably heated at a temperature in the range of 70-90 ° C. for 7-15 hours to induce a chemical addition reaction, and then slowly add hydroxides of alkali metals to the resulting reaction product and add the resulting mixture at a temperature below 70 ° C. It can be achieved by heat treatment for 2 to 10 hours to remove hydrochloric acid.

Toto Kasei KK sold as a commercial product of Ciba-Geigy sold under the trademark "Araldite MY-720" or as a product code of "YH-434". The commercial item of can be used for this invention as above-mentioned (e) epoxy compound.

(e) The preparation of (I) unsaturated ester compounds or (II) unsaturated ester compounds by the reaction of an epoxy compound with acrylic acid and / or methacrylic acid is, for example, (e) an epoxy compound with acrylic acid and / or methacrylic The acid is mixed at a ratio of (e) 0.3 to 1.2 moles, preferably 0.5 to 1.1 moles, of the fraction of acrylic acid and / or methacrylic acid per mole of epoxy group contained in the epoxy compound, and the resulting mixture is mixed. It can be achieved by heating at 60 to 150 ° C., preferably 70 to 130 ° C., in an inert solvent or in the absence of solvent, to induce the reaction, preferably in the presence of air. In order to prevent the reaction mixture from gelling by the polymerization reaction, it is preferable to use a conventional polymerization inhibitor. Examples of polymerization inhibitors include hydroquinones such as methylhydroquinone and hydroquinone and benzoquinones such as p-benzoquinone and p-toluquinone. The amount of the polymerization inhibitor to be used is preferably in the range of 0.001 to 0.5% by weight, preferably 0.005 to 0.2% by weight.

In order to shorten reaction time, it is preferable to use an esterification catalyst in this reaction. Esterification catalysts which can be used for this purpose include, for example, tertiary amines such as N, N-dimethylaniline, pyridine and triethylamine and hydrochlorides and bromates thereof; Quaternary ammonium salts such as tetramethyl ammonium chloride and triethylbenzyl ammonium chloride; Sulfonic acids such as paratoluene sulfonic acid; Sulfoxides such as dimethyl sulfoxide and methyl sulfoxide; Sulfonium salts such as trimethyl sulfonium chloride and dimethyl sulfonium chloride; Phosphines such as trimethyl phosphine and tri-n-butyl phosphine; And metal halides such as lithium chloride, lithium bromide, tin tin chloride and zinc chloride. The amount of esterification catalyst used for this purpose is 0.01 to 2.0% by weight, preferably 0.03 to 1.0% by weight.

For example, toluene or xylene can be used as the inert solvent. However, this solvent must be removed from the reaction product at the end of the reaction. Therefore, it is preferable to use the polymerizable crosslinker as a solvent at the same time in the reaction, especially when a polymerizable crosslinker which is liquid at standard room temperature is additionally used in the final composition.

Polymerizable crosslinkers usable in the present invention include known compounds for unsaturated polyester resins and vinyl ester resins, in particular styrene, alpha-methyl styrene, p-methyl styrene, t-butyl styrene, vinyl toluene and di Styrene derivatives such as vinyl benzene; (Meth) acrylic acids such as methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, tricyclodecenyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate Ester monomer; Trimethylolpropane tri (meth) acrylate, diethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate. (Meth) of polyhydric alcohols such as di (meth) acrylate of tris (2-hydroxyethyl) isocyanuric acid (meth) acrylic acid ester and 2,2-bis [4- (2-hydroxyethoxy) phenyl] propane ) Acrylate; And allyl compounds such as diallyl phthalate, diallyl isophthalate, diallyl terephthalate, and triallyl isocyanurate and triallyl cyanurate. These crosslinking agents may be used alone or in combination in the form of a mixture of two or more.

Particularly in view of copolymerizability or suitability with (A) an unsaturated ester compound or (C) a butadiene-acrylonitrile copolymer having at least one acroyl group and / or methacryloyl group in its molecule, the polymerizable cross It is preferable that binder (B) has a styrene compound represented by following General formula (VII) as an essential component.

[Wherein, R ⁷ represents a hydrogen atom or a methyl group, R ⁸ represents a hydrogen atom or an alkyl group of 1 to 5 carbon atoms.]

When alkyl group-substituted styrene is used as a main component of the polymerizable crosslinking agent (B), the cured product produced from the resin composition shows excellent stability at high temperature. Because of its availability, vinyl toluene and p-methylstyrene are particularly advantageous.

In manufacturing the vinyl ester resin which is a substrate of the production of the resin composition of the present invention, the ratio of the amount of the (A) unsaturated ester compound to the amount of the (B) polymerizable crosslinking agent is 30 to 95% by weight of the fraction of (A). %, Preferably it is in the range of 45 to 80 weight%, and the fraction of (B) is a value which is 70 to 5 weight%, Preferably it is 55 to 20 weight%. If the amount of the (A) unsaturated ester compound used is 30% by weight or less or the amount of the (B) polymerizable crosslinker used is more than 70% by weight, the resulting resin composition is not very satisfactory in mechanical strength and heat resistance. . If the amount of (A) unsaturated ester compound used is greater than 95% by weight or the amount of (B) polymerizable crosslinker used is less than 5% by weight, the resulting resin composition has secondary moldability such as curability and processability. It falls, and hardened | cured material lacks mechanical strength and heat resistance.

(C) butadiene-acrylonitrile copolymer used in the present invention having at least one acryloyl and / or methacryloyl group in the molecular unit thereof (hereinafter referred to as “(C) (meth) acryloyl group-containing butadiene- Butadiene-acrylonitrile can be used as acrylonitrile copolymer ", which is referred to simply as" acrylonitrile copolymer ". For example, a reaction product between a carboxyl group and an amino group-containing butadiene-acrylonitrile copolymer and a compound having an epoxy group and a (meth) acryloyl group in its molecular unit, (meth) acrylic acid and at least two in its molecular unit Butadiene-acrylonitrile copolymer-modified vinyl ester obtained by allowing the butadiene-acrylonitrile copolymer containing carboxyl group and amino group to participate as part of (meth) acrylic acid in the reaction between epoxy compounds having an epoxy group, and maleic acid Mention may be made of reaction products between chloride butadiene-acrylonitrile copolymers and compounds having (meth) acryloyl groups and hydroxyl groups in their molecular units. These are not the only butadiene-acrylonitrile copolymers that can be used. Other butadiene-acrylonitrile copolymers should also contain at least one acryloyl group and / or methacryloyl group which can be copolymerized with (A) unsaturated ester compound and (B) polymerizable crosslinker in their molecular unit. Can be used to meet your needs.

Butadiene- obtained by reaction of a carboxyl and / or amino group-containing butadiene-acrylonitrile copolymer, in particular in the reaction with acrylic acid and / or methacrylic acid (e) epoxy compounds The acrylonitrile copolymer-modified unsaturated ester compound, or (I) unsaturated ester compound and / or (II) unsaturated ester compound is reacted with maleate (butadiene-acrylonitrile copolymer) to (I) unsaturated ester compound and And / or (II) butadiene-acryl obtained by ring opening chemical addition reaction to succinic anhydride contained in maleated (butadiene-acrylonitrile copolymer) hydroxyl group and / or amino group contained in unsaturated ester compound The ronitrile copolymer-modified unsaturated ester compound is (C) (meth) acryloyl -They are containing butadiene-case of using a copolymer of acrylonitrile has. (C) the (meth) acryloyl group-containing butadiene-acrylonitrile copolymer is excellent in compatibility with the (A) unsaturated and (B) polymerizable crosslinking agent, and the resulting heat resistant resin composition prevents phase separation for a long time. An excellent advantage of providing a very satisfactory shelf life with sufficient security is derived.

When a butadiene-acrylonitrile copolymer containing neither acryloyl nor methacryloyl groups is used in place of the (C) (meth) acryloyl group-containing butadiene-acrylonitrile copolymer, the resulting resin composition The butadiene-acrylonitrile copolymer is unevenly dispersed in the resulting cured product. Thus, the cured product does not acquire uniform mechanical strength and shows a marked drop in stability at high temperatures.

The amount of the (C) (meth) acryloyl group-containing butadiene-acrylonitrile copolymer to be used is based on 100 parts by weight of a vinyl ester resin consisting of (A) an unsaturated ester compound and (B) a polymerizable crosslinking agent. As acrylonitrile copolymer, it is 0.5-15 weight part, Preferably it is in the range of 1-10 weight part.

(C) If the amount of the (meth) acryloyl group-containing butadiene-acrylonitrile copolymer is 0.5 parts by weight or less, the copolymer is sufficient to suppress the occurrence of cracking during the curing of the secondary molded product of the resulting resin composition. Not effective On the contrary, when this amount exceeds 15 parts by weight, a disadvantage arises in that the mechanical strength of the product obtained by curing the resulting resin composition is lowered.

Curing of the resin composition of the present invention can be achieved by a copolymerization method using a photosensitizer, a thermal polymerization method using a polymerization initiator such as an organic peroxide or an azo compound, or a room temperature polymerization method using an organic peroxide and an accelerator.

The photosensitizers used in the photopolymerization method are for example carbonyl compounds and diphenyl disulfides such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether and benzophenone and Many known compounds are represented by sulfur compounds such as tetramethyl thiuram disulfide. These photosensitizers may be used alone or in combination in the form of a mixture of two or more, or in combination with the organic peroxides mentioned below. The amount of photosensitizer used is in the range of 0.01 to 4% by weight, preferably 0.05 to 3% by weight, based on the amount of the resin composition.

Organic peroxides usable in the present invention include, for example, t-butyl peroxybenzoate, t-butyl peroxy-2-ethylhexanoate, benzoyl peroxide, cyclohexanone peroxide, methylethyl catone peroxide, and bis 4-t-butylcyclohexyl peroxydicarbonate is included. Azo compounds usable in the present invention include, for example, azobisisobutylonitrile. These compounds may be used alone or in combination in the form of a mixture of two or more. The amount of polymerization initiator to be used is in the range of 0.1 to 4.0% by weight, preferably 0.3 to 3.0% by weight based on the amount of the resin composition.

The heating temperature is generally in the range of 40 to 180 ° C, preferably 60 to 160 ° C.

Accelerators usable in the present invention include polyvalent metal salts such as cobalt, iron and manganese salts of octylic acid and naphthenic acid and organic amines such as dimethyl aniline, diethyl aniline, p-toluidine and ethanol amine. These promoters may be used alone or in combination in the form of a mixture of two or more. The amount of accelerator used is in the range of 0.001 to 3% by weight, preferably 0.05 to 2% by weight, based on the amount of the resin composition.

If necessary, in the resin composition of the present invention, silane coupling agents such as glass fibers, carbon fibers, aramid fibers and whiskers, powder reinforcing agents, fillers, thickeners, methacryl functional silane coupling agents, calcium stearate and paraffins, A release resin, a pigment and a coloring agent, an flame retardant, and a flame retardant may be incorporated to produce a composite resin composition.

The resin composition of the present invention has excellent curability that can be cured very quickly by photopolymerization and thermal polymerization and can be cured even at standard room temperature. Molded products obtained by curing the resin composition exhibit excellent thermal stability at high temperatures and have high heat deformation temperatures. Even if the resin composition is formed by a method such as resin transfer molding, which hardens itself at high temperatures or limits the content of the reinforcement to a relatively low level and tends to cause uneven distribution of reinforcement components, volume shrinkage and thermal expansion during the course of the process. The occurrence of cracking due to regional differences in coefficients is significantly suppressed. Moreover, the resin composition of the present invention enables production of a cured product exhibiting well balanced properties such as water resistance, chemical resistance and mechanical strength.

Because of the above-mentioned advantages, the resin composition of the present invention is produced at a high temperature produced by a resin for heat-resistant secondary molded parts, a resin for heat-resistant injection molded parts, a contact pressure molding method, or a filament winding method produced by a resin transistor molding method or a resin injection molding method. Resin for secondary molded articles having high temperature stability, produced by high productivity continuous molding method such as resin for large secondary molded article having high safety, extrusion molding, drawing molding method, or continuous lamination method, and sheet molding formulation having short molding cycle ( It is produced by the SMC) method or the bulk molding compounding (BMC) method and is advantageously used as the resin for the composite material.

Applications of the resin compositions of the present invention include, for example, corrosion resistant products such as tanks, pipes, ducts and scrubbers, electrical and electronic parts such as leaf springs, drive shafts, automotive parts such as wheels, printed circuit boards and various insulating parts. Components, coating materials for optical fiber cables, materials for injection molded electrical and electronic components, and coating materials and inks.

These are not all discovered by the use of the resin composition of this invention.

The invention is now described more clearly below with reference to the examples. However, it should be noted that the present invention is not limited only to these examples. Where parts and percentages are mentioned below, they are constantly based on weight.

Reference Example 1

In a reaction vessel equipped with a thermometer, a reflux condenser, an air inlet tube and a stirrer, 90 parts of N-tetraglycidyl-diaminodiphenyl methane having 34 parts of methacrylic acid and 125 epoxy equivalents (manufactured by Ciba-Geigy). Commercially available under the trademark "Araldite MY 720", 350 parts of carboxyl-terminated butadiene-acrylonitrile copolymers having a molecular weight of 3500 and a carboxyl content of 2.40% (manufactured by BF Goodrich Corp.). ), 255 parts of p-methyl styrene, 1.8 parts of triethylamine, and 0.4 parts of hydroquinone are added and heated with stirring at 115 ° C. for 5 hours. As a result, a p-methylstyrene solution of a butadiene-acrylonitrile copolymer-modified unsaturated ester compound having an acid value of zero (having a butadiene-acrylonitrile copolymer content of 47.9%) is obtained. In the following, the p-methyl styrene solution of butadiene-acrylonitrile copolymer-modified unsaturated ester compound is referred to as "methacryloyl group-containing butadiene-acrylonitrile copolymer solution (1)".

Reference Example 2

In the same reaction vessel as used in Reference Example 1, 250 parts of N-tetraglacidyl diaminodiphenyl methane having 146 parts of methacrylic acid and an epoxy equivalent of 125 (manufactured by Ciba-Geigy. "Araldite MY 720 And 100 parts of P-methyl styrene, 1.3 parts of triethylamine and 0.3 parts of hydroquinone are added and heated with stirring at 115 ° C. for 6 hours. As a result, a p-methyl styrene solution of an unsaturated ester having an acid value of 3.0 is obtained. 114 parts of p-methyl styrene are added to the solution to obtain a vinyl ester resin (1).

Reference Example 3

In the same reaction vessel as used in Reference Example 1, 118 parts of polymethylene polyaniline (Mitsui-Toatsu Chemical Co., Ltd. product) having an amino content of 128 parts of glycidyl methacrylate, represented by the following general formula: 15.8% Sold under the trademark "MIDA-150". 150 parts of vinyltoluene, 0.6 parts of methyl hydroquinone and 0.9 parts of zinc salicylate are added and heated under stirring at 8O &lt; 0 &gt; C for 8 hours.

(Wherein m represents an average value of 0.8.)

Analysis of the reaction product by nuclear magnetic resonance absorption spectroscopy confirms that glycidylmethacrylate is completely used in the reaction. In this way, a vinyl toluene solution of an unsaturated ester compound is obtained. 50 parts of vinyltoluene is added to the solution to obtain a vinyl ester resin (2).

Reference Example 4

In the same reaction vessel as used in Reference Example 1, 142 parts 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 158 parts glycidyl methacrylate, 160 parts p-methyl styrene, 0.4 Partial methyl hydroquinone and 1.0 part treethylamine are added and heated under stirring at 115 ° C. for 5 hours. Analysis of the reaction product by nuclear magnetic resonance absorption spectroscopy confirms that glycidyl methacrylate was used completely in the reaction. As a result, vinyl ester resin (3) is obtained.

[Examples 1 to 6]

The vinyl ester resins (1) to (3) obtained in Reference Examples 2 to 4 and the methacloyl group-containing butadiene-acrylonitrile copolymer solution (1) obtained in Reference Example 1 were prepared in various ratios shown in Table 1. By mixing, the resin compositions (1) to (6) of the present invention are obtained.

TABLE 1

[Control Examples 1 to 6]

The same carboxyl-terminal-acrylonitrile copolymers as those used in Reference Examples 1 or in which the vinyl ester resins (1) to (3) obtained in Reference Examples 2 to 4 are mixed, are manufactured by BF Goodrich Corp. Comparative resin compositions (1) to (6) are obtained by mixing the product under the trade name CARCTBN 1300 x 13 "with various ratios shown in Table 2.

TABLE 2

Example 7

The resin compositions (1) to (6) and the comparative resin compositions (1) to (6) obtained in Examples 1 to 6 and Control Examples 1 to 6, respectively, based on 100 parts of composition, were used in 1 part of t-butylperoxy. Mix thoroughly with 2-ethylhexanoate. The resulting mixture is placed in a fixed amount of 30 g in a test tube of 18 mm inner diameter and 180 mm deep and cured at 100 ° C. in an oil bath. Visually inspect for signs and appearance of cracks in the sample of the injection molded article. The results are shown in Table 3.

Example 8

The resin compositions (1) to (6) and the comparative resin compositions (1) to (6) obtained in Examples 1 to 6 and Control Examples 1 to 6, respectively, based on 100 parts of composition, were used in 1 part of t-butylperoxy. Mix thoroughly with 2-ethylhexanoate. Thereafter, 20 cm-square pieces of a hand-woven glass fabric (traded under the trademark of "YES-2101-N-1" manufactured by Japan Glass Fiber Mfg Co., Ltd.) are joined to the resulting mixture. Pieces of glass fabric from each sample mixture were piled into 12 wrinkles and compressed at 120 ° C. for 3 minutes at 130 kg / cm ² to obtain a laminated sheet having a glass content of 65 ± 1% and a thickness of 3 mm. The laminate thus obtained is post-cured for 1 hour at 200 ° C. in an air oven and tested for thermal stability. The results are shown in Table 3.

Thermal stability is evaluated by using a laminate test operation of size 75mm × 25mm × 3mm and determining the weight loss rate by heating and the retention of bending strength after heating according to the following formula.

% Weight loss by heating =

The weight of the glass fiber is determined by heating at 240 ° C. for 500 hours in air and then at 600 ° C. for 5 hours.

Bending strength is determined according to JIS K 6911.

TABLE 3

TABLE 3a

Reference Example 5

350 parts of carboxyl-terminal butadiene-acrylonitrile copolymers having a molecular weight of 3500 and a carboxyl group content of 2.40% in the same reaction vessel as used in Reference Example 1 (manufactured by BF Goodrich Corp.). "Hycar CTBN 1300 x 13 29.4 parts of maleic anhydride and 0.1 parts of t-butyl catechol are added and heated with stirring at 180 ° C. for 5 hours under a stream of nitrogen. Analysis of the reaction product by nuclear magnetic resonance absorption spectroscopy confirms that maleic anhydride was used completely in the reaction. As a result, maleate (butadiene-acrylonitrile copolymer) (I) is obtained.

Example 9

In the same reaction vessel as used in Reference Example 1, 10 parts of maleated (butadiene-acrylonitrile copolymer) obtained in Reference Example 5 (1) and 190 parts of vinyl ester resin (2) obtained in Reference Example 3 Was added, and heated under stirring at 100 ° C. for 3 hours. At the end of heating, the reaction product shows no change in acid value in the water-acetone mixed solvent. As a result, a resin composition 7 containing butadiene-acrylonitrile copolymer-modified unsaturated ester compound is obtained.

Example 10

In the same reaction vessel as used in Reference Example 1, 20 parts of maleated (butadiene-acrylonitrile copolymer) obtained in Reference Example 5 (1) and 180 parts of vinyl ester resin (2) obtained in Reference Example 3 Was added, and the mixture was heated with stirring at 100 ° C. for 4 hours. At the end of heating, the reaction product shows no change in acid value in the water-acetone mixed solvent. As a result, a resin composition 8 containing a butadiene-acrylonitrile copolymer-modified unsaturated ester compound is obtained.

Example 11

10 parts maleate (butadiene-acrylonitrile copolymer) obtained in Reference Example 5 (1) and 190 parts vinyl ester resin (3) obtained in Reference Example 4, in the same reaction vessel as used in Reference Example 1 Was added, and heated under stirring at 100 ° C. for 3 hours. At the end of heating, the reaction product shows no change in acid value in the water-acetone mixed solvent. As a result, a resin composition (9) containing butadiene-acrylonitrile copolymer-modified unsaturated ester compound is obtained.

Example 12

Crack signs and appearance of the injection molded articles of the resin compositions (7) to (9) obtained in Examples 9 to 11 were visually investigated according to the procedure of Example 7. The results are shown in Table 4.

Example 13

The thermal stability of the laminated sheets of the resin compositions (7) to (9) obtained in Examples 9 to 11 was tested according to the procedure of Example 8. The results are shown in Table 4.

TABLE 4

Claims (8)

(A) 30 to 95% by weight of at least one unsaturated ester compound selected from the group consisting of an unsaturated ester compound represented by the following general formula (I) and an unsaturated ester compound represented by the following general formula (II), (B) polymerizable At least one (meth) acrylic in the molecular unit thereof, based on 70 to 5% by weight of the cross-linking agent and 100 parts by weight of the vinyl ester resin consisting of (C) (A) unsaturated ester compound and (B) polymerizable cross-linking agent. A heat resistant resin composition comprising 0.5 to 15 parts by weight of a butadiene-acrylonitrile copolymer having a diary.

(Wherein R ¹ and R ⁵ are each

(Wherein R ³ and R ⁴ each represent a hydrogen atom or a methyl group) and one selected from the group consisting of hydrogen atoms, at least one of R ¹ and R ⁵ is

Wherein R ³ and R ⁴ each represent a hydrogen atom or a methyl group, and R ² and R ⁶ each represent an atom or an organic group selected from the group consisting of a hydrogen atom, a halogen atom, a methoxy group and an alkyl group of 1 to 5 carbon atoms M and n each represent 0 or an integer of 1 to 10, and x represents -O-, -S-, when n is 0,

When a divalent organic group selected from the group consisting of n is an integer of 1 to 10, -O-, -S-,

And -CH _2- . A divalent organic group selected from the group consisting of: The composition according to claim 1, wherein the (B) polymerizable crosslinking agent is a styrene compound represented by the following general formula (VIII).

(Wherein R ⁷ represents a hydrogen atom or a methyl group, and R ⁸ represents a hydrogen atom or an alkyl group of 1 to 5 carbon atoms.) The composition according to claim 2, wherein the (B) polymerizable cross-linking agent is a hydrogen atom and a methyl group in the formulas R ⁷ and R ^{8 in the} formula shown. The butadiene-acrylonitrile copolymer according to claim 1, wherein the butadiene-acrylonitrile copolymer having at least one (meth) acryloyl group in the molecular unit of (C) is (d) an epihalohydrin represented by the following general formula (VI). Chemical addition reaction is carried out to (a) an aromatic polyamine represented by the following general formula (III) or (b) an aromatic diamine represented by the following general formula (IV) to prepare an intermediate N-halohydrin, and an alkali is used to form N-halohydrin. Butadiene-acrylonitrile containing at least one group selected from the group consisting of carboxyl groups and amino groups in the reaction between an epoxy compound obtained by dehydrohalogenation reaction of a halohydrin to give a glycidyl group to (meth) acrylic acid A composition that is a butadiene-acrylonitrile copolymer-modified unsaturated ester compound prepared by having the copolymer participate as part of (meth) acrylic acid.

Wherein R ³ represents a hydrogen atom or a methyl group, Y represents a halogen atom, R ² and R ⁶ each represent an atom selected from the group consisting of a hydrogen atom, a halogen atom, a methoxy group and an alkyl group of 1 to 5 carbon atoms or An organic group, m and n each represent 0 or an integer of 1 to 10, and X represents -O-, -S-, when n is 0,

When a divalent organic group selected from the group consisting of n is an integer of 1 to 10, -O-, -S-,

And -CH _2- . A divalent organic group selected from the group consisting of: The butadiene-acrylonitrile copolymer according to claim 1, wherein (C) butadiene-acrylonitrile copolymer having at least one (meth) acryloyl group in its molecular unit is a (A) unsaturated ester of maleic acid chloride (butadiene-acrylonitrile copolymer). At least one group selected from the group consisting of a hydroxyl group and an amino group contained in the (A) unsaturated ester compound by reacting with a compound to the succinic acid inorganic material contained in the maleate (butadiene-acrylonitrile copolymer) The composition is a butadiene-acrylonitrile copolymer-modified unsaturated ester compound obtained by a ring-opening addition reaction. The method according to claim 1, 100 parts by weight of the vinyl ester resin (C) butadiene-acrylonitrile copolymer 1 to (A) consisting of 45 to 80% by weight of the unsaturated ester compound and (B) 55 to 20% by weight of the polymerizable cross-linking agent A composition containing 10 parts by weight. (A) 30 to 95% by weight (B) polymerizable crossover of at least one unsaturated ester compound selected from the group consisting of an unsaturated ester compound represented by the following general formula (I) and an unsaturated ester compound represented by the following general formula (II) At least one (meth) acryloyl group in its molecular unit, based on 70 to 5% by weight of the binder and 100 parts by weight of the vinyl ester resin consisting of (C) (A) unsaturated ester compound and (B) polymerizable crosslinking agent A butadiene-acrylonitrile copolymer having a heat-resistant resin composition containing 0.5 to 15 parts by weight, and a composite resin composition characterized in that it contains a reinforcing agent.

(Wherein R ¹ and R ⁵ are each

(Wherein R ³ and R ⁴ each represent a hydrogen atom or a methyl group) and one selected from the group consisting of hydrogen atoms, at least one of R ¹ and R ⁵ is

(Wherein R ³ and R ⁴ each represent a hydrogen atom or a methyl group), and R ² and R ⁶ each represent an atom or an organic group selected from the group consisting of a hydrogen atom, a halogen atom, a methoxy group and an alkyl group of 1 to 5 carbon atoms M and n each represent 0 or an integer of 1 to 10, and X represents -O-,-S-, when n is 0,

When a divalent organic group selected from the group consisting of n is an integer of 1 to 10 is -O-,-S-,

And -CH _2- . A divalent organic group selected from the group consisting of: The composite resin composition according to claim 7, wherein the composite resin composition is in the form of a sheet.