JPH06837B2 - Resin composition - Google Patents

Description

The present invention relates to a resin composition whose curing gives excellent mechanical properties and an intermediate material for a composite material obtained by impregnating a reinforcing material with the resin composition.

Conventionally, various resin compositions have been used as matrix resins for composite materials, but especially in the field of thermosetting resins, the resin itself has excellent mechanical properties, particularly strength, elongation and heat resistance, and a reinforcing material. The epoxy resin has been widely used because it has good adhesiveness and the strength development property of the reinforcing material is superior to other thermosetting resins. However, the strength development rate of the reinforcing material is not yet sufficient, and especially in terms of compression characteristics, its improvement has been earnestly desired. However, when attempting to improve the rigidity of the resin itself, at the same time, the heat resistance increases, so that it has the disadvantage of not only providing unnecessarily high performance but also remarkably reducing the elongation, and it cannot be used for some applications.

As a result of diligent examination of the composite material intermediate material capable of improving various mechanical properties centering on compression characteristics, the present inventors have found an additive capable of significantly improving rigidity without lowering the elongation of the resin itself, It was confirmed that the mechanical properties of various composite materials containing the matrix resin as the epoxy resin-curing agent system in which it was blended were remarkably improved.

The present invention is based on 100 parts by weight of epoxy resin, as well as (Formulas R ₁ , R ₂ , R ₃ and R ₄ may be the same or different and may be a hydrogen atom, a C _{1 to} C ₁₇ saturated or unsaturated aliphatic group, an alicyclic group, an aromatic group, a hetero group. A ring group, or R ₁ , R ₂ ,
R ₃ and R ₄ together with the nitrogen atom bonded to them represent a heterocyclic residue, and each of these groups may be substituted with a halogen atom, a nitro group, an alkoxy group, an aryloxy group or an acetyl group) Compounds represented by 1 to 10
A resin composition comprising 0 part by weight and a polyamine-based or acidic-substance-based curing agent, or a resin composition obtained by mixing a curing accelerator with the resin composition.

Examples of the compound represented by the general formula I include the following compounds. Methylamine, ethylamine, n-propylamine, n-butylamine, isopropylamine, 2-ethylhexyloxypropylamine, 3-ethoxypropylamine, di-2-ethylhexylamine, dibutylaminopropylamine, diisobutylamine, 3-methoxypropylamine , Aliphatic amines such as allylamine, secondary butylamine, isopropanolamine, 2-ethylhexylamine, cyclohexylamine, dicyclohexylamine, aniline, p-aminobenzoic acid, aromatic amines such as 3,4-xylidine, dibenzylamine , Benzylamine, acetaldehyde ammonia, 4-aminopyridine, N-aminopropylmorpholine, bisaminopropylpiperazine, piperazine, 2
-Pipecoline, piperidine, pyrrolidine, 5-fluoruracil, N-methylpiperazine, β-alanine, glycylglycine, glutamic acid, γ-aminobutyric acid, γ-aminocaproic acid, glycine and the like.

Examples of the compound represented by the general formula II include the following compounds. Epichlorohydrin, phenylglycidyl ether, cyclohexene oxide, ethylene oxide, propylene oxide, butadiene oxide, dimethylpentane dioxide diglycidyl ether, butanediol, diglycidyl ether, ethylene glycol diglycidyl ether, vinylcyclohexene dioxide, limonene dioxide, bis ( 2,3-epoxycyclopentyl) ether, divinylbenzene dioxide, diglycidyl ether of resorcin, 2-glycidylphenyl glycidyl ether, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxymethylcyclohexylcarboxylate, Butyl glycidyl ether,
Styrene oxide, p-butylphenol glycidyl ether, cresyl glycidyl ether, glycidyl methacrylate, allyl glycidyl ether, cyclohexene vinyl monooxide, dipentene monooxide, α-
Low molecular weight epoxy compounds such as binene oxide and 3- (pentadecyl) phenyl glycidyl ether.

The resin composition of the present invention comprises 1 to 100 parts by weight of compound I and 1 to 10 parts by weight of compound II based on 100 parts by weight of epoxy resin.
Contains 0 parts by weight. If the compounds I and II are less than 1 part by weight, substantial curing cannot be exhibited. Further, if both parts exceed 100 parts by weight, the heat resistance is significantly reduced. It is preferred that the combination of the substituents R ₁ , R ₂ or R ₃ , R ₄ of the compounds I and II have a highly rigid structure of an aromatic group or a heterocyclic group.

Examples of the epoxy resin include the following compounds. Diphenylol propane, diphenylol ethane,
By epoxidation of polyglycidyl ethers of diphenylol alkanes such as diphenylol methane, polyglycidyl ethers of polyhydric phenols such as novolac and resole, and cycloaliphatic compounds such as cyclohexane, cyclopentadiene and dicyclopentadiene. The produced epoxy resin, for example, (3,4-epoxy-6-methyl-cyclohexane) -methyl ester of 3,4-epoxy-6-methyl-cyclohexane-carboxylic acid, an aliphatic polyoxy compound such as ethylene glycol and glycerin Epoxyalkyl esters of carboxylic acids such as poly (epoxyalkyl) ethers, glycidyl esters of aromatic or aliphatic carboxylic acids, and the like. These are US Pat. No. 33
No. 90037, No. 2970983, No. 30671
It may be a precondensate of an epoxy resin and a curing agent as described in each specification of No. 70, or may be a simple mixture. These may be used alone or in combination of two or more.

Examples of the curing agent used in the present invention include the following compounds. o-phenylenediamine, m-phenylenediamine, 4,4-methylenedianiline, 4,4'-dianodiphenylsulfone, 3,3'-diaminodiphenylsulfone, m-xylenediamine, triethylenetetramine, Diethylenetriamine, isophoronediamine, 1,3
-Polyamines such as diaminocyclohexanementhanediamine, cyanoethylated diethylenetriamine, N-aminoethylpiperazine, methyliminobispropylamine, aminoethylethanolamine, polyetherdiamine, polymethylenediamine, phthalic anhydride, succinic anhydride, maleic anhydride , Hexahydrophthalic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid anhydride, trimellitic anhydride, itaconic anhydride, trimellitic anhydride, itaconic anhydride, citraconic anhydride, dodecenylsuccinic anhydride, methylcyclopentadiene maleic anhydride Adduct, methyltetrahydrophthalic anhydride,
Toluic acid adduct of maleic anhydride, cyclopentane tetracarboxylic acid anhydride, alkylated endoalkylene tetrahydrophthalic acid anhydride, polycarboxylic acid groups such as ethylene glycol bis trimellitate, glycerin tris trimellitate, polycarboxylic anhydride groups or Acidic substances having mixed groups thereof.

Examples of the curing catalyst include the following compounds. Boron trifluoride monoethylamine complex compounds, boron trifluoride complex compounds such as boron trifluoride piperidine complex compounds, imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, triphenyl phosphite, butane tetracarboxylic acid Acid, 1,8-diaza-bicyclo- (5.4.0) undecene-7, N- (3-chloro-4-methoxyphenyl) -N ', N'-dimethylurea, N- (4-chlorophenyl)- N ', N'-dimethylurea, N- (3-chloro-4-ethylphenyl) -N', N'-dimethylurea, N- (3-chloro-4-methylphenyl) -N ',
N'-dimethylurea, N- (3,4-dichlorophenyl)
-N ', N'-dimethylurea, N- (4-ethoxyphenyl) -N', N'-dimethylurea, N- (4-methyl-3-nitrophenyl) -N ', N'-dimethylurea, etc. Urea compounds, etc.

Generally, the combination and quantification of the epoxy resin and the curing agent are preferably in the vicinity of the stoichiometry, and when the curing catalyst is included, it is preferable to use the curing agent at a slightly lower level depending on the stoichiometry. Further, when the compounds (I) and (II) have a functional group capable of contributing to curing, it is preferable to reduce the amount of the curing agent depending on the functional group in the compound. The compounds I and II are mainly effective for the epoxy resin which is an amine-based curing agent, but exhibit some effect even for the acid anhydride type. Although the reason why these additives effectively work to improve the rigidity of the epoxy resin is not clear, a comparison was made between the hydroxyl group generated by the ring opening of the epoxy group and the hydroxyl group generated by the reaction of the compounds I and II during curing. It is considered that this is because a strong hydrogen bond is formed.

As a reinforcing material when manufacturing an intermediate material for a composite material using the resin composition of the present invention, other inorganic fibers such as glass fiber, carbon fiber, boron fiber, and silicone carbide fiber, poly-p-phenylene terephthalamide, Examples include chops, yarns, tapes, sheets, knits, mats or papers, asbestos, mica, talc, etc. made of organic fibers such as poly-p-benzamide and polyamide hydrazide, which may be used alone or Two or more kinds can be mixed and used. Further, pigments, dyes, stabilizers, plasticizers, lubricants, tars, asphalts, and other reinforcing materials can be used depending on the application. Reinforcement content is 5-80% by volume
Is preferred. Further, a thermosetting resin or a thermoplastic resin other than the epoxy resin can be used together.

Since the resin composition of the present invention contains the compounds I and II, the bending strength and elastic modulus are remarkably improved and the rigidity is also excellent. Further, by impregnating the reinforcing material with this resin composition, an intermediate material for a composite material having particularly improved rigidity can be obtained. This intermediate material can also be used in new fields such as aircraft.

Examples 1 to 13 and Comparative Examples 1 to 7 Epoxy resin (Epicoat 828: manufactured by Shell Chemical Co., Ltd.) 1 was prepared using compounds I and II shown in the following table at a ratio of 10 Phr.
It was mixed with 100 parts by weight and stirred at a temperature of 60 ° C. for 10 minutes to uniformly mix. Then diaminodiphenylmethane 3 was added to this system.
0 part by weight was added and uniformly mixed at 60 ° C. for 10 minutes to obtain a resin composition (A). Using this resin composition (A), a resin plate was molded by a celcast method under curing conditions of 90 ° C. × 1 hour and 130 ° C. × 1 hour, and a bending test was conducted. The results are shown in the table below. Further, the resin composition (A) was uniformly impregnated into the carbon fibers and aligned in one direction to prepare a sheet-like prepreg.

This prepreg was laminated and cured in a mold at 90 ° C. × 1 hour and 130 ° C. × 1 hour under the conditions of 7 kg / cm ² to prepare a composite. The measurement results of the flexural strength, flexural modulus, flexural elongation and interlaminar shear strength of this composite are also shown in the following table. From this, in the resin composition of the present invention,
It has been known that the physical properties of the resin plate are significantly improved and the mechanical properties of the composite are remarkably improved.

Claims (1)

[Claims] 1. A general formula for 100 parts by weight of an epoxy resin. as well as (In the formula, R ₁ , R ₂ , R ₃ and R ₄ may be the same or different, and are a hydrogen atom, a C _{1 to} C ₁₇ saturated or unsaturated aliphatic group, an alicyclic group, an aromatic group, Heterocyclic group, or R ₁ , R ₂ , R
₃ , R ₄ together with the nitrogen atom to which it is attached represent a heterocyclic residue, each of these groups being a halogen atom, a nitro group,
A resin composition comprising 1 to 100 parts by weight of a compound each represented by an alkoxy group, an aryloxy group or an acetyl group) and a polyamine-based or acidic substance-based curing agent, or a curing accelerator for the resin composition A resin composition comprising: