JPS61143419A - Resin composition and intermediate for composite material - Google Patents

Abstract

PURPOSE:To provide a resin composition of high floxural strength, elastic modulus and rigidity, capable of giving the titled intermediate by impregnating in reinforcer, comprising each specific amine compound and epoxy compound, epoxy resin and curing agent. CONSTITUTION:The objective resin composition can be obtained by incorporating (A) 100 pts. by wt. of an epoxy resin with (B) pref. 1-100 pts. by wt. of a compound of formula I (e.g., methylamine, 2-ethylhexypropylamine), (C) pref. 1-100 pts. by wt. of a second compound of formula II (R1-R4 are each H, 1-17C aliphatic, alicyclic, aromatic, heterocyclic hydrocarbon, etc.) (e.g., epichlorohydrin, phenyl glycidyl ether), (D) a curing agent (e.g., o- phenylenediamine) and, if needed, (E) a curing accelerator.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin composition whose cured product exhibits excellent mechanical properties, and an intermediate material for composite materials obtained by impregnating a reinforcing material with this resin composition.

Conventionally, various resin compositions have been used as matrix resins for composite materials, but in the field of thermosetting resins in particular, the excellent mechanical properties of the resin itself, especially its strength, elongation, and heat resistance, as well as its strength as a reinforcing material. Epoxy resins have been widely used because they have good adhesion and the strength development of reinforcing materials is superior to other thermosetting resins.However, the strength development of reinforcing materials is still insufficient. However, improving the stiffness of the resin itself also increases its heat resistance, which not only gives it more performance than necessary, but also significantly reduces its elongation. However, it has some drawbacks that make it unusable for some applications.

The present inventors have intensively investigated intermediate materials for composite materials that can improve various mechanical properties, mainly compression properties, and have discovered an additive that can significantly improve rigidity without reducing the elongation of the resin itself. It was confirmed that the mechanical properties of various composite materials using the epoxy resin-curing agent system as a matrix resin were significantly improved.

The present invention is applicable to the general formula %(), which is a hydrogen atom, a 01 to C17 saturated or unsaturated aliphatic group, an alicyclic group, an aromatic group, a heterocyclic group, or R1
, R2, R3, and R4 together with the nitrogen atom bonded thereto represent a heterocyclic residue, and each of these groups may be substituted with a halogen atom, a nitro group, an alkoxy group, an allyloxy group, or an acetyl group. ),
It is a resin composition consisting of an epoxy resin and a curing agent, or a resin composition formed by blending a curing accelerator into this resin composition.

The present invention further provides an intermediate material for a composite material in which the resin composition described above is impregnated with a reinforcing agent.

Examples of the compound represented by the general formula I include the following compounds. Methylamine, ethylamine, n-propylamine, n-butylamine, isopropylamine, 2-ethylhexyloxypropylamine, 6-nitoxyglobylamine, di-2-ethylhexylamine,
dibutylaminopropylamine, diisobutylamine,
Aliphatic amiacetaldehyde ammonia such as 6-medoxyprobylamine, allylamine, secondary butylamine, isopropanolamine, 2-ethylhexylamine, cyclohexylamine, dicyclohexylamine, 4-
Aminopyridine, N-aminopropylmorpholine, bisaminopropylbiverazine, piperazine, 2-pipecoline, piperidine, pyrrolidine, 5-fluorouracil,
N-methylpiperazine, β-alanine, glycylglycine, glutamic acid, γ-amino lbutyric acid, r-aminocaproic acid, glycine, etc.

Examples of the compound represented by the general formula (2) include the following compounds. Epichlorohydrin, phenylglycidyl ether, cyclohexene oxide, ethylene oxide, propylene oxide, butadiene oxide, dimethylpentane dioxide diglycidyl ether, butanesiol cyclidyl ether, ethylene glycol diglycidyl ether, vinyl cyclohexene dioxide, limonene dioxide, bis( 2,3-epoxycyclopentyl) ether, divinylbenzene dioxide,
Resorcin diglycidyl ether, 2-glycidylphenylglycidyl ether, 6,4-epoxy-6-methylcyclohexylmethyl-6,4-evoquine methylcyclohexanecarboxylate, ethylcricidyl ether, styrene oxide, p-butylphenol glycidyl ether, Low molecular weight epoxy compounds such as cresyl glycidyl ether, glycidyl methacrylate, allyl glycidyl ether, cyclohexene vinyl monoxide, dipentene monoxide, α-pinene oxide, and 3-(pentadecyl)phenyl glycidyl ether.

The resin composition of the present invention contains 1 to 100 parts by weight of Compound I and 1 to 10 parts by weight of Compound (2) per 100 parts by weight of epoxy resin.
It is preferable to contain 0 parts by weight. Compounds ■ and ■ are 1
If it is less than 1 part by weight, no substantial effect can be achieved. Moreover, if both exceed 100 parts by weight, the heat resistance will be significantly reduced. It is preferable that any combination of substituents R1, R2 or R3, R4 of compounds (1) and (2) has a highly rigid structure of an aromatic group or a heterocyclic group.

Examples of the epoxy resin include the following compounds. Polyglycidyl ethers of polyhydric phenols such as polyhydric phenols such as novolak and resol;
Epoxy resins such as 3,4-epoxy-6-methyl- produced by epoxidation of alicyclic compounds such as cyclohexane, cyclopentadiene, dicyclopentadiene, etc.
Cyclohexane-carboxylic acids (3,4-epoxy-
6-methyl-cyclohexane)-methyl esters, poly(epoxyalkyl)ethers of aliphatic polyoxy compounds such as ethylene glycol, glycerin, etc., epoxies of carboxylic acids such as glycidyl esters of aromatic or aliphatic carboxylic acids; alkyl esters, etc. These may be precondensates of epoxy resins and curing agents as described in US Pat. Nos. 3,590,057, 2,970,983, and 3,067,170, or may be simple mixtures. In addition, these may be used alone, or 2
More than one species may be used in combination.

Examples of the curing agent used in the present invention include the following compounds. 0-phenylenediamine, m-phenylenediamine, 4,4-methylenedianiline, 4,4'-
Diaminodiphenylsulfone, 5,5'-diaminodiphenylsulfone, m-xylene diamine, triethylenetetramine, diethylenetriamine, inphoronediamine, 1,6-diamitcyclohexanementhanediamine, cyanethylated diethylenetriamine, N-aminoethylpiperazine, methyl iminobispropylamine, aminoethylethanolamine, polyether diamine,
Polyamines such as polymethylene diamine, phthalic anhydride, succinic anhydride, maleic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, trimellitic anhydride, itaconic anhydride,
trimellitic anhydride, itaconic anhydride, citraconic anhydride, dodecenylsuccinic anhydride, maleic anhydride adduct of methylcyclopentadiene, methyltetrahydrophthalic anhydride, toluic anhydride adduct of maleic anhydride, cyclopentanetetracarboxylic anhydride, Acidic substances having polycarboxylic acid groups, polycarboxylic acid anhydride groups, or mixed groups thereof such as alkylated endoalkylene tetrahydrophthalic acid anhydride, ethylene glycol bistrimelite, glycerin tristrimethhenite, isophthalic acid dihydrazide, adipine Hydrazides such as acid dihydrazide and sebacic acid dihydrazide, polyamide amines, diandiamide, ketimine, etc.

Examples of curing catalysts include the following compounds. Boron trifluoride complexes such as boron trifluoride monoethylamine complex compounds and boron trifluoride piperidine complex compounds, imidazole compounds such as 2-methylimidazole and 2-ethyl-4-methylimidazole, triphenylphosphite, butanetetracarboxylic acid, 18-diaza-bicyclo-(5,4゜0
)-undecene-7, N-(3-chloro-4-methoxyphenyl) -N', N'-dimethylurea, N-(4
-chlorophenyl)-N',N'-dimethylfyvl,
N-(3-chloro-4-ethylphenyl) -N', N
'-Dimethylurea, N-(6-chloro-4-methylphenyl) -N', N'-dimethylurea, N-(3,
4-dichlorophenyl)-ys-dimethylurea, N-
(4-ethoxyphenyl) -N', N'-dimethylurea, N-(4-methyl-3-nitrophenyl) -N
urea compounds such as ',N'-dimethylurea, etc.

The combination and quantitative ratio of the epoxy resin and curing agent are preferably close to the generally stoichiometric range, and when a curing catalyst is included, it is preferable to use the curing agent at a slightly lower stoichiometric ratio. Further, when the compounds (1) and (I) have a functional group that can contribute to curing, it is preferable to reduce the amount of the curing agent depending on the functional group in the compound. Compounds and If are mainly effective for epoxy resins using amine-based curing agents, but they also exhibit some effect on acid anhydride-based curing agents. These additives work effectively to improve the rigidity of the epoxy resin (the reason is not clear, but the reason is that there is This is thought to be due to the formation of relatively strong hydrogen bonds.

As reinforcing materials for the intermediate material for composite materials of the present invention, inorganic fibers such as glass fiber, carbon fiber, boron fiber, silicone carbide fiber, etc. Examples include paper-like materials, asbestos, mica, Merck, etc., and these can be used alone or in combination of two or more. Depending on the application, pigments, dyes, stabilizers, plasticizers, lubricants, tar, asphalt, and other reinforcing materials may also be used. The content of reinforcing materials is preferably 5 to 80% by volume. Thermosetting resins and thermoplastic resins other than epoxy resins can also be used in combination.

Since the resin composition of the present invention contains Compounds I and (2), its bending strength and elastic modulus are significantly improved, and its rigidity is also excellent. Further, by impregnating a reinforcing material with this resin composition, an intermediate material for a composite material with particularly improved rigidity can be obtained. This intermediate material can also be used in new fields such as aircraft.

Examples 1 to 16 and Comparative Examples 1 to 7 Compounds I and ■ shown in the table below were mixed at a ratio of 10 Phr each into 100 parts by weight of an epoxy resin (Epicor 828 manufactured by Niji Koru Kagaku Co., Ltd.) and heated at a temperature of 60°C. Stir for 10 minutes to mix uniformly. Next, 60 parts by weight of diaminodiphenylmethane was added to this system and mixed uniformly at 60°C for 10 minutes to obtain a resin composition (A). Using this resin composition (A), 90°C for 1 hour and 16
A resin plate was molded under curing conditions of 0°C x 1 hour, and a bending test was conducted. The results are shown in the table below. In addition, resin composition (
Carbon fibers were uniformly impregnated with A) and aligned in one direction to produce a sheet prepreg.

This prepreg was laminated and cured in a mold at 90° C. for 1 hour and 160° C. for 1 hour at 7 kg/cm 2 (7) to produce a composite. The measurement results of the flexural strength, flexural modulus 1 flexural elongation, and interlaminar shear strength of this composite are also shown in the table below. From this, it was found that the resin composition of the present invention significantly improves the physical properties of the resin plate, and also significantly improves the mechanical properties of the composite.

Claims (1)

[Claims] 1. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, R_1, R_2, R_3 and R_4 may be the same) hydrogen atoms, saturated or unsaturated aliphatic groups, alicyclic groups, aromatic groups, heterocyclic groups of C_1 to C_1_7, or R_1, R_2, R_3, and R_4 are the nitrogen atoms bonded to them. together indicate a heterocyclic residue;
Each of these groups may be substituted with a halogen atom, a nitro group, an alkoxy group, an allyloxy group, or an acetyl group), a resin composition consisting of an epoxy resin, and a curing agent, or a resin composition containing a curing agent. A resin composition containing a combination of agents. 2. General formulas ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, R_1, R_2, R_3 and R_4 may be the same or different. , a hydrogen atom, a saturated or unsaturated aliphatic group of C_1 to C_1_7, an alicyclic group, an aromatic group, a heterocyclic group, or R_1, R_2, R_3, R_4 together with the nitrogen atom bonded to it form a heterocyclic ring. indicates the residue,
Each of these groups may be substituted with a halogen atom, a nitro group, an alkoxy group, an allyloxy group, or an acetyl group), a resin composition consisting of an epoxy resin, and a curing agent, or a resin composition containing a curing agent. An intermediate material for composite materials in which a reinforcing material is impregnated with a resin composition containing a compounding agent.