JPS62146927A - Intermediate for composite material - Google Patents

Abstract

PURPOSE:To obtain an intermediate for composite materials excellent in high heat resistance, water resistance and impact resistance, by impregnating a reinforcement with a resin composition formed by mixing a specified reaction product with an epoxy compound and a polyester compound. CONSTITUTION:A resin composition is obtained by mixing 100pts.wt. mixture formed by mixing a polymaleimide (A) such as a bismaleimide of formula I (where in R2 is a bivalent aromatic group or an aliphatic group) with a polycyanic ester of formula II (wherein n is 2-5 and R3 is an aromatic organic residue) or its oligomer (B) at an A to B weight ratio of 5-15/95-85 or prereaction product between components A and B with 5-100pts.wt. epoxy compound (e.g., bisphenol A diglycidyl ether) and 5-50pts.wt. polyester compound of formula III [wherein Ar is phenylene (e.g., o-phenylene), and R1 is a bivalent aliphatic group (e.g., a group of formula IV), having a softening temperature <=100 deg.C and an average MW of 500-10,000. A reinforcement such as glass fiber is impregnated with the above resin composition to obtain an intermedia for composite materials of a reinforcement content of 0.5-80vol%.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an intermediate material for composite materials that provides excellent heat resistance, water resistance and mechanical properties.

[Prior art]

Conventionally, various resin compositions have been used as matrices for composite materials, but especially in the field of thermosetting resins, in addition to the excellent mechanical properties of the resin itself (particularly strength and elongation), it is important to Epoxy resins have been widely used because they have good adhesive properties and the strength development of reinforcing materials is superior to other thermosetting resins. In recent years, there has been a strong demand for higher performance of composite materials, especially improvements in heat resistance, water resistance, and impact resistance. These pre-reactants are being considered. As a result, although the rigidity of the resin increased and the heat resistance and water resistance of the composite material improved, there were problems with a decrease in elongation and a decrease in impact resistance.

[Purpose of the invention]

The inventors of the present invention have conducted intensive studies to develop an intermediate material for composite materials that has high heat resistance, water resistance, and excellent impact resistance.
As a result, we have arrived at the present invention.

[Structure of the invention]

The present invention comprises 100 parts by weight of a mixture of a polyfunctional maleimide (CI) and a polyfunctional cyanate ester or its oligomer (I[), or a preliminary reaction product (A) of (I) and (1), an epoxy compound (B ) and 5 to 50 parts by weight of a polyester compound (C) represented by the general formula (wherein Ar is a phenylene group and R8 is a divalent aliphatic group) as a reinforcing material. This is an intermediate material for composite materials impregnated with

In the polyester compound (C) of formula (1), the phenylene group for the substituents A and r may be any of ○-phenylene group, m-phenylene group, and p-phenylene group; As the valent aliphatic group, a linear or branched aliphatic group having 2 to 6 carbon atoms is preferable, and examples thereof include the following groups. Group +CH2+, (-CR2
mo, -CH, -CI((CH3)-17CH-C2H3
, +CR2+, -CH2-CH(CH,) -CR2-
1+CI(2+-1-(-CH2)CH,(CH3)-
1+CR2) CH(CHs) CH2-1-(-
an2-) CH(C2H,)-1-CH,, -C(C
H3), -CH2-, etc.

The polyfunctional maleimide m(1) used in the present invention is a compound having two or more maleimide groups, and is represented by the general formula (wherein R2 represents a divalent aromatic or aliphatic group). In addition to bismaleimide, it includes prepolymers obtained from these bismaleimides and diamines. The bismaleimide of formula (2) can be produced by a known method in which maleic anhydride and diamine are reacted to prepare bismaleamic acid, followed by cyclodehydration. As the diamine, aromatic diamines are preferred from the viewpoint of heat resistance, but aliphatic amines may be used alone or in combination if it is desired to impart functions such as flexibility. Examples of the diamine include m-phenylenediamine, p-phenylenediamine, 4.4'-diaminodiphenylsulfone, 6.6
'-Diaminodiphenyl sulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, etc. are used.

Polyfunctional cyanate ester [(It
) is an organic compound having two or more cyanate ester groups and its oligomer, and has the general formula %Formula %(6) (where n is an integer of 2 to 5, R3 is an aromatic organic residue) This is a compound represented by Examples of polyfunctional cyanate esters include 1,3- or 1,4-dicyanatobenzene, 4,4-dicyanatobiphenyl, bis(4-cyanatophenyl)methane, and 2,2-bis(4-dicyanatobenzene).
-cyanatophenyl)ethane, 2,2-bis(4-cyanatophenyl)propane, bis(4-cyanatophenyl)sulfone, etc. are used. The polyfunctional cyanate ester described above can be used in the form of a triazine oligomer obtained by trimerizing cyanate, or in the form of a prepolymer obtained by reaction with an amine. and those used for metamorphosis.

In the present invention, the above polyfunctional maleimide (
I) and polyfunctional cyanate ester (II) alone,
Alternatively, a pre-reactant obtained by pre-reacting without a catalyst or in the presence of a catalyst is appropriately selected and used depending on the purpose.

The epoxy compound CB) used in the present invention may be any known epoxy resin, such as the following compounds. Polyglycidyl ethers of diphenylolalkanes such as diphenylolpropane, diphenylolethane, diphenylolmethane, novolacs, cresols,
Epoxy resins produced by epoxidation of polyglycidyl ethers of polyhydric phenols such as resols, alicyclic compounds such as cyclohexane, cyclopentadiene, and dicyclopentadiene, such as 6,4-epoxy-6-methyl-cyclohexane. (!1,4-Epoxy-6-methyl-cyclohexane)-methyl esters of carboxylic acids, poly(epoxyalkyl)ethers of aliphatic polyoxy compounds such as ethylene glycol and glycerin, glycidyl esters of aromatic or aliphatic carboxylic acids, etc. epoxyalkyl esters of carboxylic acids, etc. It may also be a preliminary reaction product of an epoxy resin and a curing agent as described in US Pat. No. 5,390,037, US Pat. No. 2,970,983, and US Pat.

These may be used alone or in combination of two or more. Suitable epoxy compounds include, for example, diglycidyl ether of bisphenol A or diglycidyl ether of bisphenol F, or an epoxy group/NH group ratio of 4 of these epoxy compounds and diaminodiphenylsulfone.
/1 pre-reactant is mentioned.

The polyester compound (C
) is preferably a compound in which the acid component is mainly terephthalic acid and the glycol component is mainly neopentyl glycol or ethylene glycol. The polyester compound used in the present invention needs to have a softening point of 100°C or lower, preferably 70°C or lower. When the softening point exceeds 100°C, polyfunctional maleimides,
The compatibility with the polyfunctional cyanate ester orchid and the epoxy compound becomes poor, making it difficult to obtain a uniform composition. This polyester compound has a number average molecular weight of 500 to 1
0000. In particular, it is preferably 500 to 3000. If it is less than 500, the viscosity decreases, and if it exceeds 10,000, it is not suitable because it lacks workability in mixing with other components. The polyester compound used in the present invention can be produced by a general method used in producing other linear polyesters.

The resin composition used in the present invention needs to have a composition ratio of 5 to 100 parts by weight of the B component and 5 to 501 parts by weight of the C component to 100 parts by weight of the A component. If the amount of the epoxy compound used as component B is less than 5 parts by weight, the adhesion to the substrate will be poor, and if it exceeds 100 parts by weight, satisfactory heat resistance will not be obtained. Furthermore, if the amount of the polyester compound used as component C is less than 5 parts by weight, sufficient impact resistance will not be exhibited, and if it exceeds 50 parts by weight, heat resistance and solvent resistance will be significantly reduced. The ratio (1)/(Ill) in component A is preferably 5 to 15,795 to 85. If the amount of polyfunctional maleimide M(1) is more than 15, hot water resistance improves, but a high curing temperature is required. , impact resistance decreases, and if it is lower than 5, although impact resistance improves, hot water resistance decreases, which is not preferable.

A catalyst may be added to the resin composition used in the present invention for the purpose of imparting desired properties to the cured resin product or adjusting the thermosetting properties of the resin. As a catalyst, for example, in addition to a latent curing catalyst such as a boron trifluoride amine complex compound,
Triethylenediamine, 1,8-diazabicyclo(5,
4,0) Tertiary amines such as undecene, N,N-dimethylbenzylamine, N-methylmorpholine, tri-n-butylamine, organic peroxides such as dicumyl peroxide, benzoyl peroxide, t-butyl hydroperoxide, etc. substance, zinc octylate, tin octylate, zinc naphthenate,
Examples include organic acid metal salts such as cobalt nanthenate.

The amount of catalyst to be used may be determined depending on the purpose, but from the standpoint of stability of the resin composition, the amount of catalyst used should be 0.2% based on the total resin solid component.
It is preferable to set it as 3 weight%.

Reinforcing materials for the intermediate material for composite materials of the present invention include inorganic fibers such as glass fibers, carbon fibers, boron fibers, and silicon carbide fibers, as well as poly-p-phenylene terrescleamide, poly-p-benzamide, and polyamide hydrazide. Chopped, yarn, tape, sheet, knitted, mat, compositions and asbestos made of organic fibers such as
Mica, Merck, etc., and mixtures of two or more of these are used.

Depending on the purpose, flow control agents such as fine silicon oxide powder, pigments, dyes, stabilizers, plasticizers, lubricants, tar, asphalt, etc. may also be used alone or in combination with other reinforcing materials.

When impregnating a reinforcing material with a resin composition, the resin composition is pre-reacted at a temperature of 50 to 120°C to produce a prepolymer, and this prepolymer is dissolved in a solvent such as methyl ethyl ketone and impregnated into the reinforcing material. is preferred. The content of the reinforcing material in the intermediate material for composite material is preferably 0.5 to 80% by volume. Further, thermosetting resins and thermoplastic resins other than epoxy resins can be used in combination.

12 Example 1 Bis(4-maleimidophenyl)methane, 2,2-bis(4-cyatophenyl)furopane, epoxy equivalent 17
Polyester (a) with a softening point of 25°C consisting of Epikote 807 (manufactured by Shell Chemical Co., Ltd.) of No. 2, terephthalic acid as an acid component, and neopentyl glycol as a glycol component.
were mixed in the proportions shown in the table below, and then silicon oxide fine powder A was added.
ERO8IL 380 (manufactured by Nippon Aerosil Co., Ltd.) 1.2
5 parts and 0°2 dicumyl peroxide as curing catalyst
A prepolymer was obtained by pre-reacting at 70° C. for 60 minutes. This prepolymer was sandwiched between glass plates to a predetermined thickness and cured at 180° C. for 2 hours to obtain a resin plate.

In addition, this prepolymer was dissolved in methyl ethyl ketone,
One-way prepreg (thread date 145 g/m
", resin content 66% by weight) was obtained. This prepreg was laminated on (o'l+a), and also [+45°10°/-45
°/+90°] 48 degrees, and cured at 180°C for 2 hours to obtain a composite material. Various tests were then conducted on resins and composite materials. The results are shown in the table below. The glass transition point (Tg) in the table is the jandelta MAX temperature measured with a dynamic mechanical spectrometer manufactured by Rheometrics. The hot water resistance of composite materials is
0° 16 layers of laminated material composite in 71°C water for 14 hours
121° according to ASTM D695 after being left for a day.
The determination was made by performing a compression test in the 0° direction at C. In addition, impact resistance is based on NASARP 1092,
A board with dimensions 4X'6X0°25 inches is fixed on a stand with a 6x5 inch hole, and a 1/2 inch radius /
It was determined by dropping a weight of 4.9 kg with a weight on it, applying an impact of 15,001 bins per inch of plate thickness, and then subjecting the plate to a compression test. Note that all composite data are values converted to a fiber content of 60%.

Example 2 Polyester (b) with a softening point of 20°C consisting of terephthalic acid as the acid component and a 1:1 (by weight) mixture of ethylene glycol and neopentyl glycol as the glycol component was used instead of polyester (a), and the other conditions were as follows. A resin plate and a composite material were obtained in the same manner as in Example 1. The results of various tests are shown in the table below.

Example 3 A resin plate and a composite material were obtained in the same manner as in Example 1 except that Epikote 828 (manufactured by Shell Chemical Co., Ltd.) having an epoxy equivalent of 184 to 194 was used as the epoxy resin. The test results are shown in the table below.

Example 4, Comparative Examples 1 and 2 Example 1 except that the amount of polyester (a) used was changed.
A resin plate and a composite material were obtained in the same manner as above. The test results are shown in the table below.

Example 5, Comparative Examples 6 and 4 A resin plate and a composite material were obtained in the same manner as in Example 1 except that the amount of Epicote 807 used was changed.

The test results are shown in the table below.

Examples 6 and 7 Resin plates and composite materials were obtained in the same manner as in Example 1, except that the amounts of bis(4-maleimidophenyl)methane and 2,2-bis(4-cyana-)phenyl)propane were changed. Ta. The test results are shown in the table below.

Claims (1)

[Claims] 1. A mixture of polyfunctional maleimide (I) and polyfunctional cyanate ester or its oligomer (II) or (
I group, R_1 represents a divalent aliphatic group) (C) 5-50
An intermediate material for composite materials in which a reinforcing material is impregnated with a resin composition consisting of parts by weight. 2. The intermediate material for a composite material according to claim 1, wherein the polyfunctional maleimide (I) is bismaleimide of diaminodiphenylmethane. 3. The intermediate material for a composite material according to claim 1, wherein the polyfunctional cyanate ester (II) is bisphenol A dicyanate. 4. Epoxy compound (B) is diglycidyl ether of bisphenol A or diglycidyl ether of bisphenol F, or a preliminary reaction product of these epoxy compounds and diaminodiphenylsulfone at an epoxy group/NH group ratio of 4/1. An intermediate material for a composite material according to claim 1, which is characterized by: 5. Claim 1, wherein the polyester compound (C) is a reaction product from terephthalic acid and neopentyl glycol, has a softening temperature of 100°C or less, and an average molecular weight of 500 to 10,000. Intermediate material for composite materials described in section. 6. The intermediate material for a composite material according to claim 1, which contains 0.2 to 3% by weight of silicon oxide fine powder. 7. The weight ratio of (I)/(II) in component A is 5 to 15/
95 to 85, the intermediate material for a composite material according to claim 1. 8. 0.2 boron trifluoride monoethylamine complex, dicumyl peroxide and/or zinc octylate as a catalyst
The intermediate material for a composite material according to claim 1, characterized in that the intermediate material contains ~3% by weight.