JPS61252234A - Fiber-reinforced plastic intermediate material - Google Patents

Abstract

PURPOSE:To obtain the titled intermediate material having a resin composition excellent in heat resistance and thickening property as a matrix resin, by impreg nating a reinforcing fiber with a resin composition comprising specified three compounds, a polymerization catalyst, a polyisocyanate and a reaction accelera tor. CONSTITUTION:A reinforcing fiber is impregnated with a resin composition obtained by mixing a mixture comprising 100pts.wt. mixture obtained by mixing a compound (A) selected from an OH group-containing unsaturated polyester and a reaction product between an epoxide and an ethylenically unsaturated carboxylic acid with an ethylenically or allylically unsaturated monomer (B) copolymerizable therewith and a polymerization catalyst (C) at a weight ratio of 0.1-100:100-0.1:0.1-5 and 0.1-100pts.wt. compound (D) selected from a maleimide and a mixture or prereaction product of a maleimide with a polycyanate ester with a polyisocyanate (E) in an amount corresponding to an OH/NCO ratio of 1:0.1-1.1 and 0.1-10pts.wt. per 100pts.wt. compounds A-E, reaction accelerator (F) for reaction between component E and the OH- containing compound.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a fiber-reinforced plastic (FRP) intermediate material made of a resin and reinforcing fibers having excellent curability, handling properties, and heat resistance.

Conventionally, sheet molding compound (SMC)
Resins used as matrices for fiber-reinforced plastic products such as bulk molding comparants (BMCs) and prepregs require fast thickening to reduce coating without significant polymerization and to maintain fiber cohesiveness. It had been. For this purpose, a general method has been proposed in which a carboxylic acid group is introduced into the structure of an unsaturated polyester resin composition and the viscosity is increased using magnesium oxide or the like (see US Pat. No. 2,628,209). However, since the above-mentioned method generally utilizes a reaction between a solid and a liquid, it lacks quantitative and controllability of the reaction, and the drawback is that the thickening behavior, especially the thickening level and rate, vary significantly depending on time and temperature. It had Furthermore, resin compositions based on unsaturated polyester resins generally have poor heat resistance, and there have been problems with their performance, particularly when used as composite materials for industrial materials. The present inventors have carried out research in view of the above points, and as a result, we have found that FR using a resin composition as a matrix resin that has excellent heat resistance and thickening properties with excellent quantitative and controllability.
Found a P intermediate material.

The present invention provides at least one compound selected from the group consisting of a hydroxyl group-containing unsaturated polyester (A) and a reaction product of an epoxide and an ethylenically unsaturated carboxylic acid
I), an ethylenically or allylic unsaturated monomer copolymerizable therewith (II), a catalyst for the polymerization of (I) and (I[) (1), maleimide (C') or maleimide and polyfunctional cyanide A mixture of acid esters (DJ) or a pre-reactant selected from the group consisting of one compound (IV), polyisocyanate (VI) and a reaction accelerator (VI) between isocyanate and a compound having a hydroxyl group. This is a fiber-reinforced plastic intermediate material in which reinforcing fibers are impregnated with a resin composition.

The resin composition used in the present invention can also be produced from a compound that does not have a carboxylic acid group.

The polyester (A) used in the present invention can be produced by subjecting a divalent carboxylic acid or its acid anhydride to a dehydration condensation reaction with a glycol. Examples of divalent carboxylic acids include unsaturated divalent carboxylic acids such as fumaric acid and maleic acid, phthalic acid, inphthalic acid, adipic acid, phthalic anhydride,
Saturated dicarboxylic acids such as succinic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride are used. As the glycol, diethylene glycol, globylene glycol, neohentyl glycol, butanediol, hydrogenated bisphenol A, 2,2-di(4-hydroxypropoxyphenyl)propane, etc. are used.

Examples of polyepoxides include the following compounds. diphenylolpropane, diphenylolethane,
Polyglycidyl ethers of diphenyloalkanes such as diphenylolmethane, polyglycidyl ethers of polyhydric phenols such as novolak and resol, umbrellas such as p-aminephenol, m-aminephenol, 4,4'-diaminodiphenylmethane, etc. Ami/'s Polyglyci,) &,
Epoxy resins produced by epoxidation of alicyclic compounds such as cyclohexene, cyclobentazidine, and dicyclopentadiene, methyl ester of 6,4-epoxy-6-methylcyclohexanecarboxylic acid, ethylene glycol, glycerin, etc. Glycidyl esters of aliphatic carboxylic acids, etc. Preliminary reaction products of these polyepoxides and amines or acid anhydrides may also be used. Examples of ethylenically unsaturated carboxylic acids include methacrylic acid, acrylic acid, and crotonic acid. It is preferable to use polyepoxide and ethylenic ratio. This reaction can be carried out by a known method, for example, the method described in Japanese Patent Publication No. 31472/1983.

Examples of the ethylenically or allylic unsaturated monomer (11) include styrene, vinyltoluene, styrene derivatives such as chlorostyrene, methacrylates or acrylates such as methyl methacrylate, methyl acrylate, glycidyl acrylate, glycidyl methacrylate, diallyl phthalate, etc. Examples include allyl esters.

Examples of the catalyst (1) for the polymerization of (I) and (II) include benzoyl peroxide, tertiary butyl perbenzoate, dicumyl peroxide, and other medium- to high-temperature active peroxides; methyl ethyl ketone peroxide, cyclohexamember oxide, and other medium-temperature active peroxides; Active peroxides may be mentioned. In particular, polyfunctional compounds are preferred.

The maleimide (C) used in the present invention includes maleimides having the general formula (where X is an aromatic or aliphatic divalent residue) as well as prepolymers obtained from these maleimides. The above-mentioned maleimide can be produced by a known method by reacting maleic anhydride with an amine and cyclodehydrating the resulting maleimide.As the amine, aromatic amines are preferred from the viewpoint of heat resistance.
When it is desired to impart flexibility, it is also possible to use aliphatic amines alone or in combination. Furthermore, when bismaleimide is used as the maleimide, impact resistance can be imparted by replacing a portion of the bismaleimide with monomaleimide.

Examples of amines include the following compounds: tL6゜phenylamine, O-methylphenylamine, m-methylphenylamine, p-methylphenylamine, 0-methoxyphenylamine, m-methoxyphenylamine, p
-Methoxyphenylamine, 0-chlorphenylamine, m-chlorphenylamine, p-chlorphenylamine, 6,5-dimethylphenylamine, 3,4-dimethylphenylamine, 0-aminophenol, p-aminephenol, lauryl Amine, myristylamine, palmitylamine, stearylamine, oleylamine,
Monoamines such as tertiary butylamine and cyclohexylamine;
1,4-Cyclohexanediamine, hexahydroxylylenediamine, bis(4-aminophenyl)methane, bis(4-aminophenyl)sulfone, bis(4-amino-3-methylphenyl)sulfone, bis(4-amino-
3-methylphenyl)methane, bis(4-amino-5,
5-dimethylphenyl)methane, bis(4-7minophenyl)cyclohexane, bis(4-aminophenyl)ether, 2.2-bis(4'-aminophenyl)propane, bis(a--amino-3-methylphenyl) ) Diamines such as methane and bis(4-aminophenyl)phenylmethane.

Polyfunctional cyanate ester + Dl has the general formula % (in the formula, R is an aromatic residue, and n is an integer from 2 to 5)
These are organic compounds having two or more cyanate ester groups and prepolymers thereof, such as the following compounds.

1,5-dicyanatobenzene, 1,4-dicyanatobenzene, 1,5.5-)lycyanatobenzene, 1,
3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,8-
Dicyanatonaphthalene, 2,6-dicyanatonaphthalene, 2,7-dicyanatonaphthalene, 1,3,5-
Tri7anatonaphthalene, 4.4-cyanatophenyl, bis(4-cyanatophenyl)methane, 2.2
-bis(4-7 anatophenyl)propane, 2,2-
Bis(5,5-dichloro-4-cyanatophenyl)propane, 2,2-bis(3,5-dibromo-4-cyanatophenyl)propane, bis(4-schif-)phenyl)ether, bis( 4-cyanatophenyl) sulfone, tris(4-cyanatophenyl) phosphite,
tris(4-cyanatophenyl)phosphate, cyanate ester obtained by reaction of novolak with cyanogen halide, and the like. The polyfunctional cyanate ester can be used as a pre-reactant with an amine in addition to the above-mentioned pre-reactant. Examples of the amine include those used in the synthesis and modification of maleimide described above. These pre-reactants are obtained by pre-reacting in the presence or absence of a catalyst.

As the polyisocyanate (v), 4,4'-diphenylmethane diisocyaner), 2,4-torx.

Aromatic and aliphatic polyisocyanates such as diisozoanate, 2,6-toluine diisocyanate, hexamethylene diisocyanate, metaxylylene diisocyanate, and the like.

The reaction accelerator (■) is not particularly limited as long as it catalyzes the reaction between a general isocyanate and a compound having an alcoholic OH group, but the coexistence of a tertiary amine is not appropriate. , dibutyltin dilaurate, organotin compounds such as tin octoate, and naphthenic acid metal salts such as lead naphthenate and cobalt naphthenate.

The compounding ratio of (I), (1) and value) in the present invention is sufficient as long as it satisfies general radical polymerization systems, but generally the ratio of (I) / (1) / (wound ratio by weight) is sufficient. ,
0°1-100: 100-0.1: 0.1-5 are preferred. If the catalyst content is less than 0.1, a sufficient curing rate cannot be obtained, and if it exceeds 5, the curing will be too rapid and is not suitable.

When maleimide (C) and a polyfunctional cyanate ester (DJ) are used as (rV), their blending ratio can be varied over a wide range and there is no essential limit, but for example, (C1/(DJ ratio can be used in a ratio of 1 to 99:99 to 1. Furthermore, it is preferable from the viewpoint of impact resistance that monomaleimide and bismaleimide are used in combination as maleimide (C).

The blending ratio of (I) and (III) to 100 parts by weight of the former is QV10.1-10 of the latter.
0 parts by weight is preferred. The amount of polyisocyaner (V) to be added is preferably 1:0.1 to 1.1 in terms of OH/NCO functional group ratio to the formulations of (I) to (1v). The hardness, handleability, etc. of the resin composition can be adjusted by adjusting the amount added. The addition amount of the reaction accelerator (Figure) is preferably 0.1 to 10 parts by weight per 100 parts by weight of the formulations (I) to (VI).

After mixing the above-mentioned components and impregnating reinforcing fibers with the resulting resin composition, the mixture is heated at room temperature to 60°C, particularly at room temperature to 40°C.
It is preferable to leave it at ℃ to thicken the viscosity.

The reinforcing fibers used in the present invention include inorganic fibers such as glass fibers, alumina fibers, silicon carbide fibers, and carbon fibers, and organic fibers such as polyester fibers and polyaramid fibers, and these may be used in combination as necessary. . The reinforcing fibers may be in the form of long fibers or short fibers, and may be in the form of tapes, sheets, mats, cloth, paper, strings, etc. arranged in one direction.

In addition, the resin composition may include glass, silica, alumina, quartz, mica, calcium carbonate, barium sulfate,
Powdered fillers such as clay, various coloring agents, and mold release agents such as zinc stearate and phosphate esters may also be used in combination.

Manufacturability iK of FRP intermediate material using the resin composition of the present invention
There is no particular restriction on the method, and the reinforcing fibers may be impregnated with a lacquer method using a solvent or a hot melt method without using a solvent. When using a solvent to impregnate reinforcing fibers, inert solvents such as acetone, methyl ethyl ketone,
It is preferable to use methylene chloride, chloroform, trichloroethylene, dioxane, tetrahydrofuran, benzene, toluene, and the like. Parts in the following examples mean parts by weight. The bending strength and elastic modulus are ASTM D79.
0-71, Izot impact strength was measured using a notched test piece in accordance with ASTM D 256-73.

Example 1 50 parts of maleic anhydride and 108 parts of diethylene glycol
50 parts of phthalic anhydride and 0.0 parts of hydroquinone were reacted for 6.5 hours at 140-230°C.
0.2 parts was added and reacted at 140 to 260° C. for 6.1 hours to esterify, yielding an unsaturated polyester fiber with an unsaturated acid content of 19.8%. 7 parts of diallyl phthalate monomer and 3 parts of tertiary butyl perbenzoate were added to 100 parts of this polyester and kneaded on a triple roll at 50°C for 60 minutes to obtain a composition (al). Methane (b) was added in the proportions shown in Table 1, and polymethylene polyphenylisocyanate (viscosity 25°C, 150 cps, NC) was added to 100 parts of (a).
7 parts of O content (31%), 0.0 parts of diptyltin dilaurate.
9 parts and 3 parts of zinc stearate were added and kneaded for 30 minutes using a homomixer to obtain a resin composition (c). After 120 parts of chopped strand glass fiber mat was impregnated with 100 parts of this resin composition, SMC with low stickiness was obtained by leaving the mat at 40° C. for 48 hours under closed conditions. This SMC was heated at 150°C for 6 minutes at a pressure of 30 kg.
/cm2 to obtain a molded product. The mechanical properties of this molded product are shown in Table 1.

Table 1 Example 2 95 parts of bisphenol A diglycidyl ether type epoxy resin (epoxy equivalent: 190), 39 parts of methacrylic acid, 0.7 part of lithium chloride, and 0.0 part of hydroquinone
5 parts were added and reacted at 100°C to obtain a vinyl ester. 40 parts of styrene and 2.5 parts of dicumyl peroxide were added to 60 parts of this vinyl ester, and the mixture was heated to 50°C with three rolls.
The mixture was kneaded for 60 minutes to obtain a composition (d). On the other hand, the screw (4
50 parts of -maleimidophenyl)methane and 50 parts of 2,2-bis(4-cyanatophenyl)furopane were dissolved in N-methylpyrrolidone, stirred at 40°C for 10 minutes, and then dried under vacuum to form composition (e). I got it. (d) and (e)
Add in the ratio (weight ratio) shown in Table 2, and further (d)
To 100 parts, 10 parts of polymethylene polyphenylinocyanate, 0.7 parts of diptyltin dilaurate, and 6 parts of Zeretsu UN (non-neutralizing phosphate alcohol, product of DuPont) were added, and the mixture was stirred for 20 minutes with a homomixer. A resin composition (f) was obtained. This resin composition was cast using a normal SMC machine, and then carbon fiber pyrofil EAS (product of Mitsubishi Rayon Co., Ltd.) 1 o o o o
The fibers were dropped onto the cast resin composition while being cut into 25 lengths using an ol, and at the same time, the cast resin composition was covered from above to impregnate the fibers with the resin, and then at 40°C for 48 hours. By leaving it in a sealed state, an SMC with a low stickiness and a fiber content of 50% by weight was obtained. This SMC is 150
℃ for 3 minutes at a pressure of 30 kp/cm'', and then post-cured at 170℃ for 1 hour to change the first property to the second.
Shown in the table.

Table 2 Example 6 Novolac type epoxy resin (manufactured by Shell Chemical Co., Ltd.).

42 parts of methacrylic acid, 0.7 parts of lithium chloride and 0.05 parts of hydroquinone were added to 95 parts of Epicoat 152 (epoxy equivalent: 175) and reacted at 100°C to obtain a vinyl ester resin.

A resin composition (gl) was obtained by mixing 40 parts of styrene and 2.5 parts of tertiary butyl perbenzoate with 60 parts of this vinyl ester resin.N-phenylmaleimide (h) was added to this as shown in Table 3. Add in proportion, further K (g) I
To 0 parts of D, 8 parts of polymethylene polyphenylinocyanate, 0.5 parts of diptyltin dilaurate, and 2 parts of Zerec UN were added.

A resin composition (1) was obtained by stirring for 30 minutes using a homomixer. After casting this resin composition on a polyethylene film, carbon fiber pyrofil EAS10000 fi
The fibers were impregnated with resin by aligning and uniting the fibers. This sheet was left sealed at 40° C. for 48 hours to obtain a unidirectionally aligned sheet with low tackiness and a fiber content of 60% by weight. Laminate these sheets and heat at 1508C for 3 minutes.

A molded article was obtained by curing under the conditions of 60 kg/Crn2.

target The mechanics and properties of this molded product are shown in Table 3.

Table 3 Example 4 Part of the bis(4-maleimidophenyl)methane (b) in Example 1 was replaced with N-methylphenylmaleimide (j) in the proportions shown in Table 4 to form monomaleimide. A mixture of bismaleimides (fi) was obtained. This was added to composition (a) in a ratio of (a)/(h) of 100/20, and further 7 parts of polymethylene polyphenylinocyanate and 0.9 parts of tertiary butyltin dilaurate were added to 100 parts of (a). of the resin was added and kneaded for 30 minutes using a homomixer to obtain a resin composition (1). This resin composition 100
After impregnating 120 parts of chopped strand glass fiber mat with 120 parts of chopped strand glass fiber mat, SMC with low tackiness was obtained by leaving the mat at 40° C. for 48 hours under closed conditions. This SMC is 15
It was cured at 0°C for 6 minutes under a pressure of 30 kg, 7 cm20 to obtain a molded product. The mechanical properties of this molded product are shown in Table 4.

Table 4

Claims (1)

[Claims] 1. Hydroxyl group-containing unsaturated polyester (A) and reaction product of epoxide and ethylenically unsaturated carboxylic acid (B)
At least one compound selected from the group consisting of (I
), an ethylenically or allylic unsaturated monomer copolymerizable with it (II), a catalyst for the polymerization of (I) and (II) (II
I), at least one compound (IV) selected from the group consisting of maleimide (C) or a mixture or preliminary reaction product of maleimide and polyfunctional cyanate ester (D), polyisocyanate (V), isocyanate and hydroxyl group A fiber-reinforced plastic intermediate material in which reinforcing fibers are impregnated with a resin composition consisting of a reaction accelerator (VI) and a compound having 2. The intermediate material according to claim 1, wherein the hydroxyl group-containing unsaturated polyester (A) is a reaction product of maleic acid or phthalic acid and glycol. 3. The reaction product (B) of polyepoxide and ethylenically unsaturated carboxylic acid is a polyglycidyl ether of diphenylolalkane, polyhydric phenol, polyhydric amine or epoxidized product of aliphatic compound and methacrylic acid, acrylic acid or The intermediate material according to claim 1, which is a reaction product with crotonic acid. 4. The intermediate material according to claim 1, wherein the ethylenically or allylic unsaturated monomer (II) is a styrene derivative, acrylate, methacrylate or allyl ester. 5. The intermediate material according to claim 1, wherein the catalyst (III) is benzoyl peroxide, tertiary butyl perbenzoate, methyl ethyl ketone or cyclohexamember oxide. 6. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, X is an aromatic or aliphatic divalent residue, Y is a hydrogen atom or group ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ 2. The intermediate material according to claim 1, which contains a maleimide represented by (shown) or a prepolymer obtained from this maleimide. 7. The polyfunctional cyanate ester (D) has the general formula R-(O
-C≡N)_n (in the formula, R is an aromatic residue, n is an integer from 2 to 5)
The intermediate material according to claim 1, which is an organic compound having two or more cyanate ester groups represented by the formula or a prepolymer thereof. 8. A patent claim in which the polyisocyanate is 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate or metaxylylene diisocyanate. Intermediate material according to scope 1. 9. The intermediate material according to claim 1, wherein the reaction accelerator (VI) is an organic tin compound or a metal naphthenate. 10. The intermediate material according to claim 1, wherein the reinforcing fibers are glass fibers, alumina fibers, silicon carbide fibers, boron fibers, carbon fibers, polyester fibers, or polyaramid fibers. 11. The intermediate material according to claim 1, wherein the blend ratio of (I), (II) and (III) to (IV) is 100:0.1 to 100 by weight. 12. The amount of polyisocyanate (V) added is (I) ~
For the formulation of (IV), the OH/NCO functional group ratio is 1:0.
．． The intermediate material according to claim 1, which is 1 to 1. 13. The intermediate material according to claim 1, wherein the reaction accelerator (VI) is added in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the mixtures (I) to (V). 14. The intermediate material according to claim 1, which contains 0.3% by weight or more of monomaleimide in maleimide (C).