JPS60133032A - Manufacture of low-fluidity prepreg - Google Patents

Abstract

PURPOSE:To obtain a heat-resistant titled prepreg by impregnating a reinforcing base with a composition comprising multifunctional cyanic acid ester, specific (meth)acrylate, polymerization initiator and thermosetting catalyst followed by heating. CONSTITUTION:The objective prepreg can be obtained by impregnating at room temperature a reinforcing base with a composition in a non-solvent liquid state comprising (A) multifunctional cyanic acid ester having at least two cyanate groups (e.g. 1,3- or 1,4-dicyanate benzene), its prepolymer with a number-average molecular weight 300-6,000 or its prepolymer with amine, (B) (meth)acrylate having at least one (meth)acryloyl and/or (meth)acryloxy group or its prepolymer, (C) as polymerization catalyst for the component (B), benzoyl peroxide and (D) as thermosetting catalyst, zinc octanoate followed by e.g. heating and drying. In case heat resistance is of priority, 50-99(esp. 60-85)wt% of the component (A) should be used, whereas if low-fluidity is of importance, >=50(esp. 60-85)wt% of the component (B) is to be used.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is a novel heat-resistant, low-flow prepreg (one in which molten resin flows less until it hardens during laminated molding).
Regarding the manufacturing method, it is a prepreg that has good thickness accuracy and can manufacture laminates without voids.
A polyfunctional cyanate ester containing two or more cyanato groups in the molecule, a prepolymer of the cyanate ester or a prepolymer of the cyanate ester and an amine, B1 having at least one acryloyl group or methacryloyl group in the molecule. , an acrylate or methacrylate having an acryloxy group or a methacryloxy group, or a prepolymer thereof, a C9 polymerization initiator, and a thermosetting resin composition containing a thermosetting catalyst as essential components is impregnated into a reinforcing base material, and then heated. This is a method for producing a heat-resistant, low-flow prepreg, which is characterized by polymerizing the component B above.

Conventionally, a reinforcing base material is impregnated with a resin composition containing a photopolymerizable polymer or its prepolymer and a photosensitizer. A method has been proposed in which a prepreg is produced by photopolymerization after the preparation, but it is difficult to achieve low fluidity, and it cannot be used for varnishes that use a solvent. In addition, the method of obtaining a B-stage prepreg by impregnating and drying a reinforcing base material with epoxy resin or the like to obtain a low-flow prepreg may cause variations due to uneven heating or other conditions, and some gelation may occur. It was difficult to produce a good low flow prepreg.

As a result of extensive research in order to eliminate the above-mentioned drawbacks, the inventors of the present invention have found that by adding polymerizable 7-mer, prepolymer, and its polymerization initiator to cyanate ester resin, thickness accuracy can be achieved with low flowability. We succeeded in obtaining a prepreg for manufacturing laminates that has good properties and does not generate voids, leading to the present invention.

The present invention will be explained below.

Suitable polyfunctional cyanate esters as component A of the curable resin composition of the present invention have the following general formula +i+ R(OCN)m ----(1) (m in the formula is 2 or more, Usually an integer of 5 or less, R is an aromatic organic group, and the cyanato group is bonded to the aromatic ring of the organic group. A specific example is 1.3-
or 1,4-dicyanatobenzene, 1,3.5-tricyanatobenzene, 1.3-, 1.4-. 1.6~,1.
8-. 2.6- or 2,7-dicyanatonaphthalene, 1
, 3.6-t-lycyanatonaphthalene, 4.4'-diaminobiphenyl, bis(4-dibromophenyl)methane, 2.2-bis(4-cyanatophenyl)propane, 2
, 2-bis(315-dichloro-4-cyanatophenyl)propane, 2,2-bis(3,5-dibromo-4-cyanatophenyl)propane, bis(4-cyanatophenyl)ether, bis(4-cyanatophenyl)propane, -cyanatophenyl)thioether, bis(4-cyanatophenyl)sulfone, tris(4-cyanatophenyl)phosphite, tris(4-
cyanatophenyl) phosphate, and cyanic acid esters obtained by the reaction of novolacs with cyanogen halides. In addition to these, special public interest public works in 1928
, 43-18468, 44-4791, 45
-11712, 46-41112, 47-2685
Cyanic acid esters described in No. 3 and JP-A-51-6314'9 may also be used.

Furthermore, the above-mentioned polyfunctional cyanate ester is used as a prepolymer obtained by polymerization in the presence of a mineral acid, a Lewis acid, a salt such as sodium carbonate or lithium chloride, or a phosphate ester such as tributylphosphine. be able to.

These prepolymers are sym-) formed by trimerization of cyanide groups in the cyanate ester.
Generally has a riazine ring in the molecule. In the present invention, it is preferable to use the prepolymer having a number average molecular weight of 300 to 6,000.

Furthermore, the polyfunctional cyanate esters described above can also be used in the form of prepolymers with amines.

Examples of amines that can be suitably used include meta- or para-phenylene diamine, meta- or para-gysylylene diamine, 1,4- or 1,3-cyclohexanediamine, hexahydroxylylene diamine, 4,4'-diaminobiphenyl, bis (4-aminophenyl)methane, bis(
4-aminophenyl) ether, bis(4-aminophenyl) sulfone, bis(4-amino-3-methylphenyl)methane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-aminophenyl) Cyclohex++-7,2,2-his(4-aminophenyl)propane, 2,2-bis(4-aminol-3-methylphenyl)
Propane, 2,2-bis(4-amino-3-chlorophenyl)propane, bis(4-amino-3-chlorophenyl)methane, 2,2-bis(4-amino-3,5-dibromophenyl)propane, bis (4-aminophenyl)
These include phenylmethane, 3,4-diaminophenyl-4-aminophenylmethane, and 1,1-bis(4-aminophenyl)-1-phenylethane.

Of course, the polyfunctional cyanate esters mentioned above, their prepolymers and prepolymers with amines can be used in the form of mixtures.

The acrylate or methacrylate having at least one acryloyl group, methacryloyl group, acryloxy group, methacryloxy group in the molecule of component B of the present invention, or a prepolymer thereof, refers to the heating or drying conditions in the B-stage process. It becomes a high molecular weight product by polymerizing or crosslinking with a polymerization initiator. Specifically, methyl acrylate, methyl methacrylate (hereinafter both are referred to as methyl (meth) acrylate), ethyl (meth) acrylate, butyl (meth) acrylate-1-12-hydroxy (meth) acrylate, 2-hydroxyethyl ( meth)acrylate, triethylene glycol di(meth)acrylate,
1.6-hexanethiol di(meth)adarylate, neobentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolmethane triacrylate, trimethylolpropane triacrylate , trimethylolpropane l-1J
methacrylate, tetramethylolmethane triacrylate, tetramethylolmethane trimethacrylate,
Pentaerythritol triacrylate, pentaerythritol tetraacrylate, acrylamide, N, N
-Methylene bisacrylate, N-methylolacrylamide, 3-chloro-2-oxypropyl methacrylate, resorcin bisacrylate, N,N-diacryloyl-river-phenylenediamine, N,N-dimethacryloyl-m-phenylenediamine, N -acryloyl-m-
Aminophenol acrylate, allyl methacrylate, 2.2-bis(4-acryloylphenyl)methane,
2.2-bis(3,5-dichloro-4-acryloylphenyl)propane, bis(3-chloro-4-acryloylphenyl)methane, diphenylurethane maleate acrylate-1, conifoxy acrylate, urethane acrylate, Monomers such as polyester acrylate, low molecular weight polymers, copolymers, etc. of one or more of these, and JP-A-56-26911, JP-A-56-2
No. 6950, No. 56-26951, No. 56-1107
Examples include No. 60.

Furthermore, as the polymerization initiator for component C1 of the present invention, the above-mentioned B
Any known component polymerization catalyst can be used. For example, peroxides exemplified by benzoyl peroxide, lauroyl peroxide, cabryl bertoxai F, acetyl peroxide, parachlorobenzoyl peroxide, di-terL-butyl-di-barphthalate, potassium persulfate, ammonium persulfate, sodium perborate, etc. Examples include Ab compounds such as Azobisni I.Ril. Further, the thermosetting catalyst of the present invention includes 2-methylimidazole, 2-undecylimidazole, 2-hebutadecylimidazole, 2-phenylimidazole,
2-ethyl-4-methylimidazole, 1-hensyl-
2-methylimidazole, 1-propyl-2-methylimidazole, ■-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethylimidazole, 1-
Imidazoles exemplified by cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, ■-cyanoethyl-2-ethyl-4-methylimidazole, and l-guanamineethyl-2-methylimidazole, as well as these imidazoles such as adducts of carboxylic acid or its anhydrides to N, N-
dimethylhensylamine, N,N-dimethylaniline,
N,N-dimethyltoluidine, N,N-dimethyl-p-
Anisidine, Kanohalogeno N, N-dimethylaniline,
2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, tomethylmorboline, triethanolamine, triethylenediamine, N, N,
Tertiary amines such as N', N'-tetramethylbutanediamine and N-methylpiperidine; Phenols such as phenol, xylenol, cresol, resorcinol, catechol, and phlologlizine; Lead naphthenate, lead stearate, zinc naphthenate , zinc octylate, lead oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, iron acetylacetonate; inorganic metal salts such as 5nC14, ZnCl2, AlCl3; maleic anhydride, phthalic anhydride Acid, lauric anhydride, pyromellitic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, hexahydro trimellitic anhydride,
Examples include acid anhydrides such as pyromellitic anhydride.

The amounts of the polymerization initiator and thermosetting catalyst added in the present invention are as follows:
A range of catalytic amounts in a general sense is sufficient, for example in amounts of up to 10 wt%, usually up to a few %, based on the total composition.

Examples of the reinforcing base material of the present invention include various glass cloths such as cloth, roving cloth, chopped mat, and surfacing mat, quartz glass cloth, carbon fiber cloth, and non-woven materials such as ashest, rock wool, and slag wool.
Ilb fiber fabric, wholly aromatic polyamide cloth, blended fabric of glass fiber and wholly aromatic polyamide fiber or carbon fiber, polyimide I' cloth, cotton cloth, linen cloth, felt, Graph 1-
Examples include paper, cotton paper, paper-glass blend paper, and semi-carbon fiber cloth.

The present invention provides a curable resin composition that essentially contains the above components, either as a solvent-free liquid composition at room temperature, as a varnish using a solvent, or as a colloid in which some components are dispersed in a liquid in the form of fine powder. Either the components of the present invention are impregnated into a reinforcing base material as a liquid and heated and dried, or the components of the present invention are prepared as a solid, and this is made into a fine powder and attached to the reinforcing base material by a known method such as a fluidized dipping method and heated. By fusing, a component mainly composed of the C component in the resin component is polymerized, thereby producing a low fluidity B-stage prepreg of the present invention.

Here, the usage ratio of each component in the curable resin composition is 50 to 99% of component A when heat resistance is required.
Use wt%, preferably 60-85%. Furthermore, when placing particular emphasis on low fluidity of the obtained prepreg, it is recommended to use component B in an amount of 5 kt% or more, preferably 60 to 85 wt%.

The heating and drying conditions for B-stage are as follows:
Although it varies depending on the type and amount of the components used and the type and amount of the polymerization initiator, it is generally selected appropriately from the range of 50 to 200°C.

Although the present invention is as described above, various additives can be blended into the resin component as desired, as long as the original properties are not impaired. These additives include various well-known additives such as natural or synthetic resins, fibrous reinforcing materials, fillers, dyes, pigments, thickeners, hot water solutions, coupling agents, and flame retardants. They are used in appropriate combinations depending on the situation. Such resin components include polyallyl compounds such as diallylphthale-1, divinylhenzen, diallylhenzen, trialkenyl isocyanurate and their prepolymers; dicyclopencdiene and its prepolymers; epoxy resins; phenolic resins; polyvinyl Polyvinyl acetal resins such as formal, polyvinyl acecool, and polyvinyl butyral; Phenoxy resins; Acrylic resins with 011 or C00II groups; Silicone resins; Alkyd resins; Thermoplastic polyurethane resins; Polybutadiene, butadiene-acrylonitrile copolymers, polychloroprene , butadiene-styrene copolymer, polyisoprene, butyl rubber, natural rubber, and other non-crosslinked (unvulcanized) rubber; polyethylene, polypropylene, polybutene, poly-4-methylpentene.
1. Polyvinyl chloride, vinylidene chloride resin, polystyrene, polyvinyltoluene, polyvinylphenol, A
S 4i (fat, ABS resin, MBS 434 resin, poly-4-fluorinated ethylene, fluorinated ethylene-propylene copolymer, 4-fluorinated ethylene-6-fluorinated ethylene copolymer, vinylidene fluoride, etc.) Polymers of vinyl compounds such as polycarbonate, polyester carbonate, polyphenylene ether, polysulfone, polyester, polyether zalvon, polyamide, polyaimide, polyetherimide F, polyphenylene sulfide, and low polymers of these thermoplastic resins. A single low-molecular W polymer (prepolymer) having a certain molecular weight of 10,000 or less, usually from 1,000 to several thousand, can be produced.

The conditions for manufacturing laminates using the prepreg of the present invention vary depending on the type of curing agent, catalyst, composition components, etc., but are usually selected within the range of 100 to 300"C. Heat curing It is preferable to apply pressure during the process, generally speaking, 0.1 to 500 kg/cnt
, preferably selected appropriately within the range of 5 to 150 kg/CIA.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. In addition, parts in Examples and Comparative Examples are parts by weight unless otherwise specified.

Example-1 2,2-bis(4-cyanatophenyl)propane 100
0g was preliminarily reacted at 160°C for 5 hours to obtain a prepolymer (hereinafter referred to as fa).

A prepolymer (hereinafter referred to as (b)) was obtained by preliminarily reacting 975 g of 1,4-dicyanatohenzene and 43 g of bis(4-7minophenyl)methane at 100°C for 30 minutes.

Hendyl peroxide O, Ig was added to 1000 g of glycidyl methacrylate, and a preliminary reaction was carried out at 100° C. for 30 minutes to obtain a prepolymer (hereinafter referred to as (C1)).

Furthermore, trimethylolpropane triacrylate (hereinafter referred to as (d)) was blended in the ratio shown in Table 1, and used as a polymerization initiator.
A resin composition is prepared by adding and mixing zinc octylate (OCZN) as a thermosetting catalyst, and this is impregnated into a glass fiber woven fabric under heating at 50°C and dried to prepare a prepreg. A circular hole with a diameter of 50mm was made in the center of the hole, and this was layered with a thick 35μ electrolytic copper foil, a release film was placed on the other side, and sandwiched between two thick mirror plates, 35kg/C.
Laminate molding was carried out at 175° C. for 2 hours to obtain a laminate, and the maximum flow distance of the resin flowing into the holes of this plate and other characteristics of the laminate were also measured.

The results are also listed in Table 1.

Example-2 Example-1 fb), (dl and epoxy resin (trade name, Epicoat 828; oil-based shell epoxy (structure,
(hereinafter referred to as te+) and G-te as a polymerization initiator.
r t-Butyl peroxide (DTBP) and 0CZN as a thermosetting catalyst are blended in the ratio shown in Table 1, dissolved and mixed in methyl ethyl ketone, impregnated into a wholly aromatic polyamide fiber woven fabric and dried to form a prepreg. The procedure was the same as in Example-1 except that . The results are shown in Table 1.

Comparative Example-1 Example-1 (81 alone was blended with 0CZN as a thermosetting catalyst in the ratio shown in Table 1, dissolved and mixed in methyl ethyl ketone, impregnated into a glass woven fabric and dried to prepare a prepreg. was carried out in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example-2 BPO was blended with (C) of Example-1 alone as a polymerization initiator in the ratio shown in Table 1, melted and mixed with methyl ethyl ketone, impregnated into a glass woven fabric, and dried to prepare a prepreg. The rest was the same as in Example-1. The results are shown in Table 1.

Table 1

Claims (1)

[Scope of Claims] A polyfunctional cyanate ester containing two or more cyanato groups in one molecule, a prepolymer of the cyanate ester, or a prepolymer of the cyanate ester and an amine, at least one cyanato group in the B0 molecule. 4 or more acryloyl units,
After the reinforcing base material is impregnated with a thermosetting resin composition containing a methacryloyl group, an acryloxy group, an acrylate or methacrylate containing a methacryloxy group, or a prepolymer thereof, a C0 polymerization initiator, and a thermosetting catalyst as essential components. A method for producing a heat-resistant, low-flow prepreg, characterized by polymerizing the component B under heating.