JPS61239913A - Hard resin mold - Google Patents

Abstract

PURPOSE:To attain to enhance heat resistance and humidity resistance, by using a cyanic ester resin composition as the binder resin of a metal powder or a metal fiber. CONSTITUTION:25-75 pts. wt. of a cyanic ester resin composition (A) with m.p. of 100 deg.C or less, 75-25 pts. wt. of a metal powder or a metal fiber (B) and, if necessary, a curing catalyst (C) are mixed and, after the resulting mixture is injected in a mold, the resin is gelled under heating mixture is injected in a mold, the resin is gelled under heating and further heated to be cured. The resin composition (A) consists of a polyfunctional cyanic ester represented by a general formula R(OCN)m(wherein m is an integer of 2 or more, usually, 5 or less, R is an aromatic org. group and the above mentioned cyanato group is bonded to the aromatic ring of said org. group) and the prepolymer thereof as essential components. This hard resin mold is excellent in heat resistance and abrasion resistance and can be utilized as a simple mold for molding resins having high heat resistance.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a hard resin mold, which is a type of simple mold. The present invention relates to a hard resin mold that has excellent workability and can use a process of gelling the resin at a relatively low temperature of about 100 to 140° C. in a short time.

[Conventional methods and their problems]

Conventional hard resin types mainly mix epoxy resin with metal powder or metal fibers, use tertiary amines, acid anhydrides, etc. as hardening agents, and then mix curing catalysts and then heat or heat them at room temperature. It is manufactured by a method of hardening.

However, epoxy resins usually have limited heat resistance and moisture resistance, and one way to improve this is to use high heat resistant epoxy resins such as multifunctional epoxy resins, but using this resin alone is extremely brittle and impractical. Therefore, it has become essential to mix a flexibility imparting agent, and as a result, the improvement in heat resistance has been insufficient.

[Means for solving problems]

The present inventors have significantly improved the drawbacks of the conventional method as described above, and have achieved superior heat resistance, thermal conductivity, abrasion resistance, and processability and workability compared to conventional hard resin molds. As a result of intensive study on the method of manufacturing an excellent hard resin mold,
The present invention was completed by discovering a method of using a cyanate ester resin composition as a binding resin (binder resin).

That is, the present invention comprises 25 to 75 parts by weight of a cyanate ester resin composition (A) having a melting point of 100°C or less, 75 to 25 parts by weight of metal powder or metal fiber (B), and, if necessary, a curing catalyst. This is a hard resin mold characterized by mixing (C), casting the mixture, gelling the resin by heating, and curing the resin by further heating.

The present invention will be explained below.

The cyanate ester resin composition (A) of the present invention having a melting point of 100° C. or less is a composition consisting of a polyfunctional cyanate ester represented by the following general formula (1), a prepolymer thereof, etc. as essential components, and a cyanate resin. (Japanese Patent Publication No. 41-1928, No. 45-11712, German Patent No. 44-1222, German Patent No. 1190184, etc.), cyanate ester-maleimide resin, cyanate ester-maleimide-epoxy resin (Japanese Patent Publication No. 54-30440) etc., Special Publication No. 52-3127
No. 9, USP-4110364, etc.), cyanate ester-epoxy resin (Japanese Patent Publication No. 46-41112), and the like.

1 Here, suitable polyfunctional cyanate esters have the following general formula (1) % formula % (11 (in the formula, m is an integer of 2 or more and usually 5 or less, and R is an aromatic organic group, in which the cyanato group is bonded to the aromatic ring of the organic group.Specific examples include 1゜3-
or 1,4-dicyanatobenzene, 1,3.5-tricyanatobenzene, 1.3-. 1.4-. 1.6-, L8
−． 2.6 = or 2°7-dicyanatonaphthalene, 1,
3.6-) lycyanatonaphthalene, 4,4'-diaminobiphenyl, bis(4-cyanatophenyl)methane,
2.2-bis(4-cyanatophenyl)propane; 2.
2-bis(3,5-dichloro-4-cyanatophenyl)
Propane, 2,2-bis(3,5-dibromo-4-cyanatophenyl)propane, bis(4-cyanatophenyl)ether, bis(4-cyanatophenyl)thioether, bis(4-cyanatophenyl) Sulfone, Tris (
4-cyanatophenyl) phosphite, tris(4-cyanatophenyl) phosphate, and cyanic acid esters obtained by the reaction of polycarbonate oligomers containing terminal OH groups with cyanogen halides (USP-4026
913), cyanic acid ester obtained by reaction of novolak and cyanogen halide (■5P-402275
5, USP-344807). In addition to these, Special Publications No. 41-1928, No. 43-18468, No. 4
4-4791, 45-11712, 46-411
12, 47-26853, JP-A-51-63149,
USP-3553244, 3755402, 37403
4B, 3595900.

Cyanic acid esters described in 3694410 and 4116946 can also be used.

In addition, a preform obtained by polymerizing the above-mentioned polyfunctional cyanate ester in the presence or absence of a mineral acid, a Lewis acid, a salt such as sodium carbonate or lithium chloride, a phosphate ester such as tributylphosphine, etc. Used as a polymer. These prepolymers generally have a sym-triazine ring in the molecule, which is formed by trimerization of the cyanide group in the cyanate ester.

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-phenylenediamine;
meta- or para-xylylene diamine, 1,4- or 1
．． 3-Cyclohexanediamine, hexahydroxylylenediamine, 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)cyclohexane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-
Amino-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)phenylmethane, 3.4
-diaminophenyl-4-aminophenylmethane, 1,
1-bis(4-aminophenyl)-1-phenylethane and the like.

The above-mentioned polyfunctional cyanate esters, prepolymers thereof, and prepolymers with amines can be used alone or in the form of mixtures, and the number average molecular weight of the individual and mixtures is preferably 1.500 or less, especially 300 to 1.000. A range of is preferred.

Cyanate ester-maleimide resin (Special Publication Publication No. 54-.3
0440, etc.), cyanate ester-maleimide-epoxy resin (Japanese Patent Publication No. 52-31279, etc.), and cyanate ester-epoxy resin (Japanese Patent Publication No. 46-41112). Maleimide, which is a compositional component, is a compound represented by the following general formula (2) or a prepolymer thereof.

(In the formula, R+ is an aromatic or alicyclic organic group having a valence of 2 or more and usually a valence of 5 or less, X, , x.

is hydrogen, halogen, or an alkyl group, and n is usually an integer of 2 to 5. ) Maleimides represented by the above formula are produced by a method known per se in which maleic anhydride and polyamines containing 2 to 5 amino groups are reacted to prepare maleamic acid, and then maleamic acid is cyclized by dehydration. can do. The polyamines used are preferably aromatic polyamines in terms of the heat resistance of the final resin, but if flexibility and flexibility of the resin are desired, alicyclic amines may be used alone or in combination. good. Further, it is desirable that the polyamines be primary amines from the viewpoint of reactivity, but secondary amines can also be used. Suitable amines include those exemplified as those used as prepolymers with cyanate esters, and melamines having an s-) lyazine ring;
These are polyamines made by reacting aniline with formalin and linking benzene rings with methylene bonds. In the present invention, it is preferable to use the resin in an amount of usually 25% or less of the resin component in the composition.

Epoxy resins can be any of those conventionally used as hard resins, laminates, or for electronic materials, and specifically, bisphenol A type epoxy resins, bisphenol F type epoxy resins, etc. Epoxy resin, phenol novolac type epoxy resin, Talesol novolac type epoxy resin, halogenated bisphenol A type epoxy resin, halogenated phenol novolac type epoxy resin, polyglycol type epoxy resin, alicyclic epoxy resin, etc., and these alone Or used as a mixture of two or more. In the present invention, it is preferable to use the resin in an amount of usually 50% or less of the resin component in the composition.

The cyanate ester resin composition (A) of the present invention preferably contains the above components, but in addition to these, the composition has improved viscosity behavior, adhesiveness, curability, flexibility, etc. Diaryl phthalate: resins, unsaturated polyester resins, phenolic resins, acrylic resins,
Thermosetting resins such as urethane resins; mixtures of thermoplastic resins such as thermoplastic polyurethane resins, polyolefins, and saturated polyester resins can also be used.

The metal powder or metal fiber (B) of the present invention is mainly used for the purpose of imparting thermal conductivity to a resin mold and is not particularly limited, but specific examples include iron, aluminum, copper, etc. , copper alloy, aluminum, minilam alloy, iron alloy, silver, etc.

A composition consisting of the above components (A) and (B) usually gels and hardens by heating as component (B) has the ability to act as a curing catalyst for component (A). In addition, a curing catalyst (C) is added as necessary to achieve faster and more complete curing. As such curing catalyst (C), any known curing catalyst for cyanate ester resin compositions can be used, including amines, imidazoles, organometallic salts,
Examples include inorganic metal salts and organic peroxides. Among these catalysts, those suitable for the purpose of the present invention include a single organic metal salt and a combination system of an organic metal salt and an organic peroxide. Examples of organic metal salts include zinc naphthenate, lead stearate, lead naphthenate, zinc octylate, tin oleate,
These include tin octylate, dibutyltin malate, manganese naphthenate, cobalt tephthenate, iron acetylacetone, manganese acetylacetonate, etc. Organic peroxides include benzoyl peroxide, lauroyl peroxide, caprylic peroxide, acetyl peroxide, para Examples include chlorobenzoyl peroxide, di-tert-butyl di-perphthalate, and the like.

The amount of these curing catalysts used is sufficient within the range of catalytic amounts in a general sense, for example, 10% of the total resin composition.
-t % or less, in particular 5 wt % or less.

In addition to the above-mentioned components, the composition of the present invention may also contain, for example, a chelating agent such as acetylacetone as a stabilizer in order to improve the storage stability of the composition.

The method for mixing the above components is to mix the cyanate ester resin composition and metal powder or metal fiber at a temperature of 20 to 130°C.
The mixture is then mixed using a roll, Banbury mixer, Henschel mixer, extruder or other known kneading machine, and other components are added at the same time or during kneading.

The kneading time depends on the molecular weight of the cyanate ester resin composition used, the composition component ratio, and the kneading equipment used.
The optimum conditions are selected depending on the conditions, but in general, 1 minute to
Kneading is completed within a range of 10 hours when a uniform composition is obtained.

The composition of the present invention prepared by the above method usually has a
It is a viscous liquid or a paste at temperatures below 0.degree. C., for example about 50 to 90.degree.

The hard resin mold of the present invention is formed by using this liquid or paste composition as it is, with a reinforcing base material layered thereon. The molding method is a known cast molding method,
For example, a method such as simple injection, applying pressure after injection, or placing the paste in a mold and applying pressure, preferably at a molding pressure of 0 to 1°Okg/c+4 and a temperature of 90°C or higher, preferably about 100 to 150°C. Heat and pressurize in a range to gel, then remove from the mold and heat to a temperature of 150 to 24℃.
It is manufactured by curing in, for example, a constant temperature bath at about 0°C.

The hard resin mold obtained by the above method has excellent heat resistance and abrasion resistance compared to conventional hard resin molds even when used as is, but if desired, it can be made by utilizing the electrical conductivity of the mold. The surface of the mold can also be metallized, such as by metal plating.

〔Example〕

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 based on weight unless otherwise specified.

Example-1 After mixing 30 parts of 2,2-bis(4-cyanatophenyl)propane and 70 parts of 150 mesh copper powder in powder form, the mixture was heated and stirred at 80°C for 5 minutes to make it fluid. Composition(
50PS, at 80°C) was obtained.

This composition was prepared using epoxy equivalents of 4 x 4 x 103
It was poured into an 8x8x15C11 container with a rectangular parallelepiped (core) placed in the center at 80°C, and then heated at 130°C. The composition gelled in 3 minutes. After heating for 6 minutes, the gelled product was taken out and cured by heating in a constant temperature bath at 175°C for 5 hours.

The glass transition temperature of the cured product is 220℃, and the compressive strength is 1.9.
The compressive strength after heating at 50 kg/cIA and 180°C for 2,000 hours was 1,740 kg/-.

Also, the thermal conductivity of the cured product is 4 x lo'cal/sec
crA″ccI11.

Example-2 2,2-bis(4-cyanatophenyl)propane 27
The same procedure as in Example 1 was carried out except that 3 parts of bis(4-maleimidophenyl)methane and 70 parts of 150 mesh copper powder were used.

The prepared composition had a viscosity of 70 PS (at 80°C), a gelation time of 3 minutes and 10 seconds at 130°C, and a cured product had a glass transition temperature of 223°C.

Example-3 2,2-bis(4-cyanatophenyl)propane 24
1 part, bis(4-maleimidophenyl)methane 3 parts Bisphenol A type epoxy resin (trade name: Epicote 82
The procedure was the same as in Example 1, except that 3 parts of epoxy equivalent 8.8, epoxy equivalent 184 to 194, manufactured by Yuka Shell Epoxy 1) and 70 parts of 150 mesh copper powder were used.

The prepared composition had a viscosity of 30 PS (at 80°C),
The gelation time was 2 minutes and 50 seconds at 130°C, and the glass transition temperature of the cured product was 218°C.

Example-4 After preliminarily reacting 32 parts of 1,4-dicyanatobenzene and 8 parts of bis(4-maleimidophenyl)methane at 150°C for 2 hours, 60 parts of 100 mesh iron powder was added thereto. The mixture was heated and stirred at 85°C for 5 minutes to obtain a fluid composition (IOPS, at 85°C).

A hard resin mold was manufactured in the same manner as in Example 1 except that this composition was used.

The gelation time of the composition at 130°C was 4 minutes and 1
The glass transition temperature after curing at 75°C was 230°C.

Comparative Example-l 30 parts of bisphenol A type epoxy resin (trade name: Epicote 828, Epoxy 1184-194, manufactured by Yuka Shell Epoxy ■), 70 parts of 150 mesh copper powder, 7 parts of diaminodiphenylmethane as a catalyst, benzyl dimethyl Mix 0.8 parts of amine and mix uniformly at 80°C for 5 minutes to create a fluid composition (40PS, at 80°C)
I got it.

1 A hard resin mold was manufactured in the same manner as in Example 1 except that this composition was used.

The gelation time of the composition at 130°C was 3 minutes, and the glass transition temperature after curing was 140°C.

Compressive strength is 2.000kg/cJ, 1.0 at 180℃
The compressive strength after heating for 00 hours was 1.500 kg/cj.

Example 5 A composition was prepared in the same manner as in Example 2, except that the compounds shown in Table 1 were used as the curing catalyst, and a hard resin mold was manufactured.

The results are shown in Table 1.

Example 6 The same procedure as Example 2 was carried out except that 200 mesh aluminum powder was used instead of the copper powder.

The gelation time of the composition at 130°C was 4 minutes and 40 seconds, and the glass transition temperature after curing was 220°C.

[Operation and effects of the invention]

The hard resin mold of the present invention as described above has higher heat resistance (T
g, thermal deterioration), has excellent abrasion resistance, and excellent workability, so it can also be used as a simple mold for molding resins with higher heat resistance that cannot be used with conventional epoxy resin molds. It has the feature that it can be used.

Claims (1)

[Claims] Cyanate ester resin composition with a melting point of 100°C or less (
A) 25 to 75 parts by weight and metal powder or metal fiber (B
) 75 to 25 parts by weight, and optionally a curing catalyst (C
), and after casting the mixture, the resin is gelled by heating, and the resin is further hardened by heating.