JPH0469045B2 - - Google Patents

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, and has a high heat resistance of 200°C or higher.
The present invention relates to a hard resin mold that has excellent wear resistance and thermal conductivity, and can use a process of gelling the resin at a relatively low temperature of about 100 to 140°C in a short time, and has excellent workability. [Conventional methods and their problems] Conventional hard resin molds mainly mix epoxy resin with metal powder or metal fibers, use tertiary amines, acid anhydrides, etc. as hardening agents, and then harden. It is manufactured by mixing a catalyst and curing it at room temperature or by heating. 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 the Problems] The present inventors have significantly improved the drawbacks of the conventional method as described above, and have achieved superior heat resistance, thermal conductivity, and durability compared to conventional hard resin molds. As a result of intensive research into a method for producing a hard resin mold with excellent abrasion resistance, processability, and workability, we discovered a method using a cyanate ester resin composition as a binding resin (binder resin), and developed the present invention. completed. 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-based resin composition (A) of the present invention having a melting point of 100°C or less is a composition comprising a polyfunctional cyanate ester of the following general formula (1), its prepolymer, etc. as essential components, and a cyanate resin. (Tokuko Showa 41-
No. 1928, No. 45-11712, No. 44-1222, German Patent No. 1190184, etc.), cyanate ester-maleimide resin, cyanate ester-maleimide-epoxy resin (Japanese Patent Publication No. 54-30440, etc., Japanese Patent Publication No. 1982) −
31279, USP-4110364, etc.), cyanate ester-epoxy resin (Japanese Patent Publication No. 46-41112), etc. Here, a suitable polyfunctional cyanate ester has the following general formula (1) R (OCN) _n ... (1) (m in the formula is an integer of 2 or more and usually 5 or less, and R is It is an aromatic organic group, and 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-, 1, 8-, 2, 6- or 2, 7
-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4,4'-dicyanatobiphenyl, 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-
cyanate ester (USP -4026913), and cyanic acid esters obtained by the reaction of novolak with cyanogen halides (USP-4022755, USP-344807).
In addition to these, Tokuko Sho 41-1928, Sho 43-18468,
44-4791, 45-11712, 46-41112, 47-
26853, JP-A-51-63149, USP-3553244,
3755402, 3740348, 3595900, 3694410 and
Cyanic acid esters described in 4116946 and the like 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 are smy, which is formed by trimerization of cyanide groups in the cyanate ester.
- Generally has a triazine ring in the molecule. 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 paraphenylenediamine, meta or paraxylylenediamine, 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, etc. The polyfunctional cyanate esters, prepolymers thereof, and prepolymers with amines mentioned above can be used alone or in the form of mixtures, and the number average molecular weight alone and in mixtures is preferably 1500 or less, especially 300
A range of ~1000 is preferred. Cyanate ester-maleimide resin
-30440 etc.), cyanate ester - maleimide -
Epoxy resin (Special Publication No. 52-31279, etc.) and cyanate ester-epoxy resin (Special Publication No. 46-41112)
Maleimide, which is a component of the cyanate ester resin composition represented by No. 1), is a compound represented by the following general formula (2) and its prepolymer. General formula (2): (In the formula, R ₁ is an aromatic or alicyclic organic group having a valence of 2 or more and usually a valence of 5 or less, X ₁ and X ₂ are hydrogen, halogen, or an alkyl group, and n is usually 2 to 5
is an integer. ) The 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 maleimic acid, and then maleamic acid is dehydrated and cyclized. can be manufactured. 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 listed above for use as a prepolymer with cyanate ester, and s-
These include melamines with a triazine ring, and polyamines made by reacting aniline with formalin and linking benzene rings with methylene bonds. In the present invention, it is preferably used in an amount of usually 25% or less of the resin component in the composition. In addition, epoxy resin is traditionally a hard resin type,
Any material used for laminates or electronic materials can be used. Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol. Novolak type epoxy resin, halogenated bisphenol A type epoxy resin, halogenated phenol novolak type epoxy resin, polyglycol type epoxy resin,
These are cycloaliphatic epoxy resins and the like, and are used alone or as a mixture of two or more. In the present invention, it is preferably used 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 is
The above components are preferred, but in addition to these, for the purpose of improving the viscosity behavior, adhesiveness, curability, flexibility, etc. of the composition, diallyl phthalate resin, unsaturated polyester resin, phenol resin, etc. ,
Thermosetting resins such as acrylic resins and 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. alloys, aluminum alloys, iron alloys, 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), but gelation does not occur. A curing catalyst (C) is added as necessary to achieve faster and more complete curing. Any curing catalyst (C) can be used as long as it is a curing catalyst for the cyanate ester resin composition described above, including amines, imidazoles, organic metal salts, and inorganic metal salts. , organic peroxides, etc. 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, tin octylate, dibutyltin malate, manganese naphthenate, cobalt tephthenate, iron acetylacetone, manganese acetylacetone, etc. , organic peroxides include benzoyl peroxide, lauroyl peroxide, caprylic peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di-tert-butyl-
Examples include jeperphthalate and the like. The amount of these curing catalysts used is sufficient within the range of catalyst amounts in a general sense, for example, based on the total resin composition.
It is used in amounts below 10wt%, especially below 5wt%. 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 fibers at a temperature
The mixture is mixed at 20 to 130°C 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 is appropriately selected depending on the molecular weight of the cyanate ester resin composition used, the composition component ratio, the kneading equipment used, etc., but in general,
Kneading is completed within a range of 1 minute to 10 hours when a uniform composition is obtained. The composition of the present invention prepared by the above method is usually in the form of a viscous liquid or paste at a temperature of 100°C or lower, for example, about 50 to 90°C. 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, such as simple injection, applying pressure after injection, or placing the paste in a mold and applying pressure. Preferably, the molding pressure is 0 to 0.
100Kg/cm ² , temperature 90℃ or higher, preferably 100-150
It is manufactured by heating and pressurizing it to gel at a temperature of about 150 to 240 degrees Celsius, and then removing it from the mold and curing it, for example, in a constant temperature bath at a temperature of about 150 to 240 degrees Celsius. The hard resin mold obtained by the above method can be used as is.
It has superior heat resistance and wear resistance compared to conventional hard resin molds, but if desired, the surface of the mold can be metallized, such as by metal plating, which takes advantage of the electrical conductivity of the mold. It is also possible. [Example] Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. Note that 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 form a fluid composition ( 50PS, at 80℃). This composition was applied to a 4×4 made of epoxy resin.
8x8x with a 10cm rectangular parallelepiped (core) placed in the center
It was poured into a 15 cm container 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
The compressive strength after heating at 1950 Kg/cm ² and 180° C. for 2000 hours was 1740 Kg/cm ² . Also, the thermal conductivity of the cured product is 4×10 ^-3 cal/sec cm ²
It was ℃cm. Example 2 The same procedure as in Example 1 was carried out except that 27 parts of 2,2-bis(4-cyanatophenyl)propane, 3 parts of bis(4-maleimidophenyl)methane and 70 parts of 150 mesh copper powder were used. The prepared composition had a viscosity of 70PS (at 80°C), a gelation time of 3 minutes and 10 seconds at 130°C, and a glass transition temperature of the cured product was 232°C. Example 3 24 parts of 2,2-bis(4-cyanatophenyl)propane, 3 parts of bis(4-maleimidophenyl)methane, bisphenol type A epoxy resin (trade name;
The procedure of Example 1 was repeated except that 3 parts of Epicote 828, epoxy equivalent of 184 to 194, manufactured by Yuka Ciel Epoxy Co., Ltd., and 70 parts of 150 mesh copper powder were used. The prepared composition had a viscosity of 30PS (at 80°C), a gelation time of 2 minutes and 50 seconds at 130°C, and a cured product had a glass transition temperature of 218°C. Example 4 32 parts of 1,4-dicyanatobenzene, bis(4-
(maleimidophenyl) methane and 2 parts at 150℃.
After preliminarily reacting for a time, 60 parts of 100 mesh iron powder was added thereto, and the mixture was heated and stirred at 85°C for 5 minutes to obtain a fluid composition (10PS, at 85°C). A hard resin mold was produced in the same manner as in Example 1 except that this composition was used. The gelation time of the composition at 130°C is 4 minutes, and the glass transition temperature after curing at 175°C is 230°C.
It was hot. Comparative Example 1 30 parts of bisphenol A type epoxy resin (trade name: Epicote 828, epoxy equivalent 184-194, manufactured by Yuka Ciel Epoxy Co., Ltd.), 150 mesh copper powder 70
7 and diaminodiphenylmethane as a catalyst.
0.8 parts, benzyldimethylamine 0.8 parts, 80 parts
A fluid composition (40PS, at 80°C) was obtained by uniformly mixing the mixture at 80°C for 5 minutes. A hard resin mold was produced 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. The compressive strength was 2000 Kg/cm ² , and the compressive strength after heating at 180° C. for 1000 hours was 1500 Kg/cm ² . 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,
A hard resin mold was made. The results are shown in Table 1.

[Operation and effects of the invention]

As described above, the hard resin mold of the present invention has excellent heat resistance (Tg, thermal deterioration) and abrasion resistance, and has excellent workability, compared to those using conventional epoxy resin as a binder. Because it is a mold, it has the feature that 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.

Claims (1)

[Claims] 1 25 to 75 parts by weight of a cyanate ester resin composition (A) with a melting point of 100°C or less, 75 to 25 parts by weight of metal powder or metal fiber (B), and a curing catalyst if necessary
A hard resin mold characterized in that (C) is mixed, the mixture is cast, the resin is gelled by heating, and the resin is further hardened by heating.