JPH0481487B2 - - Google Patents

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a hard resin mold, which is a type of simple mold, and which has high heat resistance, excellent abrasion resistance, and thermal conductivity. The present invention relates to a hard resin mold with excellent workability, which uses a process of gelling the resin at a low temperature of 100° C. or lower after molding, and then curing it by further heating.

[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 a method for manufacturing a hard resin mold with excellent properties, we found that a cyanate ester resin composition was used as a binding resin (binder resin), and an epoxy resin was used as a curing agent for this resin and a gelling agent for the binder resin. They discovered a method using a mixture with a metal that acts as a metal, and completed the present invention.

That is, the present invention provides 25 to 75 parts by weight of a cyanate ester resin composition (a) having a melting point of 100°C or less and a temperature
Metal powder or metal fiber 75 that does not substantially serve as a gelling catalyst for this composition (a) at temperatures below 100°C
~25 parts by weight of a mixture (A), 15 to 75 parts by weight of an epoxy resin (b) with a melting point of 80°C or lower, and a metal powder or metal powder that becomes a gelling catalyst for the composition (a) at a temperature of 100°C or lower. A curing agent composition (B) containing 85 to 25 parts by weight of fiber as an essential component and a curing catalyst (C) are mixed, this mixture is cast under heating at a temperature of 100°C or less to gel the resin, and then It is a cured resin type characterized by curing the resin by heating, and in a preferred embodiment, aluminum, zinc, an alloy thereof, or stainless steel is used as the metal powder or metal fiber, and the metal powder or metal fiber is cured. Using copper, iron or their alloys as a curing catalyst (C)
as an organometallic salt or a metal chelate compound, in particular a mixture of acetylacetone and acetylacetone metal chelate, and furthermore a curing agent composition (B).
and a curing catalyst (C) are used as a curing agent mixture.

The configuration of 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 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); 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.

Furthermore, the polyfunctional cyanate ester described above can be polymerized without a catalyst or 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. It is used as a prepolymer obtained by These prepolymers generally have a sym-triazine ring in the molecule, which is formed by trimerization of the cyanide groups 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 paraphenylene diamine, meta or para xylylene diamine, 1,4- or 1,3-cyclohexane diamine, 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)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 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 weights of the individual and mixtures are preferably 1,500 or less, particularly preferably in the range of 300 to 1,000.

Cyanate ester-maleimide resin (Special Publication 1973)
-30440 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 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. ) 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:
These include those exemplified as those used as prepolymers with cyanate esters, melamines having an s-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 total resin components including those used as the curing agent 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 preferable to use it in an amount of usually 50% or less of the total resin components including those used as the curing agent 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 to be mixed with the composition (a) of the present invention is used mainly for the purpose of imparting thermal conductivity to the resin mold.
It is not particularly limited as long as it does not substantially function as a gelation catalyst at temperatures below 100°C. Specific examples include powders or fibers of aluminum, nickel, chromium, tin, zinc, silver, gold, platinum, titanium, cobalt and their alloys, and stainless steel. Alloys and stainless steel are preferred. These metals can be used even if they are oxidized to the extent that there is no practical problem. Further, small amounts of inorganic fillers, plastic fibers, carbon fibers, etc. may also be mixed in for reinforcement.

The mixture (A) of the present invention is prepared by melt-mixing the above composition (a) and metal powder or metal fiber at a temperature usually below 100°C.

Next, the epoxy resin (b) with a melting point of 80°C or lower used in the curing agent composition (B) is of the same kind as that used in the cyanate ester resin composition (composition (a)) described above. Examples include those with a melting point of 80°C or lower. Further, examples of metal powders or fibers that serve as a gelling catalyst for composition (a) at a temperature of 100°C or lower include copper, iron, lead, manganese, magnesium, or alloys thereof and oxides thereof. Copper and iron are preferred. The curing agent composition (B) of the present invention is
25 to 85% by weight of metal powder or metal fiber is used.

The curing catalyst (C) can be any known curing catalyst for the composition (a), that is, a cyanate ester resin composition, and may include organic metal salts (including metal chelate compounds), Examples include inorganic metal salts and organic peroxides, and preferable examples include organic metal salts alone and combination systems of organic metal salts and organic peroxides. 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 di-perphthalate, etc. Among them, an acetylacetone metal salt and a combination system of an acetylacetone metal salt and acetylacetone are particularly suitable.
The amount of these curing catalysts to be used is sufficient within a general catalytic amount range, for example, from 0.01 to 5% by weight based on the total resin composition.

Furthermore, from the viewpoint of mixing operability, workability, and other aspects, it is also preferable to use a mixture in which the curing agent composition (B) and the curing catalyst (C) are mixed in advance.

A curing agent composition (B) and a curing catalyst (C) or a mixture thereof are added to the mixture (A) described above at a temperature of usually 100°C.
Below, it is preferably melted and mixed at 50 to 90℃, then poured into a mold, and the temperature is 100℃ or less, preferably 50℃.
Gel the resin at ~90℃, remove it from the mold,
The hard resin mold of the present invention is manufactured by heating and curing.

The mixing method is performed using a roll, a Banbury mixer, a Henschel mixer, an extruder, or other known kneading machines.

The kneading time is appropriately selected depending on the molecular weight of the resin component in the composition, the composition component ratio, the kneading equipment used, etc., but in general, a uniform composition is obtained within the range of 1 minute to 10 hours. Finish kneading at stage.

The composition of the present invention prepared by the above method is usually in a viscous liquid or paste form at a temperature of 100°C or lower, for example, about 50 to 90°C, so in this state, Preferably, air bubbles generated during mixing are defoamed using a vacuum.

The hard resin mold of the present invention is formed by using this viscous liquid or paste composition as it is, with an auxiliary 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 at a molding pressure of about 0 to 100 kg/ ^cm2 . Apply pressure and gel at a temperature of 100℃ or less. The product is then removed from the mold and cured, for example, in a constant temperature bath at a temperature of about 150 to 240°C.

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〕

The present invention will be explained in more detail below using Examples and Comparative Examples. In addition, parts in Examples and Comparative Examples are based on weight unless otherwise specified.

Example 1 30 parts of 2,2-bis(4-cyanatophenyl)propane and 70 parts of 150 mesh aluminum powder were mixed in powder form, and heated and stirred at 85°C for 5 minutes to form a fluid mixture (hereinafter referred to as , mixture A1,
A viscosity of 300 PS at 60°C was obtained.

On the other hand, 25 parts of bisphenol A type epoxy resin (trade name: Epicote 828, viscosity 120-150 PS, at 25°C, epoxy equivalent 184-194, manufactured by Yuka Ciel Epoxy Co., Ltd.) in which 0.03 part of iron cetyl acetone was dissolved in advance;
A fluid composition (hereinafter referred to as curing agent B1) was prepared by mixing 75 parts of 150 mesh copper powder at room temperature.
150PS, at 60℃) was obtained.

175 parts of mixture A prepared above and 125 parts of curing agent B
This is then mixed into a 4 x 4 x 10 cm rectangular parallelepiped (core) made of epoxy resin.
The mixture was poured into an 8 x 8 x 15 cm container placed in the center at 60°C and left in a constant temperature bath at 60°C, resulting in a maximum temperature of 80°C due to self-heating and gelation in 70 minutes. After 120 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 230℃, and the compressive strength is
Compressive strength after heating at 200℃ for 2000 hours at 20Kg/mm ² is
17Kg/ ^mm2 , and the thermal conductivity of the cured product is 1.9
×10 ^-3 cal/sec/cm ² /℃/cm, coefficient of linear expansion is 2.0×
^The curing shrinkage was 1.0×10 ⁻³ cm/cm.

Example 2 A mixture obtained by using 27 parts of 2,2-bis(4-cyanatophenyl)propane, 3 parts of bis(4-maleimidophenyl)methane and 70 parts of 150 mesh stainless steel powder in place of mixture A1. A cured product was obtained in the same manner as in Example 1, except that a mixture of 320 PS and 60° C. (hereinafter referred to as mixture A2) was used.

The maximum temperature was 85°C due to self-heating, and gelation occurred in 50 minutes. The glass transition temperature of the cured product was 230°C.

Example 3 24 parts of 2,2-bis(4-cyanatophenyl)propane and 6 parts of bis(4-maleimidophenyl)methane were preliminarily reacted at 150°C for 1 hour (melting point: 65°C).
Then, add 70 parts of 250 mesh aluminum powder to this.
The mixture was mixed at 70°C, the temperature was raised to 60°C, and 2 parts of acetylacetone was added and mixed to obtain a mixture having fluidity at 60°C (hereinafter referred to as mixture A3).

On the other hand, dimer acid type epoxy resin (product name: Epicoat) in which 0.07 part of zinc octylate was dissolved in advance
871, viscosity 4-9 PS, at 25°C, 30 parts manufactured by Yuka Ciel Epoxy Co., Ltd., saturated polyester resin (trade name;
Polyester 011, manufactured by Nippon Gosei Kagaku Co., Ltd.) 1 part and
70 parts of iron powder of 150 mesh was mixed at room temperature to obtain a fluid composition (hereinafter referred to as hardening agent B3).

370 parts of mixture A prepared above and 330 parts of hardening agent B
Melt and mix at 70℃ and mold into the same mold as Example-1.
When cast at 70°C and left in a constant temperature bath at 70°C, the maximum temperature reached 90°C due to self-heating, and gelation occurred in 30 minutes. After 60 minutes, remove the gel and
It was heated and cured for 3 hours in a constant temperature bath at 200°C.

The glass transition temperature of the cured product was 245°C.

Example 4 A mother mold made of ABS was molded using a room temperature curing silicone resin (product name: RTV KE1360, manufactured by Shin-Etsu Chemical Co., Ltd.), and from this silicone resin mold, a mother mold was manufactured from the same silicone resin.

This silicone resin matrix was cast, gelled, and heat cured in the same manner as in Example 3 using the same mixture (mixture of mixture A3 and curing agent B3).

As a result of comparing the dimensions of the obtained resin mold with the dimensions of the ABS mother mold, it was found that the dimensional reduction rate of the resin mold was 0.05%.

[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 compared to conventional molds using epoxy resin as a binder, and is suitable for casting resin mixtures. Because it has excellent preparation and casting workability, 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 is.

Claims (1)

[Scope of Claims] 1. 25 to 75 parts by weight of a cyanate ester resin composition (a) having a melting point of 100°C or lower and a metal that does not substantially serve as a gelling catalyst for this composition (a) at a temperature of 100°C or lower. Mixture (A) with 75 to 25 parts by weight of powder or metal fibers, and 15 to 75 parts of epoxy resin (b) with a melting point of 80°C or less.
Parts by weight and metal powder or fiber that becomes a gelling catalyst for the above composition (a) at a temperature of 100°C or less 85-25
A curing agent composition (B) and a curing catalyst (C), each of which contains parts by weight as essential components, are mixed, this mixture is cast under heating at a temperature of 100°C or less to gel the resin, and further heated to form a resin. A hard resin mold characterized by curing. 2. The hard resin mold according to claim 1, wherein the metal powder or metal fiber is aluminum, zinc or an alloy thereof, or stainless steel. 3. The hard resin mold according to claim 1, wherein the metal powder or metal fiber is copper, iron, or an alloy thereof. 4. The hard resin mold according to claim 1, wherein the curing catalyst (C) is an organic metal salt or a metal chelate compound. 5. The hard resin mold according to claim 4, wherein the curing catalyst (C) is a mixture of acetylacetone and acetylacetone metal chelate. 6. The hard resin mold according to claim 1, wherein the curing agent composition (B) and the curing catalyst (C) are used as a mixture.