JPS58206640A - Composite material of metal with thermosetting resin - Google Patents

Abstract

PURPOSE:The titled novel composite material, prepared by pressure hot molding a mixture containing a thermosetting resin, metallic fibers and a low-melting metallic powder or an ultrafine metallic powder in a specific proportion, etc., and having easy handleability, improved heat resistance, high rigidity and toughness, etc. CONSTITUTION:A composite material of a metal with a thermosetting resin, prepared by mixing 100pts. thermosetting resin, e.g. novolak type phenolic resin, with 5-400pts. metallic fibers having 20-15mm. length and about 20-200mum thickness, e.g. copper or iron, and 0.1-10pts., based on 100pts. low-melting metallic powder, e.g. tin, or ultrafine metallic powder, e.g. copper or iron, and if necessary a filler, mold releasing agent, colorant, etc., and pressure hot molding the resultant molding mixture or molding the molding mixture and heat- treating the resultant molded article at 180-250 deg.C for 10min-24hr. EFFECT:Improved moldability and heat conductivity and electric conductivity.

Description

[Detailed Description of the Invention] A novel metal/thermosetting resin composite material having To provide a molding composite material that has excellent heat resistance, high elasticity, and toughness, and has heat conductivity.

In recent years, the substitution of metal for plastic materials has been actively promoted in order to reduce weight, rationalize manufacturing processes, and reduce costs. Against this background, especially in fields where heat resistance is required, Various types of composite materials based on thermosetting resin have been proposed.

Conventionally, inorganic fibers such as glass fiber and asbestos have been used as a material to impart heat resistance and toughness to thermosetting resin molding materials, and in special cases (: is aromatic polyamide). It is known that very expensive heat-resistant organic fibers such as

When using glass fiber, good toughness can be obtained by going through a process in which long fibers remain in the molded product, but there are major restrictions on manufacturing and molding methods, and it is difficult to mold simple shapes. I can only make products. Moreover, the strength is uneven depending on the direction of the fibers (2), and because of poor heat conductivity, C
= When used, thermal deterioration of molded products is accelerated due to heat accumulation.

On the other hand, if the molded product undergoes a process that does not leave long fibers,
Workability and moldability are rated at 4, and molded products with complex shapes can also be produced. However, both rigidity and toughness are insufficient.

Other reinforcing materials also have some of the same drawbacks as glass fibers, and an economical composite material for molding that has heat resistance, high rigidity, and strength and toughness has not yet been obtained.

In order to impart 4-electroconductivity, mixing metal powder such as copper powder or copper powder into plastics is practically used in the field of conductive paints and the like. However, these plastics containing gold layer powder are not suitable as molded products as they are, but their toughness and other mechanical strengths are low, making them unsuitable as composite materials for molding that have heat resistance, high rigidity, and toughness. be.

The present inventors have modified the brittleness of the thermosetting resin 1Iiii to create a molding material that is easy to handle, has moldability, heat resistance, high rigidity, and toughness (2 excellent and 1 heat t). We conducted extensive research to obtain a composite material, and as a result, we developed a new composite material of metal and thermosetting resin.

In the present invention, 100 parts of thermosetting resin, 5 to 400 parts of metal fiber
and 100 parts of the metal fibers (for 2 parts, 0.1 to 10 parts of low melting point metal powder or ultrafine metal powder) are heated and pressure molded or after heat and pressure molded. The thermosetting resin is preferably one with excellent heat resistance;
Phenol resins, epoxy resins, unsaturated polyester resins, diallylphthalate'F resins, silicone resins, polyimide resins, or modified resins thereof can be used.

Preferably, F has a small dimensional change rate and weight change rate due to heat treatment, such as a novolak type phenol resin (this includes xylene resin, xylylene glycol dimethyl ether, etc.) (= aromatic hydrocarbons, melamine,
Triazines such as benzoguanamine, or modified novolac type phenolic resins with alkylphenols may be used), heat-resistant epoxy resins (this may be phenolic novolak type, tetraphenylethane polyglycidyl ether type, aromatic amine type, or resin). ring·
It is preferable to use a resin whose main constituent component is an epoxy resin of the formula), a diallyl phthalate resin, or a bismaleimide polyimide resin.

Of course, these include conventional curing agents and, if necessary, curing accelerators.

Among these, aromatic polycarboxylic acid anhydrides, such as trimellitic anhydride, pyromellitic anhydride, benzophenone-tetracarboxylic acid hydrate (BTDA),
Alternatively, ethylene glycol bistrimelitate (T
Phenolic novolac-type epoxy resins or bismaleimide-based polyimide resins using MEG) etc. as curing agents have very small dimensional change rates and weight change rates, and have excellent adhesion to metals (2), so they are the most This is a preferable example.

The gold fibers are preferably those in which the active atoms of the low-melting metal liquid phase or ultrafine metal wood particles easily permeate into the gaps of the metal fibers during heat treatment, that is, sintering, and are made of copper, iron, aluminum, or the like. Alloys etc. can be used.

The size of the metal fiber is 2. (1-151M, thickness 2
A material with a diameter of about 0 to 200 μm is easy to work with.

The blending amount of metal fiber is 100% of thermosetting resin containing curing agent.
5 to 400 parts, preferably 10 to 300 parts per part. If it is too small, the rigidity, toughness, and heat conductivity will not be improved, and if it is too large, the fluidity during molding will be poor and the molding will be difficult. There are many defects and non-uniform strength, and high specific gravity (secondary).

From the viewpoint of heat resistance of the thermosetting resin, it is preferable to use a metal having a melting point of 180 to 250° C. as the low melting point metal powder.

Tin, tin-lead alloy (solder), etc. can be used.

More than 90% of this powder has a ladle diameter of 300 μm or less,
It is preferable that the particles be as fine as possible from the viewpoint of dispersibility.

The ultrafine metal powder has a particle size of 90% or more and 05 μm or less, and the finer the particle size, the more easily it adheres to and diffuses into the metal fibers, making it possible to perform low-temperature sintering. For example, copper, iron, nickel, zinc, aluminum, copper, or an alloy thereof can be used.2 The amount of the low melting point metal powder or ultrafine metal powder is 0.1 to 10 parts per 100 parts of metal fiber, preferably 10. 5~
Part 5 is good. If it is too small, sintering will be incomplete, the molded product will be brittle, the rigidity will not improve, and the mechanical strength and heat resistance will deteriorate. In addition, if the amount is too low and the metal powder has a low melting point, voids will be formed in the molded product, and the mechanical strength and heat resistance will also be reduced. Ultrafine metal powder is extremely expensive.

It is preferable that the low melting point metal powder or ultrafine metal powder be thoroughly mixed with the gold fibers in advance.

The above thermosetting resin-metal formulation includes fillers,
For example, inorganic fibers such as glass fibers, gypsum fibers, carbon fibers, silicon carbide fibers, alumina fibers, heat-resistant organic fibers such as aromatic polyamide, inorganic powders such as silica, alumina, mica, charcoal, and clay, and shirasu balloons. , inorganic hollow powder such as perlite, etc., a narrow channel forming agent thereof, a surface treatment silicone agent, a coloring agent, etc. may be added.

B
Mix or knead according to Tsukasa's method to form a molding mixture,
Molded products (2 I) ψ are produced by ordinary heating and pressure molding.
Shaped. After molding, further heat treatment, that is, sintering, results in a
This heat treatment is performed at a temperature of 180 to 250°C for 10 minutes to 250°C.
It is good to carry out for 24 hours, preferably for 30 minutes to 8 hours.

In addition, when the heat treatment after molding is omitted, it is desirable that the molding time for heating and pressing is longer than usual, and is at least 10 minutes.

The composite material of the present invention is easy to handle, has excellent formability, heat resistance, high tensile strength, and toughness (= excellent heat conductivity,
It has m-character.

The reason why we were able to have these excellent properties at the same time is that the three-dimensional network structure of the thermosetting resin: Dispersed metal powder particles are bonded to each other, creating a new metal-thermosetting resin interaction. Generation of a penetrating network (IPN)

The composite material of the present invention is useful in the field of molding materials for replacing metals, which require heat resistance, high strength, and high rigidity (e.g., electronic equipment, electrical connections, etc.).

Next (=, concrete (2) will be explained by giving examples.

Example 1゜78 parts of novolac type epoxy resin, anhydrous trimelite 1
1422 parts, ) 0.4 parts of lithodimethylaminophenol and 2 parts of zinc stearate (=, premixed brass fibers (length 5 mm, thickness 60 μrn) / No. Nda powder (average particle size + 507 m) = 100 / 200 parts of 1 were added, mixed well, and kneaded with rolls to obtain a molding material.

1 compared to 78 parts of novolac type epoxy resin, anhydrous trimelite@
22 parts of trisdimethylaminophenol and 2 parts of zinc stearate (=, 200 parts of aminosilane-treated glass fiber) were added, mixed well, and kneaded with rolls to obtain a molding material of 1 grade.

Example 2 69 parts of novolac type epoxy resin, 31 parts of ethylene glycol bistrimelitate (TME()), 04 parts of trisdimethylaminophenol, 50 parts of glass fiber,
50 parts of Shirasu balloons, 1 part of r-methacryloxypropyltrimethoxysilane and 3 parts of zinc stearate were premixed with iron, fibers (length: 3 mm, thickness: 6 mm).
0μm)/tin powder (average particle diameter: 30μm) -
10072 was added, mixed well, and kneaded with rolls to obtain a molding material.

Example 3 90 parts of novolac type phenol camellia butter, 10 parts of hexamethylenetetramine, 50 parts of aminosilane-treated glass fiber
1 part of copper fiber (length 311III, thickness 80 tim) / tin powder (average particle size: 30 μm) = 100/2, which was premixed in advance with 1 part and 3 parts of stearic acid.
00 parts were added, mixed well, and kneaded with rolls to obtain a molding material.

Example 4 100 parts of bismaleimide polyimide resin (manufactured by Loos-Boulin, Kelimide), 2-methylimidazole 2
1 part and 2 parts of stearic acid (premixed aluminum fiber (length: 3 mm: thickness: 60 μin) / ultrafine aluminum powder (average particle size: 0.1 mm) -1oo
200 parts of No. 71 were added, mixed well, and kneaded with rolls to obtain a molding material.

The materials of Examples 1 to 4 and Comparative Example were molded under heat and pressure, and their performances are shown in Table 1.

Table 1 (*l) The energy required for failure was calculated from the stress curve in the bending test.

(・Roasted 2) Heat treated at 230°C for 1 hour.

Comparing Example 1 and Comparative Example, the former was found to have significantly improved bending strength, rigidity (elasticity*), fracture energy, and impact value due to heat treatment f2.

Other Examples 2 to 4 (= also similar (double strength, 141
The effect of improving I property and toughness is remarkable.

In addition, the materials of Examples 1 to 4 have excellent electrical conductivity and heat conductivity (both of which are excellent).

Claims (3)

[Claims] (1) 100 parts of thermosetting resin, 5 to 400 parts of gold-fiber
A molding mixture containing 100 parts of the metal fibers and 0.1 to 10 parts of low-melting point metal powder or ultrafine metal powder is heated and pressed, or after hot and pressed, the mixture is further heat-treated. A metal/thermosetting resin composite material that is characterized by its properties. (2) The main component of the thermosetting resin is novolak phenolic resin, heat-resistant epoxy resin, diallyl phthalate resin, or bismaleimide polyimide resin), and the metal fiber is copper, iron, aluminum, or , an alloy thereof, and the low melting point metal powder is tin or a tin-lead alloy, or the ultrafine metal powder is copper, iron,
The metal/thermosetting resin composite material according to claim 11, which is nickel, zinc, aluminum, button, or an alloy thereof. (3) Heat treatment at a temperature of 180 to 250°C for 10 minutes or more
A metal/thermosetting resin composite material according to claim 9tIJ<1j or paragraph (2), which is 24 hours.