JPS62127340A - Phenolic resin molding material - Google Patents

Abstract

PURPOSE:To increase the heat resistance and mechanical strength of the resulting moldings without causing environmental pollution, by blending a phenolic resin with glass fiber and specified mineral fiber. CONSTITUTION:This phenolic resin molding material is obtd. by blending (a) phenolic resin, (h) glass fiber having an average fiber diameter of 8-13mum and an average fiber length of 1-13mm and (c) mineral fiber having an average fiber diameter of 0.5-8mum and an average fiber length of 50-300mum, composed of 40-45wt% SiO2, 13-15wt% Al2O3 and 34-36wt% CaO as main components and having a non-fibrous material content of 5wt% or below in such an amount as to give a weight ratio of (c) to (b) of 0.3-2.0. It is preferred that the surface of the component (c) is treated with any of a silane surface treating agent, a phenolic resin, an epoxy resin and a silane treating agent-contg. phenolic resin or epoxy resin.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a phenolic resin molding material.

[Prior Art] Thermosetting resin molding materials have better mechanical strength and physical properties when heated than thermoplastic resins. Among these thermosetting resins, phenolic resin molding materials have superior heat resistance, mechanical strength, dimensional change, and creep properties compared to other resins, and are used in various mechanical and electrical parts. has been done.

In recent years, in order to reduce weight, rationalize manufacturing processes, and reduce costs by replacing metal with plastic materials,
Phenolic resin molding materials are being reviewed. In order to provide molded products with physical properties comparable to metals, glass fibers and asbestos are used alone or in combination as reinforcing fibers in phenolic resin molding materials.

(Problems to be Solved by the Invention) However, among the above-mentioned reinforcing fibers, asbestos is a polluting substance, so it is desired to discontinue its use from the viewpoint of safety and health.

Therefore, the use of glass fiber alone or a combination of glass fiber and inorganic fillers other than asbestos, such as clay, mica, silica, and calcium carbonate, is being considered as a reinforcing material. However, while glass fiber alone has excellent mechanical strength, dimensional change, creep properties, etc., when thick molded products are heat-treated at high temperatures, hair cracks and glue tend to occur inside the molded products. Cannot be used for thick molded products. Further, when glass fibers and the above-mentioned inorganic materials are used in combination, the strength decreases, which is still a problem in practical use.

The purpose of the present invention is to avoid causing the above-mentioned pollution problem, and
The object of the present invention is to provide a phenolic resin molding material from which molded products having excellent heat resistance and mechanical strength can be obtained.

[Means for solving the problem] As a result of various studies regarding the above problem, we found that the reinforcing material has an average fiber diameter of 0.5 to 8 μm and an average fiber length of 50 to 300 μm.
It was found that this problem could be solved by using a combination of mineral fiber and glass fiber.

That is, the present invention uses (a) a phenol resin, (b) an average fiber diameter of 8 to 13μ, and an average fiber length of 1 to 13t.
m glass fiber and (c) 40 to 45 wt% of Sin as the main component, Al
13 to 15 wt% of zo3, 34 to 36 wt% of CaO
The weight ratio of component (b) to component (c) (c)/ (
b) is characterized by being mixed so that it becomes 0.3 to 2.0.

The glass fiber (b) used in the present invention is preferably one that has been surface-treated with a silane-based surface treatment agent such as aminosilane, and is preferably E-glass with a low alkali content. By treating such glass fibers with a silane-based surface treatment agent, the compatibility between the glass fibers and the phenol resin becomes better, improving the moldability of the molding material, and further improving the mechanical strength and heat resistance of the molded product. improves. In addition, the length of glass fiber used is 1 to 13 cranes, and
If it is less than 13-1, the strength will be weak, and if it exceeds 13-1, the manufacturing workability will be poor.

The mineral fiber (c) used in the present invention is an artificial amorphous material made by melting raw materials such as blast furnace slag, ore containing silicic acid as a main component, and limestone in a cupola, and turning the melted material into fibers using centrifugal force. Mineral fibers are cut into arbitrary lengths and carefully processed.

Minerals usually produced in this way i! F fibers contain spherical non-fibrous substances during production, but in the mineral fiber (c) of the present invention, this spherical substance is preferably 5 wt% or less, and optimally 1 wt% or less. be.

If the content of this spherical substance exceeds 5 wt%, the strength decreases, and when the molded product is rapidly heated, cranking occurs as in the case of glass fiber alone.

In addition, the strength of this mineral fiber alone decreases.

Therefore, in order to bring out the characteristics of glass fiber and eliminate defects such as cracks, glass fiber (b) with a normal fiber diameter of 8 to 13 μm and this mineral fiber (c) were mixed at a weight ratio (c)/
(b) is 0.3 to 2.0, preferably 0.5 to 1.0. When the weight ratio is less than 0.3, cracks tend to occur, and when it exceeds 2.0, the strength decreases.

Next, the mineral fiber (c) may be used as it is, but since it does not blend well with the glass surface and the resin, it is better to perform a surface treatment. Surface treatment methods include the conventional method of using a silane surface treatment agent for glass fibers of 8 to 13 μm, the method of treating the surface with 5 to 20 W% of phenolic resin or epoxy resin, or a method of combining these methods. be. When processing with resins, pre-mix these resins with methanol, acetone, or MEK.

A 10 to 20 wt % solution is prepared using a solvent such as, and the mineral fibers are sheared using equipment such as a kneader.

As the phenolic resin (a) of the present invention, a novolak type resin is used alone or in combination with a resol type resin.

In addition, hexamine as a hardening agent, mold release agents such as stearic acid, slaked lime, alkaline earth metal oxides or hydroxides such as magnesium oxide, etc., which are blended in conventional phenolic resin molding materials, may be used as appropriate. can be added.

The phenolic resin molding material of the present invention is produced by a conventional method. For example, it is manufactured as follows. Glass fiber (b)
It is manufactured by mixing ti material fibers (c), phenolic resin, curing agent, and other additives in a mixer with strong shear such as a kneader, and passing the mixture through heating rolls to form a molding material. In this case, the glass fiber (b) and mineral fiber (c) are set at 40 to 70 wt% of the total.

This is because if it is outside this range, it becomes difficult to use it as a molding material.

(Example) The following will specifically explain based on Examples. In the Examples, parts and percentages are based on weight.

90 parts of mineral fibers with an average fiber diameter of 5 μI, an average fiber length of 150 μm, and a non-fibrous substance content of 1% or less and 50 parts of a phenolic resin (20% methanol solution) containing 2 wt% of aminosilane treatment agent Q were sheared using a kneader. The mixture was mixed and dried to produce treated mineral fiber A treated with 10% phenolic resin and 0.5% aminosilane.

The mineral fibers were treated with a methanol solution containing 0.5% aminosilane and dried to obtain a treated product B treated with 0.5% aminosilane.

Also, treated with phenol resin (20% methanol solution) in the same manner, and treated product C with 10% phenol resin treatment.
I got it.

Example 1 42 parts of phenolic resin, 5 parts of hexane, 1 part of magnesium oxide, 1 part of zinc stearate, and 27 parts of general glass fiber (average fiber diameter IO μm, average fiber length 3×) were added to 30 parts of the treated material, and the mixture was put into a kneader. The mixture was mixed at 90° C. to 100° C. using a hot roll and pulverized to obtain a molding material.

Example 2 A molding material was produced in the same manner as in Example 1 except that treated product B was used instead of treated product A.

Example 3 A molding material was produced in the same manner as in Example 1, except that treated product C was used instead of treated product.

Example 4 A molding material was produced in the same manner as in Example 1, except that untreated mineral fibers with an average fiber diameter of 5 μm, an average fiber length of 150 μm, and a non-fibrous substance content of 1% or less were used instead of the treated material. Created.

Next, as comparative examples, a molding material using only glass fiber (Comparative Example 1) and a molding material using only asbestos fiber (Comparative Example 2) were produced.

Table 1 shows the characteristics of molded products molded using the molding materials of the above Examples and Comparative Examples.

In addition, bending strength, Charpy impact strength, and insulation resistance are J
The heat resistance was measured based on Is-6911, and the heat resistance was measured after making a cylindrical molded product with an outer diameter of 50 mm, an inner diameter of 20 m, and a length of 40 m, and placing it in a solder bath at 300°C for 30 seconds. The product was cut and the internal condition was visually observed and judged (
○ No crack, × Crank).

As is clear from Table 1, the molded product using the phenolic resin molding material of the present invention contained asbestos in Comparative Example 2.
It has heat resistance equivalent to or higher than molded products using molding materials of
Moreover, it can be seen that other properties are also equivalent to glass fiber.

〔Effect of the invention〕

The phenolic resin molding material of the present invention is non-toxic and
Moreover, it was possible to produce a molded article with excellent heat resistance, mechanical strength, and insulation resistance.

Claims (1)

[Claims] 1. (a) Phenol resin, (b) average fiber diameter 8 to 13 μm, average fiber length 1 to 13 m
m glass fiber and (c) 40 to 45 wt% of SiO_2 as the main component;
Al_2O_3 13-15wt%, CaO 34-3
6 wt%, non-fibrous substance content is 5 wt% or less, average fiber diameter 0.5 to 8 μm, average fiber length 50 to 300 μm
The weight ratio of component (b) to component (c) (
A phenolic resin molding material characterized by being mixed so that c)/(b) is 0.3 to 2.0. 2. The phenolic resin molding material according to claim 1, wherein the mineral fiber (c) is surface-treated with a phenolic resin or an epoxy resin. 3. The phenolic resin molding material according to claim 1, wherein the mineral fiber (c) is surface-treated with a silane-based surface treatment agent. 4. The phenolic resin molding material according to claim 1, wherein the mineral fiber (c) is surface-treated with a phenolic resin or epoxy resin containing a silane surface treatment agent.