JPS62240353A - Molding resin composition - Google Patents

Abstract

PURPOSE:To obtain a molding resin composition giving a molded article having high crystallinity and excellent heat-resistance without using annealing stage, by compounding a specific nucleation agent to a polycyanoaryl ether. CONSTITUTION:The objective composition can be produced e.g. by compounding (A) 100pts.(wt.) of a polycyanoaryl ether composed mainly of (preferably >=90mol%) recurring unit of formula I (Ar is group of formula II-V) produced e.g. by reacting a dihydroxyl compound with a mixture of an equimolar amount of a dihalogeno-benzonitrile and an alkali metal carbonate in a solvent (e.g. mixed solvent of toluene and sulfolane) in an inert atmosphere first at <=200 deg.C and then at >=200 deg.C with (B) 0.01-3pts., preferably 1-3pts. of a nucleation agent selected from alumina, aluminum hydroxide, aluminum power, titanium dioxide and calcium fluoride and having an average particle dimaeter of preferably 20mmu-10mu.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polycyanoaryl ether molding resin composition used as a material for electronic/electrical equipment, mechanical parts, etc.

[Conventional technology]

Polycyanoaryl ether is disclosed in JP-A-47-1'4
Various types are known from Japanese Patent Laid-open No. 270 and Japanese Patent Application Laid-Open No. 59-206433. Although these polycyanoaryl ethers have excellent mechanical and thermal properties, they have a slow crystallization rate, which makes it difficult to increase the molding cycle sufficiently high when producing molded articles by thermoforming such as injection molding. The problem is that it can't be done.

[Problem that the invention seeks to solve]

The present invention solves these conventional problems and improves the productivity of polycyanoaryl ether molded products.The present invention provides a polycyanoaryl ether-based polycyanoaryl ether-based molded product that can yield molded products with a high degree of crystallinity and excellent heat resistance. The present invention aims to provide a resin composition for molding.

[Means for solving problems]

As a result of various studies to solve the above-mentioned problems, the present inventors have found that by adding a specific crystal nucleating agent to polycyanoaryl ether, a molded product with a high degree of crystallinity and a high heat distortion temperature can be produced. It was discovered that a resin composition for molding that can be used as a molding material can be obtained, and the present invention was achieved. That is, the present invention provides at least one type of crystal nucleus selected from the group consisting of alumina, aluminum hydroxide, aluminum powder, titanium dioxide, and calcium fluoride, for a part of polycyanoaryl whose main component is the formula It is characterized by containing 0.01 to 3 parts by weight of the agent.

The polycyanoaryl ether used in the present invention is CI
] is preferred. If the amount is less than 10 mol %, a copolymer containing N 2 can be used in combination.

The above polycyanoaryl ether can be produced, for example, as follows.

A mixture of a dihydroxy compound of 〇〇-Ar-OH, an equimolar amount of N, and an alkali metal carbonate such as potassium carbonate is reacted in a solvent under an inert atmosphere at a temperature of less than 200°C to form an oligomer. and then 200
The temperature is raised to above ℃ to form a high molecular weight polymer. Then,
The product is poured into methanol to precipitate the polymer.

By using a mixed solvent of a solvent that forms an azeotrope with water, such as benzene or toluene, and a dipolar aprotic solvent, such as sulfolane, the reaction can be maintained in an anhydrous state during oligomer formation. do.

The polycyanoaryl ether of the present invention is not particularly limited, but can be prepared by using p-chlorophenol as a solvent.
g/dl? It is preferable that the reduced viscosity [η sp/c) of the M degree solution at 60° C. is 0.3 to 2.0.

The crystal nucleating agent that can be used in the present invention is at least one selected from the group consisting of alumina, aluminum hydroxide, aluminum powder, titanium dioxide, and calcium fluoride. When cooled from the molten state within the molten metal, crystallization occurs without the need for a long induction period. Kaolin, talc, mica, silica, calcium carbonate, metal salts of fatty acids, etc., which are often used in polyesters, do not have an effective effect on the crystallization of polycyanoaryl ether.

The amount of the above crystal nucleating agent is polycyanoaryl ether 1
0.01 to 3 parts by weight, preferably 1
~3 parts by weight. If it is less than 0.01 part by weight, the effect of the present invention will not be achieved, and 3! l! Exceeding 1 part leads to a decrease in mechanical strength.

Further, the crystal nucleating agent preferably has an average particle diameter of 20 mμ to 10 μm.

The molding resin composition of the present invention contains a reinforcing filler such as glass fiber or carbon fiber, an antioxidant, an ultraviolet inhibitor, a lubricant, a mold release agent, a coloring agent, or an inorganic filler such as talc or mica. can be done.

The molding resin composition of the present invention preferably contains the above formulation,
The crystal nucleating agent can be uniformly dispersed by melt blending using a kneader in which two or more screws rotate in the same or different directions, or a single screw extruder in which the screws reciprocate back and forth as they rotate. It will be done.

The molding resin composition thus obtained is, if necessary, pelletized and subjected to hot-pressure molding such as injection molding to obtain a molded article.

Injection molded products can have increased crystallinity and heat distortion temperature without any particular annealing.

〔Example〕

Hereinafter, the present invention will be explained in detail based on Examples, but the present invention is not limited thereto.

Example 1 1362.3 g (8 mol) of 2,6-cyclobenzonitrile, 880.8 g (8 mol) of hydroquinone, potassium carbonate 116
0.9g, sulfolane 101, toluene 5! ! It was placed,
The temperature was raised to 160°C for 2 hours, and then the temperature was raised to 210°C for 2 hours and 30 minutes to carry out a polymerization reaction while blowing argon gas. After the reaction is complete, the product is poured into methanol to precipitate the polymer, which is recovered, crushed, washed,
Dry. As a result, 1620 g of a polymer consisting of the following repeating units was obtained.

N This polymer was prepared using p-chlorophenol as a solvent.
2g/d1 concentration? Reduced viscosity of 8 liquids at 60°C [η
sp/c) (measured in the same manner in the following examples).

It was 2 d1/g.

Next, 1.5 parts by weight of titanium dioxide having an average particle size of 20 mμ was added as a crystal nucleating agent to 100 parts by weight of this polymer, and the mixture was kneaded at 380° C. for 5 minutes. The pellets of the obtained kneaded product were injected at 380°C in an injection molding machine,
A molded article was obtained in a mold maintained at 160°C. Next, using this molded body, the degree of crystallinity was measured by X-ray diffraction method. Further, the heat distortion temperature was measured in accordance with ASTM-D-648. These results are shown in Table 1.

Example 2 The same procedure as in Example 1 was carried out except that 1.5 parts by weight of T-alumina having an average particle size of 20 mμ was added as a crystal nucleating agent to 100 parts by weight of the polymer obtained in Example 1. Table 1 shows the crystallinity and heat distortion temperature of the polymer in this case.

Example 3 To 100 parts by weight of the polymer obtained in Example 1, aluminum hydroxide powder with an average particle size of 5 μm was added as a crystal nucleating agent.
The same procedure as in Example 1 was carried out except that 5 parts by weight was added. The crystallinity and heat distortion temperature of the polymer in this case are shown in Table 1.

Example 4 100 parts by weight of the polymer obtained in Example 1 was mixed with 50 parts by weight of glass fiber as a reinforcing agent and kneaded into a pellet of a composition, and 1 part of the same titanium dioxide as in Example 1 was added as a crystal nucleating agent. The same procedure as in Example 1 was carried out except that .5 parts by weight was added. In this case, the crystallinity and heat distortion temperature of the polymer are
Shown in the table.

Comparative Example 1 The polymer obtained in Example 1 was single injection molded. Table 1 shows the crystallinity and heat distortion temperature of the polymer in this case.

Comparative Example 2 After injection molding the polymer obtained in Example 1, the molded body was annealed at 300° C. for 5 hours, and then the crystallinity and heat distortion temperature of the polymer were measured.

These results are shown in Table 1.

Comparative Example 3 The same procedure as in Example 1 was carried out except that 1.5 parts by weight of silica having an average particle diameter of tomμ was added as a crystal nucleating agent to 100 parts by weight of the polymer obtained in Example 1.

Table 1 shows the crystallinity and heat distortion temperature of the polymer in this case.

Comparative Example 4 The same procedure as in Example 1 was carried out except that 1.5 parts by weight of calcium carbonate having an average particle size of 40 mμ was added as a crystal nucleating agent to 100 parts by weight of the polymer obtained in Example 1. Table 1 shows the crystallinity and heat distortion temperature of the polymer in this case.

Comparative Example 5 The same procedure as in Example 1 was carried out except that 1.5 parts by weight of mica having an average particle size of 5 μm was added as a crystal nucleating agent to 100 parts by weight of the polymer obtained in Example 1. Table 1 shows the crystallinity and heat distortion temperature of the polymer in this case.

Example 5 2210 g of a polymer consisting of the following repeating unit was obtained in the same manner as in Example 1 except that 1488 g (8 mol) of 4°4'-biphenol was used in place of hydroquinone in Example 1.

N This polymer has a reduced viscosity [ηsp/c) of 1.5 dJ/g
Met. Next, for 100 parts by weight of this polymer,
1.5 parts by weight of the same titanium dioxide as in Example 1 was added as a crystal nucleating agent and kneaded at 370°C for 5 minutes. The pellet of the obtained kneaded material was injected at 370°C in an injection molding machine, and a molded article was created in a mold maintained at 150°C. Next, the degree of crystallinity and heat distortion temperature were measured using this molded body. These results are shown in Table 1.

Example 6 Crystal nuclei were added to 100 parts by weight of the polymer obtained in Example 5. The same procedure as in Example 5 was carried out except that 1.5 parts by weight of T-alumina, which was the same as in Example 2, was blended as I. Results first
Shown in the table.

Example 7 To 100 parts by weight of the polymer obtained in Example 5, 1.5 parts of the same aluminum hydroxide as in Example 3 was added as a crystal nucleating agent.
The procedure was the same as in Example 5 except that the parts by weight were blended. The results are shown in Table 1.

Comparative Example 6 After injection molding the polymer obtained in Example 5, the molded body was annealed at 300° C. for 5 hours, and then the crystallinity and heat distortion temperature of the polymer were measured.

The results are shown in Table 1.

Comparative Example 7 Polymer 100 obtained in Example 5! l! The same procedure as in Example 5 was carried out except that 1.5 parts by weight of the same silica as in Comparative Example 3 was added to the lit part as a crystal nucleating agent.

The results are shown in Table 1.

Example 8 1984 g of a polymer consisting of the following repeating unit was obtained in the same manner as in Example 1 except that 1269 g (8 mol) of 2°7-hydroxynaphthalene was used in place of hydroquinone in Example 1.

N The reduced viscosity [ηsp/c) of this polymer is 0.72 d
It was 1/g. Next, 1 part of the same titanium dioxide as in Example 1 was added as a crystal nucleating agent to 100 parts by weight of this polymer.
．． 5 parts by weight were blended and kneaded at 380°C for 5 minutes. The pellet of the obtained kneaded material was put into an injection molding machine for 38 minutes.
A molded article was obtained by injection at 0°C and in a mold maintained at 160°C. Next, the degree of crystallinity and heat distortion temperature were measured using this molded body.

These results are shown in Table 1.

Example 9 1.5 parts of the same T-alumina as in Example 2 was added as a crystal nucleating agent to 100 parts by weight of the polymer obtained in Example 8.
The procedure was the same as in Example 8 except that the parts by weight were blended. The results are shown in Table 1.

Example 1O The same procedure as in Example 8 was carried out except that 1.5 parts by weight of the same aluminum hydroxide as in Example 3 was added as a crystal nucleating agent to 100 parts by weight of the polymer obtained in Example 8.

The results are shown in Table 1.

Example 11 The same procedure as in Example 8 was carried out except that 1.5 parts by weight of calcium fluoride powder was added as a crystal nucleating agent to 100 parts by weight of the polymer obtained in Example 8. The results are shown in Table 1.

Comparative Example 8 After injection molding the polymer obtained in Example 8 alone,
The molded article was annealed at 300° C. for 5 hours. The crystallinity degree and heat distortion temperature of the obtained molded body were measured. The results are shown in Table 1.

Comparative Example 9 The same procedure as in Example 8 was carried out except that 1.5 parts by weight of calcium carbonate, which was the same as in Comparative Example 4, was added as a crystal nucleating agent to 100 parts by weight of the polymer obtained in Example 8. The degree of crystallinity and heat distortion temperature of the obtained molded body were measured. The results are shown in Table 1.

Margins below [Effects of the Invention] The polycyanoaryl ether molding resin composition of the present invention has a high degree of crystallinity and can obtain molded products with excellent heat resistance without annealing. It has extremely high industrial value, contributing to productivity improvement and energy conservation.

Claims (1)

[Claims] 1. Polycyanoaryl ether 100 whose main constituent is a repeating unit represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼
0.0% of at least one crystal nucleating agent selected from the group consisting of alumina, aluminum hydroxide, aluminum powder, titanium dioxide, and calcium fluoride, based on the weight part.
A molding resin composition characterized in that 01 to 3 parts by weight are blended. (In the formula, Ar has a ▲ mathematical formula, chemical formula, table, etc. ▼, ▲
There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. )