JPH03140367A - Resin composition for molding materials - Google Patents

Abstract

PURPOSE:To obtain a resin composition for molding material suitable as metal substitute material, having excellent moldability, chemical resistance, mechanical properties and heat resistance, comprising a polyphenylene sulfide resin, polyamide resin and inorganic filler. CONSTITUTION:Total 100 pts.wt. mixture of (A) 80-20wt.% resin prepared by reacting 100 pts.wt. polyphenylene sulfide resin with 0.05-3 pts.wt. silane coupling agent (e.g. aminosilane) and (B) 20-80wt.% polyamide resin comprising B1: 40-99wt.% polyamide resin prepared from xylylenediamine and an alpha,omega-straight chain aliphatic dibasic acid and B2: 60-1wt.% polyamide 66 is blended with (C) 25-150 pts.wt. inorganic filler (e.g. glass fiber).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a resin composition for a molding material comprising a polyphenylene sulfide resin, a polyamide resin, and an inorganic filler. More specifically, the present invention relates to a resin composition for a molding material that has excellent moldability and chemical resistance, and particularly has improved mechanical properties and heat resistance.

[Prior art] Polyphenylene sulfide has excellent heat resistance, flame retardancy, and rigidity, and also has excellent affinity for inorganic fillers, so its use as a molding material in combination with various inorganic fillers is being considered. .

However, when polyphenylene sulfide is used alone as a resin, there are disadvantages in molding such as brittleness against impact and a high softening temperature of the resin.

JP-A-53-6 discloses a resin composition that improves these drawbacks.
No. 9255 discloses a resin composition in which polyphenylene sulfide is blended with polyamide.

Furthermore, since polyphenylene sulfide has poor fluidity during molding, JP-A-55-135160 discloses that a small amount of polyamide resin is blended in order to improve this.

Furthermore, JP-A-59-155462 and JP-A-6
No. 1-1261.72 also discloses blending polyamide resin with polyphenylene sulfide for the purpose of improving its impact resistance and mechanical strength.

However, when these compositions or molded products are intended to replace metal materials, they still have insufficient mechanical strength and do not fully demonstrate the excellent heat resistance of polyphenylene sulfide resin. It is desired that a composition with a high degree of stability be developed.

[Problems to be Solved by the Invention] An object of the present invention is to provide a resin composition for a molding material that is excellent in moldability, water resistance, and chemical resistance, and has improved mechanical strength and heat resistance.

[Means for Solving the Problems] As a result of intensive studies, the present inventors have solved the problem by blending an inorganic filler into a resin composition consisting of a polyamide resin and a resin in which polyphenylene sulfide is reacted with a silane coupling agent. , has excellent moldability, water resistance, and chemical resistance.
Furthermore, they found that a resin composition for molding materials particularly excellent in mechanical strength and heat resistance can be obtained, and the present invention was completed.

That is, the present invention uses a resin prepared by reacting polyphenylene sulfide with a silane coupling agent.
and polyamide resin 20 to 80% by weight (here, the total weight% is 100% by weight) 10
The present invention relates to a resin composition for a molding material, in which 25 to 150 parts by weight of an inorganic filler is blended to 0 parts by weight.

Examples of the polyamide resin used in the present invention include polyamide resins obtained by polycondensation of lactams or ω-amino acids having four or more membered rings, or polycondensation of dibasic acid diamines.

Examples of the above-mentioned lactams or ω-amino acids having four or more members include ε-caprolactam, ω-laurolactam, ω-aminocaprylic acid, and ω-aminolauric acid.

Polyamides obtained from dibasic acids and diamines include geltaric acid, adipic acid, azelaic acid, sebacic acid,
Polymers obtained from dibasic acids such as speric acid, dodecanoic acid, eicosionic acid, isophthalic acid, and terephthalic acid, and diamines such as tetramethylene diamine, hexamethylene diamine, octamethylene diamine, xylylene diamine, and paraphenylene diamine. An example is a copolymer.

Specific examples of the above-mentioned polyamides include polyamide 4, polyamide 6, polyamide 12, polyamide 66, polyamide 610, polyamide 612, polymethaxylylene adipamide, polymethaxylylene adipamide, polymethaxylene glycamide, and polyhexane. Examples include, but are not limited to, methylene terephthalamide, and mixtures or copolymers thereof.

In the present invention, among the polyamides exemplified above, when meta-xylylene group-containing polyamide resin (hereinafter referred to as rMX nylon) is used, molded products exhibit particularly excellent performance in terms of mechanical properties, water resistance, heat resistance, etc. is obtained.

Among the above MX nylons, a diamine mixture of 60% by weight or more of metaxylylene diamine and 40% by weight or less of paraxylylene diamine and a C6-12 α,ω-linear aliphatic dibase are preferred. It is a polyamide resin synthesized by a polycondensation reaction with an acid such as adipic acid, sebacic acid, superric acid, undecanoic acid, and dodecanoic acid.

Considering the balance of moldability, molded product performance, etc., the above α
As the ω-linear aliphatic dibasic acid, adipic acid, sebacic acid, etc. are particularly preferred.

When polyamide 66 is mixed with MX nylon at a constant ratio and used as the polyamide resin in the resin composition of the present invention, there is an effect that the molding cycle during molding can be shortened.

The blending amount of polyamide 66 in the above mixed polyamide resin is effective over a wide range from the viewpoint of moldability, that is, shortening the molding cycle time, but when the physical performance of the molded product is also taken into consideration, MX nylon 4
It is preferably 60 to 1% by weight relative to 0 to 99% by weight (here, the total weight% is 100% by weight), and if the amount of polyamide 66 is less than this range, the expected molding cycle will be shortened. is not effective, and even if the amount is increased beyond this range, there is no effect of further shortening the molding cycle.
In addition, the strength tends to decrease due to water absorption, which is not preferable.

The polyphenylene sulfide used in the present invention is a polymer containing 70 mol% or more, preferably 90 mol% or more of repeating units represented by the following formula [I], and 30 mol% or less of the repeating units. The following formula [Irl~[,V
) may also be a copolymer containing repeating units represented by.

The silane coupling agent used in the present invention includes epoxysilane, vinylsilane, mercaptosilane, aminosilane, etc., and specifically, γ-glydoxypropyltrimethoxysilane, γ-glydoxypropylmethyljexysilane, Vinyltrichlorosilane, vinyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-
Examples include, but are not limited to, β(aminoethyl)T-aminopropyltrimethoxysilane.

Among the above-mentioned silane coupling agents, those having an amino group, an epoxy group, or a mercapto group that have particularly good compatibility with the polyamide resin are desirable.

By using the above silane coupling agent, mechanical strength or heat resistance can be improved.

The blending ratio when reacting the silane coupling agent with polyphenylene sulfide is preferably 0 parts by weight of the silane coupling agent per 100 parts by weight of polyphenylene sulfide.
．． 05 to 3 parts by weight, particularly preferably 0.1 to 2 parts by weight per 100 parts by weight of polyphenylene sulfide.

When 0.055 parts by weight or more of a silane coupling agent is added to 100 parts by weight of polyphenylene sulfide, the mechanical strength and heat resistance of the obtained molded product are improved. If 3 parts by weight or more of the ring agent is added, the molded product may become misaligned.

The reaction between the silane coupling agent and polyphenylene sulfide is achieved by placing the polyphenylene sulfide powder in a mixer such as a Henschel mixer, stirring at high speed, adding the silane coupling agent therein, and then stirring for an additional 30 to 60 minutes. Ru.

In the resin composition of the present invention, polyamide resin 20 to 8
The blending ratio of polyphenylene sulfide reacted with a silane coupling agent is 80 to 20% by weight relative to 0% by weight (here, the total weight% is 100% by weight).
.

If the blending ratio of polyamide resin exceeds the above range, the expected chemical resistance, water resistance, and heat resistance performance may not be sufficient.
Furthermore, if the blending ratio of the polyamide resin is less than the above range, the fluidity will be poor and the moldability will be reduced.

To improve moldability, it is generally necessary to raise the resin temperature during molding, but if the resin temperature is too high, gas will be generated due to heat aging of the polyamide, resulting in practical problems such as poor appearance. .

Examples of the inorganic filler used in this application include glass fiber, carbon fiber, calcium titanate, calcium carbonate, mica, silica, and kaolinite.

The above-mentioned inorganic filler may be selected depending on the purpose of use of the composition of the present invention.
Although preferred materials can be blended as appropriate, glass m-fibers are used when ordinary mechanical strength is to be improved.

The amount of the inorganic filler added is 25 parts by weight based on 100 parts by weight of the resin composition made of the polyamide resin and polyphenylene sulfide reacted with the silane coupling agent.
~150 parts by weight is preferred.

If the amount of the inorganic filler (1) is less than 25 parts by weight based on 100 parts by weight of the resin composition consisting of the polyamide resin and polyphenylene sulfide, the mechanical properties, heat resistance, etc. may be insufficient. If the amount is more than 150 parts by weight, the fluidity of the composition in the molten state may decrease, causing problems during injection molding, and the surface condition of the molded product may also deteriorate.

Various additives commonly used for polymeric materials, such as stabilizers, facial dyes, mold release agents, lubricants, fillers, etc., can be appropriately blended into the composition of the present invention, if necessary.

The resin composition for molding materials of the present invention is produced by a method of melt-kneading using a conventional vented extruder or similar equipment. The melt-kneading temperature is preferably 5 to 50°C higher than the softening temperature of the resin composition.

EXAMPLE 1 The present invention will be specifically described below with reference to Examples and Comparative Examples.

In Examples and Comparative Examples, "parts" represent parts by weight. still,
Mechanical properties and heat distortion temperature (HDT) were determined according to the following method.

Tensile strength: ASTM D638 Tensile modulus: ASTM D638 Bending strength:
ASTM D790 Flexural Modulus: ASTM
D790 Izot Impact Strength: ASTM D256 Heat Deformation Temperature: ASTM D648 (Load: 1
8.6kg/cm') Reference Example 1 Polyphenylene sulfide (()
$) Manufactured by Torblen, product name Nidoprene T-4) 10
0 parts by weight, and while stirring at 200 rpm, T-
1 part by weight of aminopropyltriethoxysilane (manufactured by Chisso Ki, trade name: Sila Ace APS-B 5330) was gradually added.

After the addition was completed, stirring was continued for 60 minutes at room temperature to obtain a polyphenylene sulfide resin reacted with a silane coupling agent.

Example 1 Number average molecular weight obtained by polycondensation from metaxylylene diamine and adipic acid [6o].

O polymethaxylylene adipamide (hereinafter referred to as "polyamide MXD6J") 2.L 5 parts, number average molecular weight 18
000 Polyamide 66 (Toshi G-Kasei, Product Name: CM
3001N) 3.5 parts, polyphenylene sulfide resin 42 reacted with the silane coupling agent obtained in Reference Example 1
glass fiber chopped strand (manufactured by Asahi Fiberglass ■, product name: C3O3JAFT)
After blending 30 parts of -2), the mixture was melt-kneaded using a single-screw extruder at a cylinder temperature of 300°C, extruded into strands, cooled with water, further cut into pellets, and then dried to form pellets. A resin composition was obtained.

Next, various test pieces were molded from the above pelletized resin composition using an injection molding machine under conditions of a mold temperature of 130°C and a cylinder temperature of 280°C. The tensile strength, flexural strength, flexural modulus, and isot impact strength of the molded product were measured.

These results are shown in Table 1.

Comparative Example 1 In Example 1, untreated polyphenylene sulfide (trade name Nidoprene T-4, manufactured by Toblen Co., Ltd.) was used as a substitute for polyphenylene sulfide reacted with a silane coupling agent. Pellets were produced by the method. Using this material, various test pieces were molded by injection molding, and the physical properties of the molded products were measured. The results are shown in Table 1.

Example 2 1 part of T-mercaptotrimethoxysilane was added to 100 parts of polyphenylene sulfide (e)) (manufactured by Frene, trade name Nido-Bren T-4), and silane coupling was performed in the same manner as in Reference Example 1. A polyphenylene sulfide resin was obtained by reacting the agent with the polyphenylene sulfide resin.

This polyphenylene sulfide resin and the components shown in Table 2 were blended in the proportions shown in Table 2, and pellets were produced in the same manner as in Example 1.

Various test pieces were molded by injection molding using the above pellets, and the physical properties of the molded products were measured. Second result
Shown in the table.

Comparative Example 2 Pellets were produced in the same manner as in Example 1 using each component shown in Table 2.

Various test pieces were molded by injection molding using the above pellets, and the physical properties of the molded products were measured. Second result
Shown in the table.

[Effect of the invention] A resin composition for a molding material obtained by blending a polyphenylene sulfide resin made by reacting polyphenylene sulfide with a silane coupling agent, a polyamide resin, and an inorganic filler has excellent moldability, water resistance, and chemical resistance. It has excellent mechanical strength and heat resistance, and is extremely useful as a substitute material for metals.

Table 1

Claims (6)

[Claims] (1) Consists of 80-20% by weight of a resin made by reacting polyphenylene sulfide with a silane coupling agent and 20-80% by weight of a polyamide resin (here, the total weight% is 1% by weight)
A resin composition for a molding material comprising 25 to 150 parts by weight of an inorganic filler to 100 parts by weight of the resin composition. (2) Polyamide resin and xylylenediamine α, ω-
The resin composition for a molding material according to claim 1, which is a polyamide resin obtained from a linear aliphatic dibasic acid. (3) Polyamide resin and xylylenediamine α, ω-
Polyamide resin 40 obtained from linear aliphatic dibasic acid
The resin composition for a molding material according to claim 1, which is a mixed polyamide resin comprising ~99% by weight of polyamide and 6,660~1% by weight of polyamide (the total weight% being 100% by weight). (4) The resin composition for a molding material according to claim (1), wherein the silane coupling agent is aminosilane or mercaptosilane. (5) The resin made by reacting polyphenylene sulfide with a silane coupling agent is polyphenylene sulfide 10
The resin composition for a molding material according to claim 1, wherein 0.05 to 3 parts by weight of a silane coupling agent is mixed and reacted with 0 parts by weight. (6) The resin composition for a molding material according to claim (1), wherein the inorganic filler is glass fiber.