JPH0337260A - Resin composition - Google Patents

Abstract

PURPOSE:To improve the heat resistance, impact strength, and moldability by compounding a polyphenylene sulfide resin, nylon 66, and an epoxidized olefin copolymer in a specified ratio. CONSTITUTION:A glycidyl ester of an alpha,beta-unsatd. carboxylic acid (e.g. glycidyl acrylate) is copolymerized with an olefin to give an epoxidized olefin copolymer. Then 100 pts.wt. the sum of 30-90wt.% polyphenylene sulfide resin and 70-10wt.% nylon 66 with a relative viscosity (in 96% sulfuric acid, at 25 deg.C, in 1g/dl concn.) of 2.0-6.0 is compounded with 2-50 pts.wt. the epoxidized olefin copolymer to give a resin compsn. 80-60 pts.wt. the resin compsn. is mixed with 20-40 pts.wt. glass fiber, or 50-30 pts.wt. the resin compsn. is mixed with 50-70 pts.wt. (1:3)-(3:1) mixture of glass fiber with CaCO3.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a thermoplastic resin composition having excellent heat resistance, mechanical properties, and moldability, and which can be used in automobiles, electrical appliances, etc. by injection molding or extrusion molding. It is a useful molded product in the electronic and mechanical fields.

[Conventional technology 1] The fields of application of engineering plastics have been expanding more and more in recent years, and their use in the automobile, electric, and electronic fields has increased significantly in particular. As a result, user demands for plastics have become more diverse and highly functional, and meeting these demands has become a technological challenge. However, these diversified and highly functional demands cannot be fully met with a single material alone, and therefore polymer alloys have recently been actively used to meet these demands.

Nylon 66 and polyphenylene sulfide resin (hereinafter referred to as P)
A resin composition consisting of PS (referred to as PS) is a known polymer alloy (Japanese Unexamined Patent Publication No. 53-69255) and was developed against the background of the above-mentioned requirements. Although such a resin composition has an excellent tensile strength of about 6001<g/cn+'', its impact strength is not necessarily satisfactory.

That is, its Izot impact strength is about 3 to 51 (gcm/
cm, which is an insufficient value for engineering plastics.

[Problems to be Solved by the Invention] In view of the above-mentioned circumstances, an object of the present invention is to develop a resin composition that maintains the excellent properties of a resin composition made of nylon 66 and PPS while improving its impact resistance. The purpose is to obtain a composition.

[Means and effects for solving the problem] As a result of intensive research for this purpose, the present inventors found that PP5 (A), nylon 66 resin (I3), and epoxy group-containing olefin copolymer (C) (A)/(B) =30/70~9
It has been discovered that a thermoplastic resin composition with a ratio of 0/10 achieves the above object, and the present invention has been achieved.

It is preferable that the PPS used in the present invention is a polymer in which 90 mol% or more consists of the structural unit ←(■-8+; if it is less than 90 mol%, the crystallinity decreases and the heat resistance is 0.
It is difficult to obtain satisfactory mechanical properties. It should be noted that the polymer may contain other copolymerized units as long as it is less than 10 mol%. Examples of such copolymerized units include trifunctional groups (e.g. -8- in C), ether units (e.g. C -o-CD-s -), sulpon units (e.g. -so in (c) , <■-8-), meta-bonding unit (
Examples include '-@-''-). It is also possible to cause crosslinking by heating the polymerized polymer.

Although there are various methods for synthesizing PPS composed of such structural units, a method of reacting p-dihalobenzene with an alkali sulfide or an alkaline earth metal sulfide in a polar organic solvent is suitable, and the polymerization conditions are 200 to 350°C. The temperature, pressure within the polymerization system and polymerization time are appropriately determined depending on the type of catalyst used and the desired degree of polymerization.

The nylon 66 resin used in the present invention includes a copolyamide whose main constitutional unit is a polyhexamethylene adipamide unit obtained from hexamethylene diamine and adipic acid, and a mixed polyamide. The copolymerization component or mixed component is not particularly limited, and known amide-forming components can be used. Typical examples of copolymerized components include 6-aminocaproic acid, 11-aminoundecanoic acid, 12
- Amino acids such as aminododecanoic acid and para-aminomethylbenzoic acid, lactadiamines such as ε-caprolactam and ω-lauryllactam, dodecamethylenediamine, 2
, 2.4-/2,4.4-1-limethylhequinamethylenediamine, 5-methylnonamethylenediamine, metaglysilylenediamine, baraxylylenediamine, 13-bis(aminomethyl)cyclohexane, 1,4-bis (aminomethyl)cyclohexane, l-amino-3-aminomethyl-3,5,5-)limethylcyclohexane, bis(
3-methyl-4-aminocyclohexyl)methane, 2,
Diamines such as 2-bis(4-aminocyclohexyl)propane, bis(aminopropyl)piperazine, aminoethylpiperazine, and adipic acid, speric acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 12-chloroterephthalic acid , 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, diglycolic acid, and other dicarboxylic acids. Examples include polyamides consisting of the following components. Crystalline polyamide is preferred.

Regarding the degree of polymerization of nylon 66 resin, the relative viscosity is usually 2.
．． Nylon 66 within the range of 0 to 6,0 can be arbitrarily selected. The relative viscosity here refers to the relative viscosity at 25° C. in 96% sulfuric acid at a concentration of 1 g/dβ.

The epoxy group-containing olefin copolymer used in the present invention is
Direct copolymerization of glycidyl esters of α, β-unsaturated carboxylic acids with olefins, and graphs for polyolefins and polyolefin copolymers! - Manufactured by known methods such as copolymerization.

The α,β-unsaturated carboxylic acid used here (in the formula,
R is a hydrogen atom or a lower alkyl group. ), examples of which include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, etc. Among them, glycidyl methacrylate is preferably used.

Such an epoxy group-containing olefin copolymer (D) usually has a heptanomer having these functional groups as a constituent component. It ranges from 0.05 to 5% by weight, preferably from 0.05 to 5% by weight. These epoxy radical-containing reflexine copolymers are commercially available from Sumitomo Chemical Co., Ltd. under the name "rBond Fast".

In the present invention, the mixing ratio of P P S (A) and nylon 66 resin (13) is (A)/(B) =
It ranges from 30/70 to 90/10, and P P S (
If the content of A) exceeds 90% by weight, the improvement effect of PPS will be reduced, and if it is less than 30% by weight, the original properties of PPS will be largely lost, which is not preferable. Among them, the preferred mixing ratio is (A)/(B) = 40/60~
It is 80/20.

The amount of the epoxy group-containing olefin copolymer (C) added is determined by the amount of the epoxy group-containing olefin copolymer (C) that is
) Total amount of (A) + (B) 2 to too parts by weight
50 parts by weight, preferably in the range from 5 to 30 parts by weight. If the amount of the epoxy group-containing olefin copolymer added is more than 50 parts by weight, it is undesirable because the mechanical strength, thermal properties, molding processability, etc. of the resulting molded article will deteriorate. Further, if the amount is less than 2 parts by weight, the effect of the present invention will be small and it will be difficult to achieve the present invention.

Further, the resin composition of the present invention can be added with an inorganic filler as necessary to improve rigidity and the like. Suitable fillers include glass U&fiber and calcium carbonate with a particle size of 0.5-5μ.

The amount of glass fiber (E) to be added is preferably mixed in a weight ratio of (E)/(D) = 20/80 to 40/60 with respect to the total resin composition (D). A particularly preferable range is (E)/
(D)=30/70 to 50/50.

Also, calcium carbonate (F) used as an inorganic filler
A particle size in the range of 0.5 to 5μ is suitable for maintaining physical properties and workability, and a particularly preferable particle size range is 1 to 3μ. The calcium carbonate (F) used, the glass fiber (E), and the resin composition (D) are blended so that the relationship of (E)/(F) = 1/3 to 3/1 is satisfied. Preferable in terms of physical properties and processability.

The resin composition of the present invention may also contain a plasticizer such as an aromatic hydroxy derivative, such as 2-ethylhexyl-p-hydroxybenzoate, a sulfonic acid amide, such as benzenesulfone butyramide, or a small amount of a mold release agent. , a coupling agent, a coloring agent, a lubricant, a heat-resistant stabilizer, a weather-resistant stabilizer, a foaming agent, a rust preventive agent, a flame retardant, a flame retardant aid such as antimony trioxide, etc. may be added.

The resin composition of the present invention can be prepared by various known methods. For example, the raw materials are mixed uniformly in advance in a tumbler or Henschel mixer (mixer), and then subjected to a -screw or twin-screw extrusion. There is a method of supplying it to a machine etc., melting and kneading it, and then preparing it as pellets.

[Example] Examples 1 to 8. Comparative Examples 1 to 4 Nylon 66 (Leona 1300J, manufactured by Asahi Kasei Industries, Ltd.), PPS (rToblen J T-4, Toblen Corporation), and epoxy group-containing olefin copolymer (rBond First E) manufactured by Sumitomo Chemical ) in the weight percent ratio shown in Table 1 in ■ blender, and co-rotating twin-screw extrusion 4 with the cylinder temperature set at 40°C for one part of the hopper, 300°C for the center, and 310°C for the tip. 1 (PCM30 manufactured by Ikegai Tekko Co., Ltd.) to obtain pellets by a conventional method. The resulting pellets were subjected to a normal injection molding method, with the cylinder temperature set at 40°C at the tip, 295°C at the center, 300°C at the tip, and 140°C at the mold temperature, and various physical properties were measured. . Tensile test is JIS
K6911, impact test was measured based on ASTM D-256.

(Margins below) Table 1 Examples 9 to 12. Comparative Example 5.6 Example 1.2. The resin composition pellets obtained in Example 3.4 and Comparative Example 1.2 were mixed with glass fiber (manufactured by Nippon Electric Glass Co., Ltd., grade name 717P, fiber diameter 13 μm) and calcium carbonate (manufactured by Shiraishi Calcium ■, particle size 2 μm white). 31O) were mixed and extruded at a cylinder temperature of 310° C. using PCM30 manufactured by Ikegai Tekko Co., Ltd. The obtained physical property values are shown in Table 2.

(The following is a blank space) Table 2 [Effects of the Invention] As described above, the resin composition of the present invention has each component blended with good compatibility, has a good molded product appearance, has high thermal shape stability, and can withstand high temperatures. It is a resin composition that maintains excellent mechanical properties even in the atmosphere and has excellent impact strength, and is a highly practical molding material with excellent physical properties as an engineering plastic.

Claims (3)

[Claims] (1) Polyphenylene sulfide resin (A), nylon 66 resin (B), and epoxy group-containing olefin copolymer (C) (A)/(B) = 30/70 to 90/10 (C)/{( A)+(B)}=2/100~50/10
A resin composition characterized by being blended in a weight ratio of 0. (2) A resin composition comprising the resin composition (D) according to claim (1) and glass fiber (E) in a weight ratio of (E)/(D) = 20/80 to 40/60. . (3) The resin composition (D) according to claim (1), glass fiber (E) and calcium carbonate (F) having a particle size of 0.5 to 5μ
) and (E) + (F)/(D) = 50/50 to 70/30 (E
)/(F)=1/3 to 3/1.