JPS63301252A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in heat resistance, moldability and impact strength, by mixing nylon 46 with a polyphenylene sulfide, an epoxy group-containing olefin copolymer and an acid anhydride-containing olefin copolymer at a specified ratio. CONSTITUTION:The purpose thermoplastic resin composition is obtained by mixing 90-40wt.% nylon 46 with 5-50wt.% polyphenylene sulfide, 1-20wt.% epoxy group-containing olefin copolymer obtained by copolymerizing an olefin with an unsaturated glycidyl monomer (e.g., glycidyl acrylate/propylene copolymer) and 1-20wt.% acid anhydride-containing olefin copolymer obtained by copolymerizing an olefin with an alpha,beta-unsaturated dicarboxylic acid anhydride (e.g., maleic anhydride/propylene copolymer). The obtained thermoplastic resin composition is suitable for producing moldings used in the fields of automobiles, electronic devices, etc.

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.

(Prior Art) The field of application of engineering plastics has been expanding more and more in recent years, and in particular, their use in the automobile, electrical, and electronic fields has increased significantly. As a result, user demands for plastics have become more diverse and sophisticated, 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.

The resin composition consisting of nylon 46 and polyphenylene sulfide is a well-known polymer alloy (Japanese Patent Laid-Open No. 1983-1999).
126170) was developed based on such demands. Such a resin composition has a tensile strength of about 100
0Kg/cd, flexural modulus 31, 000Kg/
cJ, heat distortion temperature (18,6Kg/- under load) approx. 17
Although it has excellent performance at 0°C, its impact strength is not necessarily satisfactory.

That is, the Izod impact strength is approximately 6 g-cm/cr.
n, which is an insufficient value for engineering plastics. Although impact strength is an extremely important property for engineering plastics,
Regarding the resin composition composed of nylon 46 and polyphenylene sulfide, there have been no reports of attempts to improve this or to obtain a material with increased impact strength.

(Problems to be Solved by the Invention) In view of the above circumstances, an object of the present invention is to improve the impact resistance of the resin composition while maintaining the excellent properties of the resin composition composed of nylon 46 and polyphenylene sulfide. The objective is to obtain a resin composition.

(Means and effects for solving the problem) The present inventors have conducted extensive research for the above purpose. The present invention was achieved based on the discovery that a thermoplastic resin composition obtained from (D) an acid anhydride-containing olefin copolymer achieves all of the objects.

That is, the present invention is an epoxy group-containing olefin copolymer obtained by copolymerizing (A) 46.90 to 40% by weight of nylon, (B) 50 to 5% by weight of polyphenylene sulfide, and (C) an unsaturated glycidyl monomer. Combined with 20-1% by weight (
D) A thermoplastic resin composition comprising 20 to 1% by market weight of an acid anhydride-containing olefin copolymer obtained by copolymerizing an α,β-unsaturated dicarboxylic acid anhydride.

Nylon 46 used in the present invention includes polytetramethylene adipamide obtained from tetramethylene diamine and adipic acid, a copolyamide having tetramethylene adipamide units as a main constituent unit, and a mixed polyamide. The copolymerization component or mixed component is not particularly limited, and known amide-forming components can be used. Representative examples of copolymerized components include 6-aminocaproic acid, 11
-Amino acids such as aminoundecanoic acid, 12-aminododecanoic acid, para-aminomethylbenzoic acid, lactams such as ε-caprolactam and ω-lauryllactam, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2.4- /2゜4.4-) lynchylhexamethylenediamine, 5-methylnonamethylenediamine, metaxylylenediamine, paraxylylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1.4-bis(aminomethyl) ) Cyclohexane, 1-
Amino-3-aminomethyl-3,5,5-trimethylcyclohexane.

Bis(3-methyl-4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, bis(aminopropyl)piperazine.

diamines and adipic acid, such as aminoethylpiperazine;
Speric acid, azelaic acid, sebacic acid.

Dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid.

Examples include dicarboxylic acids such as 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, and diglycolic acid, and mixed polyamides include polyamides made of these components. Can be done.

The method for producing nylon 46 used in the present invention is arbitrary. For example, methods disclosed in JP-A-56-149430, JP-A-56-149431, JP-A-58-83029, and JP-A-61-43631.

In other words, first, a prepolymer with a small amount of cyclic end groups is produced under specific conditions, and then this is solid-phase polymerized in a steam atmosphere to prepare high-viscosity nylon 46, or 2-pyrrolidone or N- It is particularly preferable to use one obtained by heating in a polar organic solvent such as methylpyrrolidone. There is no limit to the degree of polymerization of Nylon 46.1 Nylon 4 usually has a relative viscosity within the range of 2.0 to 6.0.
6 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/di.

The polyphenylene sulfide used in the present invention is 9
It is preferable that 0 mol % or more is a polymer consisting of the structural unit ÷ CXS. If it is less than 90 mol %, crystallinity decreases and it is difficult to obtain a polymer with satisfactory heat resistance, mechanical properties, etc. It should be noted that the polymer may contain other copolymerized units as long as it is less than 10 mol%. Examples include such copolymerized units (eg, i''-).

It is also possible to cause slight crosslinking by heating the polymerized polymer.

There are various methods for synthesizing polyphenylene sulfide composed of such structural units, but a method in which p-dihalobenzene and alkali sulfide or alkaline earth metal sulfide are reacted in a polar organic solvent is suitable.
A temperature of ~350°C is commonly used, and the 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 unsaturated glycidyl monomer, which is a copolymerization component of the epoxy group-containing olefin copolymer used in the present invention, has one unsaturated bond in one molecule that can be copolymerized with the olefin monomer. A monomer having one or more groups.

For example, unsaturated glycidyl esters represented by the general formula % formula % () (where R1 represents a hydrocarbon group having an olefinically unsaturated bond) and the general formula % formula %) (where Y is -C1h -C- or -C5-0-, and R+ is the same as the explanation of formula (1).) and the general formula (here, R+ is the same as the explanation of formula (1)) The same as in the explanation.P1 is hydrogen or a methyl group.

Itaconic acid diglycidyl ester, butenetricarboxylic acid monoglycidyl ester, butenetricarboxylic acid diglycidyl ester, butenetricarboxylic acid triglycidyl ester, p-styrenecarboxylic acid glycidyl ester, allyl glycidyl ether, 2-methylallyl glycidyl ether.

Styrene p-glycidyl ether or p-glycidylstyrene, 3,4-epoxy-1-butene.

3.4-Epoxy-3-methyl-1-butene, 3,4-
Examples include epoxy-1-pentene, 3,4-epoxy-3-methyl-1-pentene, 5,6-epoxy-1-hexene, and vinylcyclohensen monoxide.

Examples of the olefinically unsaturated monomer that is a copolymer component of the epoxy group-containing olefinic copolymer used in the present invention include the following.

Olefins such as ethylene, propylene, butene-1, decene-1°octacene-1, and styrene.

Vinyl esters containing 2 to 6 carbon atoms in the saturated carboxylic acid component2, such as vinyl acetate, vinyl propionate, vinyl benzoate, etc.Methyl acrylic acid and methacrylate containing 1 to 8 carbon atoms in the saturated alcohol component -, ethyl-, propyl-, butyl-12-
Esters such as ethylhexyl, cyclohexyl, dodecyl, octadecyl, maleic acid diester,
Vinyl chloride, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, N-vinyl lactams such as N-vinylpicolidone or N-vinyl caprolactam and acrylamide compounds, secondary acids N
-vinylcarboxylic acid amide, N-vinyl-N-alkylcarboxylic acid amide, and the like.

Among the above-mentioned olefinically unsaturated monomers, ethylene, propylene, vinyl acetate and acrylic esters are particularly useful for bonding.

The copolymerization ratio of unsaturated glycidyl monomer in the epoxy group-containing olefin copolymer used in the present invention is 0.05 to 95 mol%, preferably 0.1 to 50 mol%.

The α,β-unsaturated dicarboxylic acid anhydride, which is a copolymerization component of the acid anhydride-containing olefin copolymer used in the present invention, has the following formula (where R1 and R2 represent hydrogen, an alkyl group, or a halogen group). ), examples of which include maleic anhydride, methylmaleic anhydride, chloromaleic anhydride, citraconic anhydride, butynylsuccinic anhydride, and tetrahydrophthalic anhydride.

α and β used as necessary as copolymerization components of the acid anhydride-containing styrenic copolymer used in the present invention
- Specific examples of unsaturated carboxylic acid esters include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and 2-ethyl methacrylate.
- methacrylic esters such as hydroxyethyl, acrylic esters such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, etc., or mixtures thereof. Further, as a monomer copolymerizable with ethylene, α,β-unsaturated carboxylic acid ester, and α,β-unsaturated dicarboxylic acid anhydride, styrene is used.

Styrenic compounds such as α-methylstyrene and vinyltoluene, α such as acrylonitrile and methacrylonitrile,
β-unsaturated nitrile, acrylic acid.

Examples include α, β-unsaturated carboxylic acids such as methacrylic acid, vinyl acetate, vinyl ether, etc., and these can also be copolymerized if necessary.

The copolymerization ratio of α, β-unsaturated dicarboxylic acid anhydride in the acid anhydride-containing olefin copolymer used in the present invention is 0.05 to 95 mol%, preferably 0.1 to 5
It is 0 mol%. As a method for producing such an epoxy group-containing olefin copolymer or an acid anhydride-containing olefin copolymer, a so-called known radical copolymerization method may be used.

Examples include a method in which a radical generator is present in an olefin homopolymer or an olefin copolymer, and one or more of the unsaturated monomers having the above groups are subjected to a radical graft reaction in the presence or absence of a solvent or dispersion medium. be able to. In particular, when grafting is carried out in a molten state, the desired product can be obtained in a very short time with a simplified procedure by using a melt mixer such as an extruder, kneader, or panburi mixer.

The blending amounts of nylon 46 and polyphenylene sulfide in the thermoplastic resin composition of the present invention are nylon 46 and polyphenylene sulfide.
~40% by weight, 50~5M polyphenylene sulfide
The blending ratio of nylon 46 and polyphenylene sulfide is preferably such that the amount of nylon 46 increases in terms of percentage.

In addition, the blending amounts of the epoxy group-containing olefin copolymer and the acid anhydride-containing olefin copolymer used as impact resistance agents are each in the range of 20 to 1% by weight, and the epoxy group-containing olefin copolymer The blending ratio of the acid anhydride-containing olefin copolymer and the epoxy group/acid anhydride equivalent ratio is preferably 1:9 to 9:1.

Additionally, in the thermoplastic resin composition of the present invention, additives such as heat stabilizers, oxidation stabilizers, light stabilizers, lubricants, pigments, flame retardants, plasticizers, and the like may be further mixed.

Also glass fiber, metal fiber, potassium titanate whisker,
Fibrous reinforcement such as carbon fiber, talc.

Filler reinforcing agents such as calcium carbonate, mica, glass flakes, milled fibers, metal flakes and 2 metal powders may be incorporated. In particular, glass fiber is added to 10 to 90% of the thermoplastic resin composition of the present invention.
By incorporating up to 50% by weight, not only the mechanical strength and heat resistance are significantly improved, but also the water resistance is further improved, which is preferable for achieving the object of the present invention.

The present invention will be explained in more detail with reference to Examples below.

(Example) Examples 1 to 5. Comparative Examples 1 to 3 Nylon 46 (rSTANYLJ Netherlands DSM
Company, 25°C in 96% sulfuric acid, concentration 1g/d7! relative viscosity of 3.2) and polyphenylene sulfide (rRY
TONj p-4 manufactured by Phillips Petroleum, USA), an epoxy group-containing olefin copolymer (BONDINE LX-4110J Sumitomo Chemical), and an acid anhydride-containing olefin copolymer (BONDINE LX-4110J Sumitomo Chemical). (manufactured by DF Co., Ltd.) in the weight percent ratio shown in Table 1 using a blender, and dried for 16 hours under a reduced pressure of 80°C.
The mixture was melt-kneaded using a co-rotating twin-screw extruder set at 300°C in the center and 310°C in the tip to obtain pellets in a conventional manner. The obtained pellet was heated to 80°C I Tor.
After drying for 16 hours under reduced pressure of Physical properties were measured. Bending test is AST
MD-790, impact test was measured based on ASTM D-256, and heat distortion temperature was measured based on 8 STM [+-848].

The spiral length was measured using an Archimedean spiral with a 5nn+ semicircular cross section.

(Effects of the Invention) As specifically shown in Table 1, it is clear that the thermoplastic resin composition of the present invention has significantly improved impact strength while maintaining heat resistance and moldability compared to the comparative example. be.

Patent applicant: Unitika Co., Ltd. Shizuka Tezai ↑ Masaaki ↑ (spontaneous) March 9, 1986

Claims (1)

[Claims] (1) (A) Nylon 46, 90-40% by weight and (B)
20 to 1% by weight of an epoxy group-containing olefin copolymer obtained by copolymerizing 50 to 5% by weight of polyphenylene sulfide and (C) an unsaturated glycidyl monomer, and (D) α, β
- A thermoplastic resin composition comprising 20 to 1% by weight of an acid anhydride-containing olefin copolymer obtained by copolymerizing an unsaturated dicarboxylic acid anhydride.