JPH02169659A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To improve the impact resistance while maintaining the heat distortion resistance, chemical resistance and stiffness of a thermoplastic resin compsn. by compounding an acid anhydride-contg. olefin polymer and an epoxy group- contg. vinyl polymer into a resin compsn. comprising polyarylate and polyamide. CONSTITUTION:100 pts.wt. resin compsn. comprising 20-80wt.% polyarylate (e.g. a reaction product of bisphenol A with a 3:7 mixture of terephthalic acid and isophthalic acid) and 80-20wt.% polyamide is blended with 1-30 pts.wt. acid anhydride-contg. olefin polymer (e.g. maleic anhydride-contg. ethylene- propylene copolymer) and 1-30 pts.wt. epoxy group-contg. vinyl polymer (e.g. copolymer of glycidyl methacrylate, acrylonitrile and styrene in the wt. ratio of 10:20:70) to give a thermoplastic resin compsn., which has a good balance among above-mentioned properties and an excellent processability.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a thermoplastic resin composition that has excellent heat deformation resistance, impact resistance, and rigidity, and also has excellent moldability. More specifically, the present invention relates to a thermoplastic resin composition obtained by adding an acid anhydride-containing olefin copolymer and an epoxy group-containing vinyl copolymer to a composition consisting of polyarylate and polyamide.

[Conventional technology]

Resin compositions made of polyarylate and polyamide have been known for a long time and have excellent heat deformation resistance, chemical resistance, etc., but are not satisfactory in terms of impact resistance. Various attempts have been proposed in the past. For example, Japanese Patent Application Laid-Open No. 62-277462 proposes adding an impact strength imparting material consisting of a mixture of an epoxy group-containing ethylene copolymer and an acid anhydride-containing olefin copolymer. However, although this method improves the impact resistance to some extent, the heat deformation resistance, rigidity, etc. are significantly reduced, and it cannot be said to be a preferable method.

[Problem that the invention seeks to solve]

The object of the present invention is to improve the impact resistance of a resin composition made of polyarylate and polyamide while maintaining the excellent heat deformation resistance, chemical resistance, and rigidity of the tube. That is, the present invention has excellent heat deformation resistance, impact resistance, and rigidity, and
The object of the present invention is to provide a molding material having excellent moldability.

[Means for solving problems]

As a result of intensive studies aimed at achieving this object, the present inventors have developed a resin composition consisting of polyarylate and polyamide (
The inventors have discovered that the above object can be achieved by adding an acid anhydride-containing olefin copolymer (B) and an epoxy group-containing vinyl copolymer (C) to A), and have completed the present invention. .

That is, the present invention provides a resin composition (A>1
A thermoplastic resin composition obtained by adding 1 to 30 parts by weight of an acid anhydride-containing olefin copolymer (B) and 1 to 30 parts by weight of an epoxy group-containing vinyl copolymer (C) to 00 parts by weight. The content is as follows.

The resin composition (A) used in the present invention consists of polyarylate and polyamide.

The polyarylate used in the present invention includes at least one selected from terephthalic acid, isophthalic acid, or functional derivatives thereof, and 141-RI+ Rt selected from the group consisting of an alkylene group or an alkylidene group. , R3, Ra, R'-1
R't, R'x.

R'4=one selected from the group consisting of a hydrogen atom, a halogen atom, or a hydrocarbon).

Above-mentioned - The maximum expressed bisphenols are 4,
4'-dihydroxy-diphenyl ether, bis(4-
hydroxyphenyl)-sulfide, bis(4-hydroxyphenyl)-sulfone, bis(4-hydroxyphenyl)-bton, bis(4-hydroxyphenyl)-
Methane, bis(4-hydroquine-3,5-dimethyl)-
Methane, 1,1-bis(4-hydroquinphenyl)-phenylethane, bis(4-hydroxyphenyl)-diphenylmethane, bis(4-hydroxy-35-difluorophenyl)-methane, 2,2-bis(4- Hydroxy-3,5-dichlorophenyl)-propane, bis(4-
hydroxyphenyl)-cyclohexylmethane, t, t
-bis(4-hydroxyphenyl)-cyclohexane,
2゜2-bis(4-hydroxynaphthyl)-propane,
Examples include 2.2-bis(4-hydroxyphenyl)-propane. Furthermore, if necessary, one or more selected from the above bisphenols and other divalent compounds, such as 4
, 4'-dihydroxyphenyl, dihydroxynaphthalene, hydroquinone, and the like can be used.

The derivatives of terephthalic acid or isophthalic acid used in the present invention are dichlorides or alkyls of these acids,
It is a diester such as alcohol, and the nucleus may be substituted with a halogen atom or an alkyl group.

The polyarylate used in the present invention is produced by methods such as interfacial polymerization, solution polymerization, and melt polymerization. The intrinsic viscosity is preferably in the range of 0.2 to 1.5 (chloroform solution, 30°C). Anything outside this range is unfavorable from the viewpoint of Ui impact resistance, melt viscosity during molding, etc.

The polyamide used in the present invention has -max (Rs, R
h, R,: phenylene group or alkylene group).

The polyamide used in the present invention includes those produced by a condensation reaction of a diamine and a dibasic acid, a self-condensation reaction of an amino acid, and a polymerization reaction of a lactam.

Examples of the polyamide used in the present invention include polytetramethylene adipamide, polyhexamethylene adipamide, polycaprolactam, and polyhexamethylene sebamide. Further, it may be a copolymer of two or more types of F, or a mixture of two or more types. Solution viscosity is relative viscosity: 2
．． 0 to 5.0 (1% concentrated sulfuric acid solution, 25°C) is preferable,
Outside this range, impact resistance, chemical resistance, moldability, etc. deteriorate, which is not preferable.

The acid anhydride-containing olefin copolymer CB) used in the present invention is a homopolymer of olefins such as polyethylene, polypropylene, polybutene-1, or an ethylene-propylene copolymer, an ethylene-butene-1 copolymer, Ethylene-propylene-diene copolymer, ethylene-vinyl acetate copolymer, etc., containing an alicyclic carboxylic acid anhydride or α,β-unsaturated dicarboxylic acid anhydride having a cis-type double bond in the ring. It is contained as a copolymerization component. Examples of alicyclic carboxylic acid anhydrides having a cis-type double bond in the ring include cis-4-cyclohexene-1,2-dicarboxylic acid, endo-bicyclo-[2°2.1)-5-hebutene-2 , 3-dicarboxylic acid and the like are exemplified. Examples of the α,β-unsaturated dicarboxylic anhydride include maleic anhydride, methylmaleic anhydride, chloromaleic anhydride,
Examples include citraconic anhydride.

As a copolymerization component of the acid anhydride-containing olefin copolymer (B), methacrylic acid esters such as methyl methacrylate and ethyl methacrylate, ethyl acrylate, butyl acrylate, and acrylic acid 2, which can be copolymerized as necessary, are used. -Acrylic esters such as ethylhexyl, styrene, α-
Aromatic vinyl compounds such as methylstyrene, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, etc. may be copolymerized.

Further, the copolymerization ratio of unsaturated dicarboxylic acid anhydride in the acid anhydride-containing olefin copolymer (B) is 0.01 to
30% by weight, preferably 0.05-20% by weight.

If it is outside this range, the impact resistance will decrease or the molding processability will deteriorate, which is undesirable. Any graft copolymer may be used.

The epoxy group-containing vinyl copolymer (C) used in the present invention is a copolymer consisting of an unsaturated glycidyl compound and a vinyl compound. Examples of unsaturated glycidyl compounds include unsaturated glycidyl esters, unsaturated glycidyl ethers, and epoxy alkenes, and specific examples include glycidyl acrylate, glycidyl methacrylate, itaconate diglycidyl ester, styrene carboxylic acid glycidyl ester, 3. Examples include 4-epoxy-1-butene. Vinyl compounds include aromatic vinyl compounds such as styrene, α-methylstyrene, and methylstyrene, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, methacrylic acid ester compounds such as methyl methacrylate and ethyl methacrylate, and butyl acrylate. , acrylic acid esters such as ethyl acrylate and 2-ethylhexyl acrylate.

One or more of these unsaturated glycidyl compounds and vinyl compounds can be used as required.

The copolymerization ratio of the unsaturated glycidyl compound in the epoxy group-containing vinyl copolymer (C) is 0.1 to 50% by weight, preferably 1 to 30% by weight, and outside this range, the impact resistance , rigidity, moldability, etc. are reduced, which is undesirable.

The composition ratio of polyarylate and polyamide in the resin composition (A) used in the present invention is 20 to 80% by weight of polyarylate and 80 to 20% by weight of polyamide. Further, the acid anhydride-containing olefin copolymer (B) added to the resin composition (A) is 1 to 30 parts by weight, preferably 3 to 20rR11 parts, based on the resin composition (A). The vinyl copolymer (C) is 1 to 30 parts by weight, preferably 3 to 20 parts by weight, and the ratio of (B) and (C) used is 9/1 to 1/9 in terms of weight ratio. Preferred resin composition (
If the composition ratio of polyarylate and polyamide in A), the amounts of (B) and (C) added, and their ratio are outside the above ranges, heat deformation resistance, impact resistance, rigidity, moldability, and resistance will deteriorate. It is preferable because the drug properties etc. are lowered, but it is not preferable.

The thermoplastic resin acid product of the present invention obtained as described above further contains lubricants such as wax, stabilizers such as phosphites and phenols, ultraviolet absorbers, pigments, flame retardants, Plasticizers, fillers, etc. can be added. Mixing and pelletizing can be carried out by various methods. For example, a resin composition (A) consisting of polyarylate and polyamide, an acid anhydride-containing olefin copolymer (B), and an epoxy group-containing vinyl copolymer. All or part of two or more types of coalescing (C) may be mixed first and pelletized, and then mixed with the rest, or (A), (B) and (C) may be mixed simultaneously,
It may be pelletized.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited in any way by these.

Examples 1 to 6 and Comparative Examples 1 to 5 Resin composition (A) Polyarylate: one produced from a mixture of 2,2-bis(4-hydroxyphenyl)propane and terephthalic acid/isophthalic acid-3/7. , with an intrinsic viscosity of 0.6.

Polyamide: "Amilan C?11026 (polycaprolactam)" manufactured by Toshi ■.

Acid anhydride-containing olefin copolymer (B); ethylene-
A product obtained by adding 1% by weight of maleic anhydride to 99% by weight of a propylene copolymer, and further adding dil-tert-butyl peroxide, mixing at room temperature, extruding the mixture at 200°C using a single screw extruder, and causing a reaction.

Melt index is 1.5g/10 minutes (250℃
2.2 kg load).

Epoxy group-containing vinyl copolymer (C) nigericidyl methacrylate/acrylonitrile/styrene = 10/
20/TO (weight ratio), melt index is lQg/
10 minutes (measured at 125°C x 2.2 kg load).

Polyarylate, polyamide of the resin composition (A),
The acid anhydride-containing polyolefin copolymer (B) and the epoxy group-containing vinyl copolymer (C) were mixed in the proportions shown in Table 1, vacuum dried at 80°C for 10 hours, and then dried at 270°C. It was pelletized using a twin screw extruder. Test pieces were obtained by injection molding using the obtained pellets, and various measurements were performed. The results obtained are shown in Table 1.

As is clear from Table 1, the resin composition of the present invention has excellent impact resistance, heat deformation resistance, rigidity, and moldability.

Izot impact qa strength (kg-cm/cm): A
STM D-256゜1/8 inch, with non-stop, 23℃ Falling ball strength (br-m): Test piece 3N thickness, half-break height x L weight, measurement temperature -30℃ Flexural modulus (kg/cd) ): ASTM D-79
0.23℃ heat deformation point ('C): ASTM D-
648,4,6kg/-load molding processability = 5 oz injection molding machine, cylinder temperature 280℃, mold temperature 80℃
A box-shaped molded product weighing approximately 100 g was molded at °C, and short shots, coloring, flow marks, warping, silver, and surface uniformity were observed with the naked eye and evaluated using the following evaluation criteria;
O: Almost no defects observed △: Slightly noticeable defects ×: Significant defects [Operations/Effects] As described above, according to the present invention, heat deformation resistance, impact resistance and It is possible to provide a resin composition that not only has well-balanced rigidity and the like but also has excellent moldability.

Claims (1)

[Claims] 1. Polyarylate 20-80% by weight and polyamide 80
1 to 3 of the acid anhydride-containing olefin copolymer (B) to 100 parts by weight of the resin composition (A) consisting of ~20% by weight.
0 parts by weight and epoxy group-containing vinyl copolymer (C) 1~
A thermoplastic resin composition containing 30 parts by weight.