JPH02169664A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To prepare a thermoplastic resin compsn. excellent in the resistances to heat distortion, impact and chemicals and processability by compounding a resin compsn. comprising a polyarylate and a polyamide with a copolymer obtd. by graft copolymerizing a specific compd. onto a rubberlike elastomer. CONSTITUTION:100 pts.wt. resin compsn. comprising 20-80wt.% polyarylate and 80-20wt.% polyamide is compounded with 1-40 pts.wt. graft copolymer obtd. by graft copolymerizing 70-5wt.% at least one monomer selected from the group consisting of vinyl monomer, unsatd. glycidyl compd., alpha,beta-unsatd. dicarboxylic anhydride, and alpha,beta-unsatd. carboxylic acid onto a 30-95wt.% rubberlike elastomer. The resulting resin composition has a good balance among the heat distortion resistance, impact resistance, stiffness, etc., and has 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 chemical resistance, and also has excellent moldability. be. More specifically, the present invention relates to a thermoplastic resin composition comprising a copolymer obtained by graft copolymerizing a polyamide, a rubber-like elastomer, and a specific compound with a polyarylate.

[Conventional technology]

Resin compositions made of polyarylate and polyamide have been known for a long time and are excellent in heat deformation resistance, chemical resistance, etc., but are not satisfactory in terms of impact resistance. Various attempts to overcome these drawbacks have been proposed in the past. For example, JP-A-62-283146 proposes a method of adding a mixture of an epoxy group-containing ethylene copolymer and an acid anhydride-containing ethylene copolymer. However, with this method, the compatibility between the additive and the polyarylate or polyamide is not sufficient, so the particle size of the additive may vary depending on the crosstalk conditions, or agglomeration may occur, resulting in poor impact resistance. physical properties are unstable,
This is not a preferable method as it may cause defects on the surface of the molded product.

[Problem that the invention seeks to solve]

The object of the present invention is to maintain the excellent heat deformation resistance, chemical resistance, etc. of a resin composition made of polyarylate and polyamide, improve impact resistance, and reduce variation. That is, the present invention provides a molding material that has excellent heat deformation resistance, impact resistance, and chemical resistance, as well as excellent moldability.

[Means for solving problems]

As a result of intensive studies to achieve this object, the present inventors found that the above-mentioned composition was made from a copolymer obtained by graft copolymerizing polyarylate, polyamide, and a specific monomer in the presence of a rubber-like elastic body. The inventors have found that the object can be achieved and have completed the present invention.

That is, the present invention provides a resin composition (A) 1 consisting of Boryaryl [20 to 80% by weight and 80 to 20% by weight of polyamide].
00 parts by weight, a vinyl compound, an unsaturated glycidyl compound, α, β in the presence of 30 to 95% by weight of a rubber-like elastic material.
- At least one type of jlt form selected from unsaturated dicarboxylic anhydrides and α,β-unsaturated carboxylic acids from 70 to
Graft copolymer (13) copolymerized with 5 weight percent weight
The thermoplastic resin composition contains 1 to 40 parts by weight of .

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

The polyarylate used in the present invention contains at least one selected from terephthalic acid, isophthalic acid, or functional derivatives thereof, and a general group (-X-: O, S).
, S(h, C.

One selected from the group consisting of an alkylene group or an alkylidene group, RlR,, Ri, Ra, R'+, R't, R
'3゜Ro: hydrogen atom, halogen atom is one selected from the group consisting of hydrocarbons).

The bisphenols represented by the above general formula include 4.
4'-dihydroxy diphenyl ether, bis(4-
hydroxyphenyl)-sulfide, bis(4-hydroxyphenyl)-sulfone, bis(4-hydroxyphenyl)-ketone, bis(4-hydroxyphenyl)-
Methane, bis(4-hydroxy-3,5-dimethyl)-
Methane, 1,1-bis(4-hydroxyphenyl)-phenylethane, bis(4-hydroxyphenyl)-diphenylmethane, bis(4-hydroxy-3°5-difluorophenyl)-methane, 2,2-bis(4 -Hydroxy-3,5-dichlorophenyl)-propane, bis(4
-hydroxyphenyl)-cyclohexylmethane, 1,
Examples include 1-bis(4-hydroxyphenyl)-cyclohexane, 2.2-bis(4-hydroxynaphthyl)-propane, and 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, etc. 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 solution viscosity is an intrinsic viscosity of 0.2 to 1.5 (chloroform solution, 30°C
) is preferable. Those outside this range are not preferred in terms of impact resistance, heat deformation resistance, moldability, etc.

The polyamide used in the present invention has the general formula (Its,
R-Rt? The polyamide used in the present invention includes those produced by the condensation reaction of a diamine and a dibasic acid, the self-condensation reaction of an amino acid, and the polymerization reaction of a lactam.

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

The graft copolymer (B) used in the present invention is obtained by graft polymerizing a specific monomer in the presence of a rubbery elastic material.

The rubber-like elastic body preferably has a glass transition temperature (Tg) of 0°C or lower, more preferably -40°C or lower. Specifically, diene rubbers such as polybutadiene, butadiene-styrene copolymer, styrene-butadiene-styrene triblock copolymer, butadiene-butyl acrylate, and acrylic rubbers such as butyl polyacrylate and 2-ethylhexyl polyacrylate are used. Examples include rubber, olefin rubber such as ethylene-propylene copolymer, and ethylene-propylene-diene copolymer. The gel content of the rubber-like elastic body is not particularly limited, but it is preferably 10 times larger.The shape is not particularly limited, such as powder pellets, crumbs, or latex, but the average particle size of the latex-like material is 0.305 mm. ~2.0 microns are preferred.

The monomer to be graft copolymerized is at least one selected from vinyl compounds, unsaturated glycidyl compounds, α,β-unsaturated dicarboxylic acid anhydrides, and α,β-unsaturated carboxylic acids.

Examples of vinyl compounds include styrene, methylstyrene,
Aromatic vinyl compounds such as α-methylstyrene, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-(meth)acrylate Examples include (meth)acrylic acid ester compounds such as ethylhexyl.

Examples of the α,β-unsaturated dicarboxylic acid anhydride include maleic anhydride, methylmaleic anhydride, chloromaleic anhydride,
Examples include citraconic anhydride.

Examples of α,β-unsaturated carboxylic acids include acrylic acid and methacrylic acid.

Examples of unsaturated glycidyl compounds include glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl ester, styrene carboxylic acid glycidyl ester,
Examples include 3.4-epoxy-1-butene.

The composition ratio of the specific monomers used in the present invention is not particularly limited, but includes 50-100% by weight of vinyl compound, 0-50% by weight of α,β-unsaturated dicarboxylic acid anhydride,
0 to 50% by weight of α-β-unsaturated carboxylic acid and O to 50% by weight of unsaturated glycidyl compound are preferable, and the composition ratio in the vinyl compound is not particularly limited, but aromatic vinyl compound 20% by weight is preferable. ~90% by weight, vinyl cyanide compound 0~40% by weight, and (meth)acrylic acid ester compound θ~80~11% are preferable.

The composition ratio of the rubbery elastic body and the specific monomer is preferably in the range of 30 to 95% by weight of the rubbery elastic body and 70 to 5% by weight of the specific compound. Outside this range, impact resistance, rigidity, etc. There are particular restrictions on the production method of graft copolymers obtained by graft polymerizing a specific monomer in the presence of a rubber-like elastic material, which is undesirable as it may cause deterioration or defects on the surface of the molded product. Instead, methods such as solution polymerization, suspension polymerization, bulk polymerization, and emulsion polymerization can be employed.

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. The amount of the graft copolymer (B) added to the resin composition (A) is 1 to 40 parts by weight, more preferably 5 to 30 parts by weight, based on 100 parts by weight of the resin composition (A). It is. Composition ratio of polyarylate and polyamide of resin composition (A),
If the amount of the graft copolymer (B) added is outside the above range, heat deformation resistance, impact resistance, moldability, chemical resistance, etc. may decrease, and the surface properties of the molded product may decrease. I don't like it.

The thermoplastic resin composition of the present invention obtained as described above may further contain 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 in various ways.For example, polyarylate, polyamide and graft copolymer may be mixed simultaneously and pelletized, or all of polyarylate or polyamide and graft copolymer may be mixed together and pelletized. Alternatively, a part may be mixed first and pelletized, and then the remaining part may be mixed and pelletized.

(Examples) 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.

Example 1-11 and Comparative Examples 1-7 Resin composition (A): Polyarylate: manufactured from a mixture of 2,2-bis(4-hydroxyphenyl)propane and terephcuric acid/isophthalic acid-3/7 , with an intrinsic viscosity of 0.6.

Polyamide; "Amilan CM1026 (polycaprolactam)" manufactured by Toshi ■ Graft copolymer (A) The following B-1-B-7 were used; S-t: average particle size 0.25 microns, gel content 83
% polybutadiene (latex type) 70% by weight
(solid content), a mixture of 15% by weight of styrene and 15% by weight of methyl methacrylate was graft copolymerized by emulsion polymerization, salted out with calcium chloride, washed with water, dehydrated, and dried.

F3-2 Same as B-1, 10% by weight (solid content) of polybutadiene, 4% by weight of glycidyl methacrylate, 8% by weight of acrylonitrile, and 18% by weight of styrene were graft copolymerized by emulsion polymerization, and then chlorinated. Salted out with magnesium, washed with water, dehydrated, and dried.

B-3: Average particle size 0.29 microns, gel content 86
Weight% polybutyl acrylate (in latex form)
65% by weight, 2% by weight of maleic anhydride, 14% by weight of styrene.
A mixture consisting of 3% by weight of acrylonitrile and 16% by weight of methyl methacrylate was graft copolymerized by emulsion polymerization, salted out with calcium chloride, washed with water, dehydrated, and dried.

B-4 = average particle size O, 36:: Chron, gel content 5
0% by weight of ethylene-propylene-diene copolymer (latex) 60% by weight, 4% by weight of methacrylic acid, 21% by weight of styrene, 5% by weight of acrylonitrile.
A mixture consisting of 10% by weight of butyl acrylate was graft copolymerized by emulsion polymerization, and salted out with calcium chloride,
Washed, dehydrated, and dried.

B-5! It was produced in the same manner as B-1 using the same polybutadiene as B-1. However, it is obtained by graft copolymerizing 99% by weight of polybutadiene with 1% by weight of methyl methacrylate.

B-6: Produced in the same manner as B-1 using the same polybutadiene as B-1. However, polybutadiene 10% by weight,
A product obtained by graft copolymerization of a mixture of 85% by weight of styrene and 5% by weight of acrylonitrile.

B-7 = Ethylene-propylene copolymer (EPR) with an average molecular weight of 100,000 and an ethylene content of 1173% by weight.

Polyarylate, polyamide of the resin composition (A),
The graft copolymer (B) and EPR were mixed in the proportions shown in Table 1, vacuum dried at 80°C for 10 hours, and pelletized using a two-wheel extruder at 270°C. 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 physical properties such as impact resistance, heat deformation resistance, and rigidity, and is also excellent in moldability.

Isotto? li"!" strength (klF-cm/cm)
: ASTM D-256° 1/8 inch, with notch, 23°C Falling ball strength [pupil/m]: Test piece 3 thickness, measurement temperature -30
°C, half-height at failure x ball weight tensile strength (lur/m): ASTM D-638,
23℃ heat deformation temperature (t): ASTM D-64
13,4,6kg/el17W Heavy molding processability: Cylinder temperature 280℃, mold temperature 8 with 5oz injection molding machine
Approximately 100 g of box-shaped molded products were molded at 0° C., and coloring, flow marks, warpage, silver, SHOTRA 9 No. 1, and surface uniformity were observed with the naked eye, and J17 evaluation was performed according to 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, 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. 20 to 80% by weight of polyarylate and polyamide 80
A vinyl compound, an unsaturated glycidyl compound, an α,β-unsaturated dicarboxylic acid anhydride and A thermoplastic resin composition containing 1 to 40 parts by weight of a graft copolymer (B) obtained by graft copolymerizing 70 to 5% by weight of at least one monomer selected from α,β-unsaturated carboxylic acids. thing. 2. The monomers to be graft copolymerized in the presence of the rubbery elastomer include 50 to 100% by weight of vinyl compounds, 0 to 50% by weight of unsaturated glycidyl compounds, and 0 to 10% of α,β-unsaturated dicarboxylic acid anhydrides. 50% by weight and 0 α,β unsaturated carboxylic acids
The resin composition according to claim 1, comprising 50% by weight.