JPH06892B2 - Thermoplastic resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition having excellent impact resistance, heat resistance, processability, and chemical resistance.

<Prior Art> Polyarylene polyether polysulfone has excellent heat resistance and electrical characteristics, and is used for electronic parts such as switch covers, computer housings, electric tool housings, automobile parts such as diaphragms and meter covers. Widely used in food containers such as trays and the like.

On the other hand, since these resins have low mechanical properties, particularly low impact strength, poor processability, and are expensive, they have hitherto been disclosed in JP-B-46-37896, JP-B-49-27668 and JP-A-54-97655. As proposed, polyarylene polyether polysulfone and ABS
A composition comprising a resin is also used in each field.

<Problems to be Solved by the Invention> However, although these compositions show some improvement in impact resistance and workability,
It has inferior chemical resistance, and has a serious drawback that the appearance of the product is changed or cracked when it comes into contact with gasoline, brake oil or the like.

The present inventors have arrived at the present invention as a result of intensive research to improve impact resistance, processability and chemical resistance without sacrificing the excellent heat resistance of polyarylene polyether polysulfone.

That is, it comprises a polyarylene ether polysulfone (A), a styrene-based copolymer (B), and a modified polyolefin (C) consisting of an olefin and one or more other monomers copolymerizable therewith. And a thermoplastic resin composition excellent in impact resistance, heat resistance, processability and chemical resistance.

The present invention will be described in detail below.

○ Polyarylene polyether polysulfone (A) The polyarylene polyether polysulfone (A) used in the present invention is a polymer in which an arylene unit is present together with an ether and a sulfone bond, and, for example, 2,2-bis- ( Those prepared from 4-hydroxyphenyl) propane and 4,4'-dichlorodiphenyl sulfone and 4,4'-dichlorodiphenyl sulfone with bisphenol of benzophenone or bisphenol of acetophenone or bisphenol of vinylcyclohexene or 4,4'- Included are several similar reaction products such as those made with dihydroxydiphenyl sulfone.

The structural formulas include the following. These may be used alone or in combination of two or more.

Those represented by the above structural formulas (1) and (2) are particularly preferable.

Other thermoplastic resin (B) Examples of the other thermoplastic resin (B) in the present invention include polystyrene, rubber-reinforced polystyrene, AS resin, styrene polymers such as ABS resin, and the like, not to mention alone. It also means a mixture of two or more kinds.

In particular, a styrene polymer, which will be described in detail below, or a mixture of the styrene polymer and one or more other thermoplastic resins is preferable.

The styrene-based polymer is a polymer containing an aromatic vinyl compound such as styrene, α-methylstyrene, p-methylstyrene, and chlorostyrene as an essential component, and includes a homopolymer of an aromatic vinyl compound and an aromatic vinyl compound. A copolymer comprising a vinyl compound and another copolymerizable compound, a graft polymer obtained by polymerizing an aromatic vinyl compound alone or in combination with another copolymerizable compound in the presence of a rubbery polymer, and further It also means a mixture of styrene polymers (homopolymers, copolymers, graft polymers).

Other copolymerizable compounds constituting the above-mentioned copolymer or graft polymer, acrylonitrile, unsaturated nitrile compounds such as methacrylonitrile (i), methyl (meth) acrylate, ethyl (meth) acrylate,
Unsaturated carboxylic acid alkyl ester such as butyl (meth) acrylate (ii), unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, citraconic anhydride or unsaturated dicarboxylic acid anhydride (ii
i), maleimide compounds (iv) such as maleimide, methylmaleimide, ethylmaleimide, N-phenylmaleimide, and O-chloro-N-phenylmaleimide.

Specific examples of the copolymer include the following various copolymers. Styrene-acrylonitrile copolymer,
α-methylstyrene-acrylonitrile copolymer, styrene-methylmethacrylate copolymer, α-methylstyrene-acrylonitrile-methylmethacrylate copolymer, styrene-maleic anhydride copolymer, styrene-acrylonitrile-maleic anhydride copolymer Polymer, styrene-maleimide copolymer, styrene-N-phenylmaleimide copolymer, styrene-acrylonitrile-N-phenylmaleimide copolymer.

Further, as the rubbery polymer constituting the graft polymer,
Diene polymers such as polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer
(i), ethylene-propylene copolymers, ethylene-propylene-non-conjugated diene (ethylidene norbornene, dicyclopentadiene, etc.) copolymers and other ethylene-propylene polymers (ii), chlorinated polyethylene (iii), poly Examples thereof include acrylic rubber (iv) typified by butyl acrylate, ethylene-vinyl acetate copolymer (V), and the like.

Specific examples of the graft polymer include the following various graft polymers. Acrylonitrile-diene rubber-styrene polymer, methylmethacrylate-diene rubber-styrene polymer, acrylonitrile-ethylene-propylene rubber-styrene polymer, acrylonitrile-acrylic rubber-styrene polymer, acrylonitrile-chlorinated polyethylene- Styrene polymer, styrene-diene rubber-maleic anhydride polymer.

In the present invention, not only chemical resistance but also from the viewpoint of the balance between processability and impact resistance, particularly as the styrene-based polymer, the above-mentioned graft polymer or graft polymer and other homopolymer or copolymer It is preferably a mixture of

These various styrene-based polymers can be produced by a bulk polymerization method, a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, and a combination thereof.

Modified Polyolefin (C) The modified polyolefin (C) in the present invention is a copolymer of an olefin and one or more other monomers copolymerizable therewith.

Particularly, a ternary copolymer composed of an olefin and an unsaturated dicarboxylic acid anhydride and an unsaturated carboxylic acid alkyl ester, and a binary or ternary copolymer composed of an olefin and glycidyl methacrylate or those and vinyl acetate are preferable.

Further, as the olefin-unsaturated dicarboxylic acid anhydride-unsaturated carboxylic acid alkyl ester terpolymer, olefin 50 to 98.5% by weight, unsaturated dicarboxylic acid anhydride 0.5 to 10% by weight and unsaturated A terpolymer comprising 1 to 40% by weight of a carboxylic acid alkyl ester is preferred.

If the olefin component is less than 50% by weight, the effect of improving the chemical resistance tends to be poor, and if it exceeds 98.5% by weight, the compatibility becomes poor and the impact resistance tends to be lowered or the molded article tends to be delaminated. It is in.

If the unsaturated dicarboxylic acid anhydride component is less than 0.5% by weight, a good dispersed form of the modified polyolefin (terpolymer) cannot be obtained, so that excellent impact resistance cannot be obtained.
If it exceeds 5% by weight, thermal stability and processability tend to be reduced.

Further, when the unsaturated carboxylic acid alkyl ester component is less than 1% by weight, the compatibility between the polyarylene polyether polysulfone (A) and the styrene polymer (B) is poor,
On the other hand, if it exceeds 40% by weight, not only the chemical resistance cannot be sufficiently improved, but also the heat resistance, the rigidity and the like are deteriorated to deteriorate the balance of mechanical properties.

Particularly, from the viewpoint of chemical resistance, impact resistance, processability and heat resistance, olefins of 55 to 96% by weight, unsaturated dicarboxylic acid anhydrides of 1 to 8% by weight and unsaturated carboxylic acid alkyl esters of 3 to 37% by weight are used. A terpolymer is preferred.

As a binary or terpolymer containing olefin and glycidyl methacrylate or vinyl acetate and those, 50 to 98.5% by weight of olefin, 1.5 to 50% by weight of glycidyl methacrylate or glycidyl methacrylate and vinyl acetate. Is. Binary or terpolymers are preferred.

Examples of the olefin include ethylene, propylene, butene-1, and 4-methylpentene-1, and ethylene and propylene are particularly preferable. The unsaturated dicarboxylic acid anhydride, maleic anhydride, citraconic anhydride,
Examples thereof include aconitic anhydride, and maleic anhydride is particularly preferable. Examples of the unsaturated carboxylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate and hydroxymethyl (meth) acrylate, and particularly ethyl acrylate and butyl acrylate. preferable.

The modified polyolefin (C) can be produced by various methods.

For example, an olefin-unsaturated dicarboxylic acid anhydride-unsaturated carboxylic acid alkyl ester terpolymer supplies olefin to the first zone of a cylindrical autoclave equipped with a blade-type stirrer and then to the second zone. , A radical initiator such as t-butyl 2-ethyl-perhexanoate, which is supplied with a monomer mixture of unsaturated dicarboxylic acid anhydride and unsaturated carboxylic acid alkyl ester and is further dissolved in a hydrocarbon fraction in the third zone. Injecting 1000-2000 atm
There is a method of polymerizing under pressure. Also, olefin-glycidyl methacrylate (vinyl acetate copolymer)
Are those compounds in the presence of a radical generator at 50 to
There is a method of contacting at 4000 atm and 40 to 300 ° C.

○ Composition There is no particular limitation on the compounding ratio of the polyarylene polyether polysulfone (A), the styrene-based polymer (B) and the modified polyolefin (C), but there is no limitation on impact resistance, processability, heat resistance and chemical resistance. From the viewpoint of physical property balance, (A) is 10 to 90 parts by weight, (B) is 90 to 10 parts by weight, and 100 parts by weight in total of the polyarylene polyether polysulfone (A) and the styrene polymer (B), and The modified polyolefin (C) is preferably 0.5 to 200 parts by weight per 100 parts by weight of the total of (A) and (B).

The polyarylene polyether polysulfone (A), the styrene polymer (B) and the modified polyolefin (C) can be mixed using a known mixer such as a Banbury mixer, a single-screw extruder or a twin-screw extruder. .

Examples of the mixing method include a batch mixing method in which three components are simultaneously mixed, a two-step mixing method in which any two components are mixed and then the third component is mixed.

At the time of mixing, known additives such as antioxidants, ultraviolet absorbers, antistatic agents, lubricants, dyes and pigments, and reinforcing agents such as glass fibers, metal fibers and carbon fibers can be appropriately added.

Examples will be described below, but the present invention is not limited thereto.

Example After producing the styrene polymers (B-1 to 6) and the modified polyolefins (C-1 to 6) shown below, commercially available polyarylene polyether polysulfone (A) and Table-1 are shown.
Based on the compounding ratios shown in Nos. 2 to 2, they were melt-kneaded in a Banbury mixer to obtain various thermoplastic resin compositions.

Various test pieces were prepared from the obtained composition by an injection molding machine and provided for evaluation.

The test results are shown in Tables 1-2.

-Polyarylene polyether polysulfone (A) -General formula The polymer represented by.

-Styrene-based polymer (B) -B-1: Styrene-acrylonitrile copolymer By a known suspension polymerization method, 71% by weight of styrene, 29% by weight of acrylonitrile, and an intrinsic viscosity (30 ° C, dimethylformamide) of 0.65 A copolymer was obtained.

B-2: Styrene-maleic anhydride copolymer A copolymer having 87% by weight of styrene, 13% by weight of maleic anhydride and an intrinsic viscosity (30 ° C., dimethylformamide) of 0.58 was obtained by a known bulk polymerization method. .

B-3: Styrene-N-phenylmaleimide-acrylonitrile copolymer By a known emulsion polymerization method, 67% by weight of styrene, 10% by weight of N-phenylmaleimide, 23% by weight of acrylonitrile, intrinsic viscosity (30 ° C., dimethylformamide) 0 ．
63 copolymers were obtained.

B-4: acrylonitrile-diene rubber-styrene polymer, weight-average particle diameter 0.43 μm, by a known emulsion polymerization method.
100 parts by weight of polybutadiene rubber latex (solid content 50 parts by weight) having a gel content of 85% by weight, 35 parts by weight of styrene and 15 parts by weight of acrylonitrile were graft-polymerized to obtain a polymer having a rubber content of about 50% by weight.

B-5: Acrylonitrile-ethylene-propylene rubber-styrene polymer 43 parts by weight of propylene, 100 parts by weight of ethylene-propylene-ethylidene norbornene having an iodine value of 13, 100 parts by weight of styrene and 170 parts by weight of acrylonitrile were prepared by a known solution polymerization method. Graft-polymerized to give a rubber content of about 1
5% by weight of polymer was obtained.

B-6: Styrene-diene rubber-maleic anhydride polymer By a known bulk suspension polymerization method, 10% by weight of polybutadiene rubber with 75% by weight of gel, 75% by weight of styrene and 15% by weight of maleic anhydride were graft-polymerized. A polymer having a rubber content of about 10% by weight was obtained.

-Modified Polyolefin (C) -C-1 to 2: Ethylene-maleic anhydride-ethyl acrylate terpolymer Copolymer t-butyl dissolved in hydrocarbon fraction using a cylindrical autoclave equipped with a blade stirrer The monomer mixture was polymerized at 185 ° C. and 1600 atm in the presence of 2-ethylperhexanoate to obtain 60% by weight of ethylene, 4.5% by weight of maleic anhydride and 35.5% by weight of ethyl acrylate.
To obtain 92% by weight of ethylene, 1.5% by weight of maleic anhydride and 6.5% by weight of ethyl acrylate.

C-3: Ethylene-maleic anhydride-butyl acrylate terpolymer In the same manner as in C-1 and C-2, a terpolymer of 70% by weight of ethylene, 4% by weight of maleic anhydride and 26% by weight of butyl acrylate is used. Got united.

C-4 to 5: Ethylene-maleic anhydride-ethyl acrylate terpolymer In the same manner as in C-1 to 2, terpolymer of ethylene 45% by weight, maleic anhydride 5% by weight and ethyl acrylate 50% by weight. Copolymer C-4 and 96% by weight of ethylene, 3.5% by weight of maleic anhydride and 0.5 of ethyl acrylate
Weight% of terpolymer C-5 was obtained.

C-6: Ethylene-glycidyl methacrylate-vinyl acetate terpolymer By the same method as for C-1 and C-2, 80% by weight of ethylene, 10% by weight of glycidyl methacrylate and 10% of vinyl acetate were used.
Weight% of terpolymer C-6 was obtained.

<Effects of the Invention> The composition of the present invention comprising polyarylene polyether polysulfone, other thermoplastic resin and modified polyolefin has excellent impact resistance, heat resistance, processability, and chemical resistance, and therefore, conventional polysulfone or Polysulfone / ABS
It can be used not only in the field in which was used, but also in the field requiring more impact resistance, heat resistance and chemical resistance.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C08L 51/06 LLJ 7142-4J

Claims (4)

[Claims] 1. A polyarylene polyether polysulfone (A), a styrene polymer (B), and a modified polyolefin (C) comprising olefin and one or more other monomers copolymerizable therewith. And the compounding ratio of (A) and (B) is 10 in total of (A) and (B).
(A) 10 to 90 parts by weight, (B) 90 to 0 parts by weight
10 parts by weight, and the mixing ratio of (C) is (A) and (B)
The total amount is 0.5 to 200 parts by weight per 100 parts by weight of the thermoplastic resin composition. 2. The modified polyolefin (C) comprises 50 to 98.5% by weight of olefin and 0.5 of unsaturated dicarboxylic acid anhydride.
The thermoplastic resin composition according to claim 1, which is a terpolymer comprising 10 to 10% by weight and 1 to 40% by weight of an unsaturated carboxylic acid alkyl ester. 3. A ternary copolymer of modified polyolefin (C) comprising 55 to 96% by weight of ethylene and / or propylene, 1 to 8% by weight of maleic anhydride, and 3 to 37% by weight of ethyl acrylate and / or butyl acrylate. The thermoplastic resin composition according to claim 1, which is a united body. 4. The modified polyolefin (C) is a binary or ternary copolymer composed of olefin and glycidyl methacrylate or those and vinyl acetate.
The thermoplastic resin composition according to item.