JPH0357941B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a rubber-reinforced thermoplastic resin composition that has excellent impact resistance, processability, and heat resistance. Rubber-reinforced thermoplastic resins, such as ABS resin, MBS resin, and AES resin, have excellent performance such as impact resistance and processability, and are used in a wide range of fields such as light electrical appliances, vehicles, and miscellaneous goods. However, as the field of use expands, materials with better impact resistance, processability, and heat resistance are desired. For this reason, increasing the rubber content in rubber-reinforced thermoplastic resins, introducing other compounds (copolymerization) such as α-methylstyrene and maleic anhydride, and adding other polymers such as polycarbonate and saturated polyester, etc. However, impact resistance and processability are inherently contradictory properties, and it is extremely difficult to improve both. Nothing is satisfying. In view of this situation, the present inventors conducted extensive research into improving rubber-reinforced thermoplastic resins, and found that by blending a small amount of saturated polyester resin and polyolefin-modified resin into rubber-reinforced thermoplastic resins, the heat resistance was reduced. The present invention was achieved by discovering that both impact resistance and processability can be improved without the above-mentioned problems. The rubber-reinforced thermoplastic resin in the present invention is a rubber selected from diene rubber or ethylene-propylene rubber, and an aromatic vinyl compound, a vinyl cyanide compound, and other copolymerizable vinyl compounds. It is a mixture of a graft polymer obtained by graft polymerization of two or more kinds of compounds, or a copolymer obtained by copolymerizing such a graft polymer and two or more kinds of compounds selected from the above-mentioned compound group. The diene rubber used in the present invention includes:
Examples of the ethylene-propylene rubber include polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, and ethylene-propylene copolymer, ethylene-propylene-nonconjugated diene copolymer, etc. , one type or two or more types can be used. Examples of aromatic vinyl compounds include styrene, α-
Examples include methylstyrene, vinyltoluene, etc.
One type or two or more types can be used. Examples of vinyl cyanide compounds include acrylonitrile, methacrylonitrile, etc., and one or more types can be used. Other copolymerizable vinyl compounds include acrylic acid, maleic acid, fumaric acid, maleic anhydride, maleic imide, (meth)
Methyl acrylate, ethyl (meth)acrylate,
Examples include butyl (meth)acrylate, and one or more types can be used. Particularly preferred are (meth)acrylic acid esters. The rubber content in the rubber-reinforced thermoplastic resin is not particularly limited either, but it is preferably 5 to 40% by weight (per 100% by weight of the rubber-reinforced thermoplastic resin).
Furthermore, there is no particular restriction on the composition ratio of each compound, but 20 to 80% by weight of aromatic vinyl compounds and 20 to 80% by weight of vinyl cyanide compounds and/or other vinyl compounds.
Preferably it is 80% by weight (based on 100% by weight of all compounds), more preferably 50-80% by weight of aromatic vinyl compounds and 20-50% by weight of vinyl cyanide compounds and/or other vinyl compounds. Manufacturing methods for rubber-reinforced thermoplastic resins (graft polymers and copolymers) include emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization, emulsion-suspension polymerization, and bulk-suspension polymerization. etc. Examples of saturated polyester resins include polyethylene terephthalate, polytetramethylene terephthalate, polybutylene terephthalate, and polyester-ether block polymers having a polyester hard segment and a polyether soft segment. Synthesized from dimethyl acid and ethylene glycol. Among these, one or more types can be used as the saturated polyester resin. Although there is no particular restriction on the molecular weight of the saturated polyester resin, it is preferable that the intrinsic viscosity is 0.4 to 1.6 dl/g. Furthermore, polyolefin-modified resins include copolymers of olefins and unsaturated carboxylic acids or derivatives thereof, copolymers of olefins and unsaturated epoxy compounds, and polyolefins containing unsaturated carboxylic acids or derivatives thereof or unsaturated epoxy compounds. Grafted polymers and some of their olefins replaced with other ethylenically unsaturated compounds (co-)
It is a resin mainly composed of olefin selected from the group consisting of polymers. Among these, polyolefin-modified resins using unsaturated epoxy compounds are particularly preferred. The molecular weight of the polyolefin-modified resin is not particularly limited, but it is preferably melt flow index "MFR" (JIS K6760, 190°C) 1 to 100 g/10 minutes. Olefins include ethylene, propylene,
Examples include butene-1,4 methylbentene-1, and one or more types can be used. Particularly preferred are ethylene and propylene. Examples of unsaturated carboxylic acids or derivatives thereof include monocarboxylic acids such as acrylic acid and methacrylic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride; ) Carboxylic acid alkyl esters such as methyl acrylate and ethyl (meth)acrylate, etc., and one type or two or more types can be used. The unsaturated epoxy compound is a compound having an unsaturated group copolymerizable with olefin and an epoxy group in the molecule. For example, the following general formulas (), () and ()
These are unsaturated epoxy compounds such as unsaturated glycidyl esters, unsaturated glycidyl ethers, epoxy alkenes, and P-glycidyl styrenes. (R ₁ is a C ₂ to 18 hydrocarbon group having an ethylenically unsaturated bond.) (R ₂ is a C ₂ to 18 hydrocarbon group having an ethylenically unsaturated bond. X is CH ₂ -O-,

[expression] or

[Formula]. ) (R ₃ is a C ₂ to 18 hydrocarbon group having an ethylenically unsaturated bond. _{R 4} is hydrogen or a methyl group.) Specifically, glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl esters, butene Carboxylic acid esters, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-P-glycidyl ether,
3,4-epoxybutene, 3,4-epoxy-3
-Methyl-1-butene, 3,4-epoxy-1-
Examples include pentene, 3,4-epoxy-3-methylpentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide, and P-glycidylstyrene, and one type or two or more types can be used. In addition, as ethylenically unsaturated compounds, olefins, vinyl esters containing C _{2 to 6} in the saturated carboxylic acid component, acrylic and methacrylic esters and maleic esters containing C _{1 to 8} in the saturated alcohol component , vinyl halides, vinyl ethers, N-vinyl lactams, carboxylic acid amides, etc., and one type or two or more types can be used. The resin composition of the present invention contains 80 to 99% by weight of the above-mentioned rubber-reinforced thermoplastic resin and 0.5% by weight of the saturated polyester resin.
~19.5% by weight and 0.5% polyolefin modified resin
Consisting of ~19.5% by weight. Outside this range, it is not possible to improve both impact resistance and processability without reducing heat resistance. Furthermore, there are no restrictions on the method and order of mixing these, and any known mixer can be used. Also, when mixing, known dyes and pigments, stabilizers,
It is also possible to add plasticizers, antistatic agents, ultraviolet absorbers, lubricants, fillers, etc. EXAMPLES The present invention will be specifically explained below using Examples, but the present invention is not limited thereto. Examples and Comparative Examples Based on the compounding ratios shown in Table 1, rubber-reinforced thermoplastic resin, saturated polyester resin, and polyolefin-modified resin, or polyethylene, and chlorinated polyethylene were melt-kneaded at once to form compositions (sample numbers 1 to 1).
23) was obtained. The impact resistance, processability and heat resistance of the obtained composition are shown in Table 2. The resins used are as follows. (1) Rubber-reinforced thermoplastic resin (1-A) 30% by weight of a graft polymer consisting of 50 parts by weight of polybutadiene, 35 parts by weight of styrene and 15 parts by weight of acrylonitrile, and 70 parts by weight of α-methylstyrene and 30 parts by weight of acrylonitrile. A mixture consisting of 70% by weight of copolymer. “Heat-resistant ABS resin” (1-B) 40% by weight of a graft polymer consisting of 50 parts by weight of ethylene-propylene-ethylidene norbornene, 35 parts by weight of styrene and 15 parts by weight of acrylonitrile, 70 parts by weight of α-methylstyrene and 30 parts by weight of acrylonitrile. A mixture consisting of 60% by weight of a copolymer consisting of: “Heat resistant
AES resin (1-C) 25 parts by weight of polybutane diene, 55 parts by weight of styrene
A graft polymer consisting of parts by weight and 20 parts by weight of acrylonitrile. “ABS resin” (1-D) 25% by weight of a graft polymer consisting of 40 parts by weight of polybutadiene, 20 parts by weight of styrene, 25 parts by weight of methyl methacrylate and 15 parts by weight of acrylonitrile, and a copolymer consisting of 70 parts by weight of styrene and 30 parts by weight of acrylonitrile. polymer 75
A mixture consisting of % by weight. “ABSM resin” (1-E) A graft polymer consisting of 15 parts by weight of polybutadiene, 70 parts by weight of methyl methacrylate and 15 parts by weight of styrene. “MBS resin” (2) Saturated polyester resin (2-A) Polyethylene terephthalate “PET”
(Intrinsic viscosity 0.85dl/g) (2-B) Pributylene terephthalate “PBT”
(Intrinsic viscosity: 1.15 dl/g) (3) Polyolefin modified resin (3-A) A copolymer (MFR40) consisting of 90 parts by weight of ethylene and 10 parts by weight of ethyl acrylate. "E-EA" (3-B) A copolymer (MFR3) consisting of 90 parts by weight of ethylene and 10 parts by weight of glycidyl methacrylate.
"E-GMA" (3-C) A copolymer (MFR7) consisting of 80 parts by weight of ethylene, 10 parts by weight of glycidyl methacrylate and 10 parts by weight of vinyl acetate. “E-GMA-
VA” (3-D) Modified polyethylene (PFR3) made by grafting maleic anhydride (5 parts by weight) onto polyethylene (95 parts by weight). “E-MAH” (4) Polyethylene (MFR50) (5) Contains chlorine Chlorinated polyethylene (MFR3) with an amount of 35% by weight

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Claims (1)

[Claims] 1 Rubber selected from diene rubber or ethylene-propylene rubber, aromatic vinyl compound,
A graft polymer obtained by graft polymerizing two or more compounds selected from the group consisting of vinyl cyanide compounds and other copolymerizable vinyl compounds, or such a graft polymer and two types selected from the above-mentioned compound group. 80-99% by weight of a rubber-reinforced thermoplastic resin made of a copolymer of the above compounds;
0.5 to 19.5% by weight of saturated polyester resin and copolymer of olefin and unsaturated carboxylic acid or its derivative, copolymer of olefin and unsaturated epoxy compound, polyolefin and unsaturated carboxylic acid or its derivative, or unsaturated epoxy compound Polyolefin-modified resins mainly composed of olefins selected from the group consisting of polymers grafted with olefins and (co)polymers in which a portion of these olefins is substituted with other ethylenically unsaturated compounds 0.5 to 19.5
% by weight of a rubber-reinforced thermoplastic resin composition.