JPH0116269B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel thermoplastic resin composition that has excellent impact resistance, weather resistance, processability, and weld strength. Polycarbonate resin (hereinafter referred to as PC) is widely known as an engineering plastic having excellent impact resistance and heat resistance. In addition, we have developed a mixture of PC and ABS resin (acrylonitrile-diene rubber-styrene polymer) that reduces the price of PC and improves the thickness dependence of moldability and impact strength. A mixture of PC with improved properties and AES resin (acrylonitrile-ethylene/propylene rubber-styrene polymer) (Japanese Unexamined Patent Publication No. 48-48547) is also widely known. However, PC-AES resin compositions tend to cause flow marks and delamination on the surface of molded products.
In addition, in injection molding, which is the most common molding method, it is necessary to change the number of gates and the flow state of the resin depending on the shape and size of the molded product, so there are always places where resin flowing in different directions intersects. , a so-called "weld part" occurs, but in conventional compositions, the strength of the weld part, "weld strength"
Currently, it is difficult to say that it is a material that is practically excellent, as it is insufficient in terms of practical moldability. As a result of intensive research into improving the weld strength of such resin compositions made of polycarbonate resin and AES resin, the present inventors have found that an olefin copolymer containing an epoxy group is blended into a composition made of polycarbonate resin and AES resin. It was discovered that by doing so, a composition having excellent weld strength as well as impact resistance, weather resistance, heat resistance, and processability can be obtained, and the present invention was achieved based on this finding. That is, the present invention provides polycarbonate resin (A)
Provided is a thermoplastic resin composition characterized in that an epoxy group-containing olefin copolymer (C) is blended into a resin composition consisting of 10 to 90% by weight of AES resin (B) and 90 to 10% by weight of AES resin (B). It is. The thermoplastic resin composition of the present invention will be explained in detail below. Examples of the polycarbonate resin (A) include aromatic polycarbonate, aliphatic polycarbonate, aliphatic-aromatic polycarbonate, and the like. Generally, it is a polymer or copolymer consisting of bisphenols such as 2.2-bis(4-oxyphenyl)alkanes, bis(4-oxyphenyl)ethers, bis(4-oxyphenyl)sulfones, sulfides, or sulfoxides. It is a polymer using bisphenols substituted with halogen depending on the purpose. Furthermore, AES resin (B) will be explained. AES
The resin is a graft polymer consisting of an ethylene-propylene rubbery copolymer and one or more compounds each selected from at least two groups of aromatic vinyl compounds, vinyl cyanide compounds, and other polymerizable monomer compounds. (b-1) A copolymer (b- 2) It is a resin consisting of 0 to 90% by weight. The ethylene-propylene rubbery copolymer constituting the graft polymer (b-1) is a binary copolymer (EPR) consisting of ethylene and propylene, or a ternary copolymer consisting of ethylene, propylene, and a non-conjugated diene. (EPDM), etc., and one or more types are used. Examples of the non-conjugated diene in the terpolymer (EPDM) include dicyclopentadiene, ethylidene norbornene, 1.4-hexadiene, 1.4-cycloheptadiene, and 1.5-cyclooctadiene. The molar ratio of ethylene to propylene in the binary copolymer (EPR) and terpolymer (EPDM) is preferably in the range of 5:1 to 1:3. Further, in the terpolymer (EPDM), it is preferable that the proportion of non-conjugated diene is in the range of 2 to 50 in terms of iodine value. Graft polymer (b-1) and copolymer (b
-2) The aromatic vinyl compound constituting
Examples include styrene, α-methylstyrene, α-chlorostyrene, vinyltoluene, etc., and one or more types can be used. In particular, styrene is preferably used. Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile, and one or more types can be used. Acrylonitrile is particularly preferably used. Furthermore, other polymerizable monomer compounds include methyl, ethyl,
Examples include acrylic ester compounds and methacrylic ester compounds such as propyl, butyl, benzyl, and hexyl, and one or more types can be used. In particular, methyl methacrylate is preferably used. One or more compounds selected from at least two groups of the above-mentioned aromatic vinyl compounds, vinyl cyanide compounds, and other polymerizable monomer compounds are used. The weight ratio of these compounds and the rubbery copolymer in the graft polymer (b-1) can be selected within an appropriate range depending on the purpose. normal compound
90 to 30% by weight and 10 to 70% by weight of the rubbery copolymer are preferably used. All known methods can be used to produce the graft polymer (b-1) by polymerizing a compound in the presence of a rubbery copolymer. Examples include suspension polymerization, bulk polymerization, emulsion polymerization, and solution polymerization. AES resin (B) is graft polymer (b-1) 100~
10% by weight and copolymer (b-2) 0-90% by weight
It becomes more. If the content of the copolymer (b-2) exceeds 90% by weight, that is, if the content of the graft polymer (b-1) is less than 10% by weight, sufficient impact resistance cannot be obtained. The composition ratio of polycarbonate (A) and AES resin (B) is 10 to 90% by weight of polycarbonate and AES resin.
It is 90-10% by weight. If the amount of polycarbonate (A) is less than 10% by weight, the heat resistance will drop significantly, which is undesirable.
Moreover, if it exceeds 90% by weight, workability will decrease and weld strength will not be improved. Preferably it is 30 to 70% by weight of polycarbonate (A). The epoxy group-containing olefin copolymer (C) is a copolymer consisting of an unsaturated epoxy compound and an olefin, or these and an ethylenically unsaturated compound. There is no particular restriction on the composition ratio of the epoxy group-containing olefin copolymer (C), but unsaturated epoxy compounds
It is preferably 0.05 to 95% by weight. The unsaturated epoxy compound is a compound having an epoxy group and an unsaturated group copolymerizable with an olefin and an ethylenically unsaturated compound 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 is a _C2-18 hydrocarbon group having an ethylenically unsaturated bond.) (R is a _C2-18 hydrocarbon group having an ethylenically unsaturated bond. X is _-CH2 -O-,

[expression] or

[Formula]. ) (R is a _C2-18 hydrocarbon group having an ethylenically unsaturated bond. R' is hydrogen or a methyl group.) Specifically, glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl esters, butene carboxyl 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 or more of them can be used. Examples of the olefin include ethylene, propylene, butene-1, 4-methylpentene-1, etc., and one or more types can be used. Examples of ethylenically unsaturated compounds include 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, Examples include vinyl halides, vinyl ethers, N-vinyl lactams, and carboxylic acid amides, and one or more types can be used. When copolymerizing an unsaturated epoxy compound and an olefin, these ethylenically unsaturated compounds are added in an amount of 50% by weight or less, especially 0.1 to 45% by weight based on the total compound.
Copolymerized. The epoxy group-containing olefin copolymer (C) can be produced by various methods. For example, an unsaturated epoxy compound and an olefin, in some cases an ethylenically unsaturated compound, are combined in the presence of a radical generator for 50 to
Examples include a method of contacting at 4000 atm and 40 to 300°C, and a method of preparing a polymer by mixing an unsaturated epoxy compound with polypropylene and irradiating it with gamma rays under high vacuum. There is no particular restriction on the amount of the epoxy group-containing olefin copolymer (C), but polycarbonate resin (A)
It is particularly preferable that the amount is 0.1 to 40 parts by weight per 100 parts by weight of the AES resin (B) and AES resin (B). If it is less than 0.1 part by weight, there is a problem with dispersibility, and if it exceeds 40 parts by weight, there is a tendency for layer peeling to occur in the molded product. There is no restriction on the mixing order of the polycarbonate resin, AES resin, and epoxy group-containing olefin copolymer; only two of these three components may be mixed in advance, and then the remaining one component may be added and mixed; The three components may be mixed all at once. In addition, known additives such as stabilizers, antistatic agents, lubricants, dyes and pigments may be appropriately blended during mixing. Examples will be described below, but the present invention is not limited thereto. Examples and Comparative Examples Polycarbonate resin, AES resin, and epoxy group-containing olefin copolymer were mixed at once based on the blending ratio shown in Table 1 to obtain various compositions (sample numbers 1 to 12). Table 2 shows the physical properties of the obtained composition. The AES resin and epoxy group-containing olefin copolymer used in the present examples and comparative examples were obtained by the following formulation. Note that the polycarbonate resin and polyethylene resin are commercially available. Γ Polycarbonate resin (A) “Panlite L-1250W” manufactured by Teijin Chemicals Γ AES resin (B) Graft polymer (b-1) Iodine value 8.5, Mooney viscosity 61, propylene content 43% by weight, ethylidene norbornene as diene component 550 parts by weight of EPDM containing 3000 parts by weight of n-hexane and 1500 parts by weight of ethylene dichloride were dissolved in 300 parts by weight of styrene, 150 parts by weight of acrylonitrile and 11 parts by weight of benzoyl peroxide.
Parts by weight were added and polymerized at 65°C for 10 hours in a nitrogen atmosphere. The polymerization solution was brought into contact with a large excess of methanol, and the precipitate precipitated was separated and dried to obtain a graft polymer (rubber content approximately 54%). Copolymer (b-2) 70% by weight of styrene and 30% by weight of acrylonitrile
0.1 part by weight of t-dodecyl mercaptan was added to 100 parts by weight of a mixed solution of 2% by weight, prepolymerized in bulk at 90°C for 3 hours, and then 210 parts by weight of water,
Add 1.0 parts by weight of methylcellulose and 0.3 parts by weight of benzoyl peroxide and mix in an aqueous dispersion system from 30°C to 90°C.
The temperature was increased to 100 mL and the polymerization was continued for 10 hours. After dehydration, a copolymer (intrinsic viscosity 0.50) was obtained. Γ Epoxy group-containing olefin copolymer (C) Typical autoclave type polyethylene production equipment: Ethylene monomer compressed to 2000 kg/cm ² and glycidyl methacrylate, or these and vinyl vinegar residue together with a catalyst (di-t-butyl peroxide). The copolymer (C) was added and maintained at 150 to 300°C with stirring for several minutes to undergo bulk polymerization, and the copolymer (C) was separated through a separator and taken out. Γ Polyethylene "Sumikasen Hard 2703" manufactured by Sumitomo Chemical Co., Ltd. - Weld strength - Two gates with a gate spacing of 100 mm (each 2.5 x 2.0
Inject molten resin (260℃) from 3mm thick
Create a test piece of 150mm in length and width. Place the test piece in a jig (height 80 mm, inner diameter 120 mm, outer diameter 126
mm). A 1Kg steel ball is dropped onto the center of the test piece in a cold room adjusted to -30℃, and the maximum energy value (Kg cm) that does not destroy the test piece is determined.

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Claims (1)

[Scope of Claims] 1. 10 to 90% by weight of polycarbonate resin (A), at least an ethylene-propylene rubbery copolymer, an aromatic vinyl compound, a vinyl cyanide compound, and other polymerizable monomer compounds. 100 to 10% by weight of a graft polymer (b-1) consisting of one or more compounds selected from two groups, and at least two groups of aromatic vinyl compounds, vinyl cyanide compounds, and other polymerizable monomer compounds. A copolymer consisting of one or more selected compounds (b
-2) AES resin (B) consisting of 0 to 90% by weight 90 to 10
1. A thermoplastic resin composition characterized in that an epoxy group-containing olefin copolymer (C) is blended into a resin composition of % by weight. 2. The composition according to claim 1, which contains 0.1 to 40 parts by weight of the epoxy group-containing olefin copolymer (C) per 100 parts by weight of the resin composition. 3. The composition according to claim 1, wherein the epoxy group-containing olefin copolymer (C) is a copolymer consisting of an epoxy group-containing compound and an olefin. 4. The composition according to claim 1, wherein the epoxy group-containing olefin copolymer (C) is a copolymer consisting of an epoxy group-containing compound, an olefin, and an ethylenically unsaturated monomer. 5. The composition according to claim 4 or 5, wherein the olefin is one or more compounds selected from ethylene and α-olefin. 6. The composition according to claim 6, wherein the α-olefin is propylene.