JPH0142301B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel thermoplastic resin composition that has excellent impact resistance, heat resistance, moldability, and particularly low-temperature weld strength. Traditionally, efforts have been made to improve the moldability of polycarbonate resin by adding rubber-reinforced thermoplastic resins such as ABS resin to polycarbonate resin, and to reduce the thickness dependence of impact strength. 15225, 39-71, 42-11496, 51-
11142, etc., and all of the compositions have improved apparent moldability, for example, the flow rate in Koka type flow. However, 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 points where resin flowing in different directions intersects. , a so-called "weld part" is formed, but in conventional compositions, the strength of this weld part ("weld strength") is not sufficient. In particular, the weld strength at low temperatures is low, and at present it is difficult to say that it is a practically excellent material. As a result of intensive research into improving the weld strength of such compositions made of polycarbonate resin and rubber-reinforced resin, the present inventors have discovered that it is possible to blend a specific copolymer into a composition of polycarbonate resin and rubber-reinforced resin. The inventors have discovered that this method significantly improves weld strength in addition to impact resistance, heat resistance, and moldability, and has thus arrived at the present invention. That is, the present invention provides polycarbonate resin A
The composition is made by blending an olefin-unsaturated carboxylic acid alkyl ester copolymer C into a composition consisting of a rubber-reinforced thermoplastic resin B, and has excellent impact resistance, heat resistance, and moldability, as well as low-temperature weld strength. The present invention provides a thermoplastic resin composition with excellent properties. 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 2,2-bis(4-oxyphenyl)
A polymer or copolymer consisting of bisphenols such as alkanes, bis(4-oxyphenyl) ethers, bis(4-oxyphenyl)sulfones, sulfides, or sulfoxides, and is substituted with halogen depending on the purpose. It is a polymer using bisphenols. One or more types of these can be used. Rubber reinforced thermoplastic resin B means that in the presence of rubber,
This resin is obtained by graft polymerization of one or more compounds selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, and unsaturated carboxylic acid alkyl ester compounds. In addition, such resin is
It may contain a (co)polymer produced during graft polymerization or a separately produced (co)polymer consisting of the above-mentioned compound. The composition ratio of rubber and compound in rubber-reinforced thermoplastic resin B is not particularly limited, but it is preferably 3 to 70% by weight of rubber and 97 to 30% by weight of compound. In addition, as a compound, aromatic vinyl compound 40
~80% by weight and vinyl cyanide compounds and/or
or unsaturated carboxylic acid alkyl ester compound
Preferably, the mixture is comprised between 60 and 20% by weight. The particle size of resin B is also not particularly limited, but is preferably from 0.05 to 5μ, particularly preferably from 0.1 to 0.5μ. Rubbers constituting the rubber-reinforced thermoplastic resin B include conjugated diene rubbers such as polybutadiene, butadiene-styrene copolymers, butadiene-acrylonitrile copolymers, ethylene-propylene copolymers, ethylene-propylene-nonconjugated diene copolymers, etc. Examples include ethylene-propylene rubber such as polymers, acrylic ester rubber such as polybutyl acrylate, butyl acrylate-styrene copolymer, chlorinated polyethylene, ethylene-vinyl acetate copolymer, etc., and one or more of them may be used. be able to. Examples of aromatic vinyl compounds include styrene, α-
Examples include methylstyrene, dimethylstyrene, vinyltoluene, etc., and one or more types can be used. Styrene is particularly preferred. Examples of vinyl cyanide compounds include acrylonitrile, methacrylonitrile, and the like, and one or more types can be used. Acrylonitrile is particularly preferred. Examples of unsaturated carboxylic acid alkyl ester compounds include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl acrylate,
Examples include hydroxyethyl methacrylate, hydroxypropyl methacrylate, etc., and one or more types can be used. Particularly preferred is methyl methacrylate. Examples of methods for producing the rubber-reinforced thermoplastic resin B include emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization, emulsion-suspension polymerization, and bulk-suspension polymerization. There is no particular restriction on the composition ratio of polycarbonate resin A and rubber-reinforced thermoplastic resin B, but polycarbonate resin A is 10 to 90% per total composition (A + B).
Preferably, the rubber reinforced thermoplastic resin B is 90 to 10% by weight. If polycarbonate resin A is less than 10% by weight, heat resistance and weld strength tend to decrease,
Moreover, if it exceeds 90% by weight, processability and appearance tend to deteriorate. The olefin-unsaturated carboxylic acid alkyl ester copolymer C is a copolymer consisting of an olefin and an unsaturated carboxylic acid alkyl ester, or these and other ethylenically unsaturated compounds.
There is no particular restriction on the composition ratio of olefin-unsaturated carboxylic acid alkyl ester copolymer C, but olefin is 30 to 95% by weight, unsaturated carboxylic acid alkyl ester 5 to 70% by weight, and other ethylenically unsaturated compounds. It is preferably 0 to 20% by weight. Olefins include ethylene, propylene,
Examples include butene-1, 4-methylpentene-1, etc., and one or more types can be used. Particularly preferred are ethylene and propylene. As unsaturated carboxylic acid alkyl ester,
Examples include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, etc., and one or more types can be used. Particularly preferred is ethyl acrylate. Other ethylenically unsaturated compounds include olefins, vinyl esters containing C ₂ to ₆ in the saturated carboxylic acid component, and C ₁ to ₈ in the saturated alcohol component.
acrylic and methacrylic esters and maleic esters, vinyl halides, vinyl ethers, N-vinyl lactams,
Examples include carboxylic acid amides, and one or more types can be used. The olefin-unsaturated carboxylic acid alkyl ester copolymer can be produced by a known method. There is no particular restriction on the amount of olefin-unsaturated carboxylic acid alkyl ester copolymer C, but
It is particularly preferable that the amount is 0.1 to 40 parts by weight per 100 parts by weight of the total of polycarbonate resin A and rubber-reinforced thermoplastic 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, rubber-reinforced thermoplastic resin, and olefin-unsaturated carboxylic acid alkyl ester copolymer; only two of these three components are mixed in advance, and then the remaining one component is added. They may be mixed, or the three components may be mixed all at once. Further, as a mixing method, there may be mentioned a known mixing method using a Banbury mixer, a single screw extruder, a twin screw extruder having a kneading block, or the like. Also, during mixing, it is sufficient to add polyolefin resins such as polyethylene and polypropylene ethylene-propylene copolymers, as well as known dyes and pigments, stabilizers, plasticizers, antistatic agents, ultraviolet absorbers, lubricants, fillers, etc. It is possible. The present invention will be specifically explained below using Examples, but the present invention is not limited thereto. Examples and Comparative Examples Polycarbonate resins, rubber-reinforced thermoplastic resins, and olefin-unsaturated carboxylic acid alkyl ester copolymers were mixed at once based on the blending ratios shown in Table 1 to obtain various compositions. Table 2 shows the physical properties of the obtained composition. The rubber-reinforced thermoplastic resins (ABS resin and AES resin) used were obtained by the following formulation, and the olefin-unsaturated carboxylic acid alkyl ester copolymer and polycarbonate resin were commercially available. Γ Rubber reinforced thermoplastic resin B - ABS resin - 50 parts by weight of styrene-butadiene copolymer latex (5/95, 90% gel), 35 parts by weight of styrene and 15 parts by weight of acrylonitrile were mixed in the presence of a redox initiator using a known method. After polymerization based on the emulsion graft polymerization method, it was mixed with separately polymerized styrene-acrylonitrile (70/30) copolymer latex at a ratio of 1:1 (ABS-1) and 1:2 (ABS-2). . ABS resin (ABS-1 and ABS-2) with graft particles with an average particle size of 0.35μ after salting and drying
I got it. -AES resin- 30 parts by weight of ethylene-propylene-ethylidene norbornene copolymer (45/50/5), 50 parts by weight of styrene
parts by weight and 20 parts by weight of acrylonitrile were polymerized in the presence of benzoyl peroxide based on a known solution polymerization method to obtain a polymer. Styrene-acrylonitrile (70/30) produced separately from the obtained polymer
1:1 (AES-1) and 1:2 with copolymer
(AES-2) and mix at a ratio of AES resin (AES-2).
-1 and AES-2) were obtained.

【table】

[Table] - 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 on 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.

Claims (1)

[Scope of Claims] 1. A composition comprising a rubber-reinforced thermoplastic resin B obtained by polymerizing an aromatic vinyl compound, a vinyl cyanide compound, and/or an unsaturated carboxylic acid alkyl ester compound in the presence of polycarbonate resin A and rubber. 1. A thermoplastic resin composition characterized by blending an olefin-unsaturated carboxylic acid alkyl ester copolymer C into a thermoplastic resin composition. 2. Polycarbonate resin A per total composition
10 to 90% by weight, and rubber-reinforced thermoplastic resin B
The thermoplastic resin composition according to claim 1, wherein the content is 90 to 10% by weight. 3. 0.1 olefin-unsaturated carboxylic acid alkyl ester copolymer C per 100 parts by weight of the composition.
40 parts by weight of the thermoplastic resin composition according to claim 1. 4 Olefin-unsaturated carboxylic acid alkyl ester copolymer C is a copolymer consisting of 30 to 95% by weight of olefin, 5 to 70% by weight of unsaturated carboxylic acid alkyl ester, and 0 to 20% by weight of other ethylenically unsaturated compounds. The thermoplastic resin composition according to claim 1, which is a composite. 5. The thermoplastic resin composition according to claim 4, wherein the olefin is one or more compounds selected from ethylene and α-olefin. 6. The thermoplastic resin composition according to claim 5, wherein the α-olefin is propylene.