JPH0725979B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Field of Industrial Application> The present invention comprises a so-called engineering plastic such as polycarbonate, polyamide, saturated polyester, polyphenylene ether, and polyarylate, and a rubber-reinforced styrene resin and an oxazoline-modified copolymer,
The present invention relates to a thermoplastic resin composition having excellent impact resistance (notched Izod).

<Prior art> Rubber-reinforced styrene resins such as ABS resin, EPDM rubber as a rubber component, AES resin using acrylic rubber, and AAS resin have excellent physical property balance and dimensional stability and are used in a wide range of fields. Has been done. Among them, there are many applications to the automobile field, but in this case, heat resistance or chemical resistance such as gasoline resistance and brake oil resistance always becomes a problem, and improvement in this respect has been an important issue. On the other hand, polycarbonate, polyphenylene ether, polyarylate, etc. are known as polymers having excellent heat resistance, and polyamide and saturated polyester are known as polymers having excellent chemical resistance, but there are problems in moldability, impact resistance, dimensional accuracy, etc. is there. Therefore, it has been proposed to blend a rubber-reinforced styrene resin such as ABS resin with these engineering plastics (Japanese Patent Publication No. 38-15225, Japanese Patent Publication No. 39-71, US Pat. No. 338343).
5, Japanese Examined Sho 38-23476, Japanese Examined Sho 47-30421). However, such a resin composition has a problem that sufficient impact resistance cannot be obtained.

<Means for Solving Problems> The inventors of the present invention have made earnest studies on improvement of the above-mentioned problems in quality of the composition comprising the engineering plastic and the rubber-reinforced styrene resin, and as a result, the engineering plastic and the rubber-reinforced styrene have been obtained. The inventors have found that a thermoplastic resin composition excellent in impact resistance (notched Izod) can be obtained by mixing a system resin and a specific oxazoline-modified copolymer in a specific ratio, and reached the present invention.

That is, the present invention, polycarbonate, polyamide,
A composition comprising 10 to 90 parts by weight of one or more engineering plastics (A) selected from the group consisting of saturated polyester, polyphenylene ether and polyarylate and 90 to 10 parts by weight of rubber-reinforced styrene resin (B). 0.1 to 20% by weight of vinyl oxazoline per 100 parts by weight,
An oxazoline-modified copolymer (C) consisting of 50 to 89.9% by weight of an aromatic vinyl monomer and 10 to 49.9% by weight of another copolymerizable vinyl monomer is added in an amount of 0.1 to 50 parts by weight. The present invention provides a thermoplastic resin composition comprising:

The present invention will be described in detail below.

The engineering plastic (A) used in the present invention is one or more selected from the group consisting of polycarbonate, polyamide, saturated polyester, polyphenylene ether and polyarylate, and a dihydric phenol and a carbonate precursor, for example, phosgene,
Aromatic polycarbonate obtained by reaction of diphenyl carbonate, 6-nylon, 66-nylon,
Polyamide such as 6/66 copolymer nylon, 46-nylon, 12-nylon, etc., saturated polyester such as polyethylene terephthalate, polybutylene terephthalate, general formula (R ₁ , R ₂ , and R ₃ are the same or different alkyl groups, aryl groups, halogen, hydrogen, and other monovalent residues.) Polyphenylene ether, divalent phenol and aromatic dicarboxylic acid, For example, polyarylate obtained by reaction with terephthalic acid, isophthalic acid, etc. is shown, and one or more of them can be used.

The rubber-reinforced styrenic resin (B) in the present invention is obtained by polymerizing an aromatic vinyl-based monomer in the presence of a rubber-like polymer and another vinyl-based monomer copolymerizable as necessary. A graft copolymer or a graft copolymer thereof,
It is a mixture with an aromatic vinyl-based polymer obtained by polymerizing an aromatic vinyl-based monomer and optionally another copolymerizable vinyl-based monomer.

Examples of the rubber-like polymer that constitutes the rubber-reinforced styrene resin (B) include polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer and other diene rubber-like polymers, ethylene-propylene copolymer, and ethylene. -Non-diene rubbery polymers such as propylene-non-conjugated diene copolymer, acrylic rubbery polymer, and chlorinated polyethylene are exemplified, and one kind or two or more kinds can be used. These rubbery polymers are produced by emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization and the like.

The particle size and gel content of the rubber-like polymer when produced by emulsion polymerization are not particularly limited, but the average particle size is 0.1 to 1 μm and the gel content is 0 to 95%.
Is preferred.

Aromatic vinyl monomers include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene,
p-methylstyrene, t-butylstyrene, α-methylvinyltoluene, dimethylstyrene, chlorostyrene,
Dichlorostyrene, bromostyrene, dibromostyrene and the like are exemplified, and one or more kinds can be used.
Particularly, styrene and α-methylstyrene are preferable.

Other vinyl monomers copolymerizable with the aromatic vinyl monomer include vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. Unsaturated carboxylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, and 2-ethylhexyl methacrylate, maleimide, N-phenylmaleimide, N-methylmaleimide, N-cyclohexylmaleimide, and other maleimide-based monomers are exemplified. One kind or two or more kinds can be used. Acrylonitrile, methyl methacrylate and N-phenylmaleimide are particularly preferable.

As the graft polymerization method, known emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization or a combination thereof may be used.

The aromatic vinyl-based monomer constituting the aromatic vinyl-based polymer used by mixing with the graft copolymer and the other copolymerizable vinyl-based monomer are each used in the graft copolymer. Any one kind or two or more kinds can be selected and used from the same group. As the polymerization method of the polymer, known emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or a combination thereof may be used.

The composition ratio of the rubber-like polymer and the monomer in the rubber-reinforced styrene resin is not limited, but preferably the rubber-like polymer
20-80% by weight and 80-20% by weight of monomer. The composition ratio of the aromatic vinyl-based monomer and the other vinyl-based monomer in the monomer is not particularly limited, but the aromatic vinyl-based monomer 10 to 100% by weight, particularly 30 to 70%. % By weight, 90 to 0% by weight of other vinyl monomers, and particularly 70 to 30% by weight are preferable.

The oxazoline-modified copolymer (C) used in the present invention means 0.1 to 20% by weight of vinyloxazoline, 50 to 89.9% by weight of an aromatic vinyl monomer, and 49.9 to 40% of another vinyl monomer which can be copolymerized. It is a copolymer composed of 10% by weight.

As vinyl oxazoline, 2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline,
4,4-Dimethyl-2-vinyl-2-oxazillin, 4,4-
Dimethyl-2-vinyl-5,6-dihydro-4H-1,3-oxazine, 4,4,6-trimethyl-2-vinyl-5,6-dihydro-4H-1,3-oxazine, 2-isopropenyl -2-
Oxazoline, 4,4-dimethyl-2-isopropenyl-
2-oxazoline etc. are illustrated, and it is used by 1 type (s) or 2 or more types. Particularly preferred is 2-vinyl-2-oxazoline.

Examples of the aromatic vinyl-based monomer and the other copolymerizable vinyl-based monomer are the same as those exemplified in the section of the graft copolymer, and they are used alone or in combination of two or more. be able to. Aromatic vinyl monomers are styrene and α-methylstyrene, and other vinyl monomers are acrylonitrile, methyl methacrylate,
N-phenylmaleimide is preferred.

If the amount of vinyl oxazoline is less than 0.1% by weight, the impact resistance of the finally obtained composition will be poor, and if it exceeds 20% by weight, the flowability will be poor, such being undesirable. If the aromatic vinyl-based monomer or other vinyl-based monomer is out of the above range, the composition is inferior in impact resistance, which is not preferable.

In particular, 0.5 to 15% by weight of vinyl oxazoline, 60 to 84.5% by weight of aromatic vinyl-based monomer, and 15 to 39.5% of other vinyl-based monomer.
An oxazoline modified copolymer which is wt% is preferred.

The method for producing the vinyl oxazoline modified copolymer,
Known emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or a combination thereof may be used. There is no particular limitation on the molecular weight, but the weight average molecular weight is preferably 10,000 to 1,000,000.

The thermoplastic resin composition of the present invention comprises the above-mentioned engineering plastic (A), rubber-reinforced styrene resin (B), and oxazoline-modified copolymer (C), and its constitution is (A) and (B). (A) 10 to 90 parts by weight, preferably 20 to 80 parts by weight, based on the total amount of 100 parts by weight, (B)
90 to 10 parts by weight, preferably 80 to 20 parts by weight, and (C) 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight, per 100 parts by weight of the total amount of (A) and (B).

If the composition ratio is outside the above range, sufficient impact resistance cannot be obtained.

Engineering plastic (A), rubber-reinforced styrene resin (B) and oxazoline modified copolymer (C)
There is no limitation on the order of mixing and the state thereof, depending on the form of pellets, beads, powder, etc. (A), (B)
Examples of the method include simultaneous mixing of the three components (C) and (C), and a method of premixing the specific two components and mixing the remaining components. As a mixing method, a known method such as a Banbury mixer, a roll or an extruder can be adopted.

Incidentally, if necessary, an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, a lubricant, a dye, a pigment, a plasticizer, a flame retardant,
Additives such as glass fibers, metal fibers, carbon fibers, metal flakes, reinforcing agents, and fillers can be added. Further, a thermoplastic resin such as polyacetal, polymethylmethacrylate, or vinyl chloride can be appropriately mixed.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

The numbers of parts and percentages are shown on a weight basis.

Reference Example 1 Engineering plastic (A) PC: Polycarbonate “Caliver 300-10” manufactured by Sumitomo Nogatak Co., Ltd. PA: 6-nylon PBT manufactured by Unitika Co., Ltd. Polybutylene terephthalate “Toughpet” manufactured by Mitsubishi Rayon Co., Ltd. PBT N-1000 "PPE: 2.6-Dimethylphenol, di-n-butylamine, cupric bromide and toluene were used, polymerization was carried out at 30 ° C while blowing oxygen, followed by detouching purification and intrinsic viscosity (25 ° C,
0.50 dl / g of polyphenylene ether (in chloroform) was obtained.

PAR: Unitika Polyarylate “U Polymer”
U-100 "Reference Example 2 Production of Rubber Reinforced Styrenic Resin (B) ABS-1: Acrylonitrile by emulsion polymerization in the presence of 50 parts (solid content) of polybutadiene latex having an average particle size of 0.41μ and a gel content of 88%. Copolymerize 15 parts and 35 parts of styrene
ABS graft copolymer latex (graft rate 45%, free acrylonitrile-styrene copolymer intrinsic viscosity 0.
43) was manufactured. The intrinsic viscosity was measured at 30 ° C. in dimethylformamide. (The same applies hereinafter, unit: 100 ml / g) Separately, a copolymer latex consisting of 25 parts of acrylonitrile and 75 parts of styrene by the emulsion polymerization method (intrinsic viscosity 0.56)
Was prepared and mixed with an ABS graft copolymer latex so as to have a rubber content of 30%, followed by salting out, separation and recovery using magnesium sulfate.

ABS-2: Copolymerized with 15 parts of acrylonitrile and 35 parts of styrene by emulsion polymerization in the presence of 50 parts (solid content) of polybutadiene latex having an average particle size of 0.45μ and a gel content of 83%.
ABS graft copolymer latex (graft ratio 35%, free acrylonitrile-styrene copolymer intrinsic viscosity 0.
33), and salting out and separating with magnesium sulfate,
Recovered.

ABS-3: ABS graft copolymer latex obtained by the method of ABS-2 and acrylonitrile 25 separately obtained by emulsion polymerization
Part, and a copolymer latex consisting of 75 parts of α-methylstyrene (intrinsic viscosity 0.58) were mixed so that the rubber content was 30%, and then salting out, separation and recovery were performed using magnesium sulfate.

AES: ethylene-propylene-ethylidene norbornene copolymer (EPDM, iodine value 21, Mooney viscosity 75, propylene content 50%) 50 parts, acrylonitrile 15 parts and styrene 35
Part AES graft copolymer (graft ratio 52%, free acrylonitrile-styrene copolymer intrinsic viscosity 0.
63) was produced by the solution polymerization method. After the polymerization, it was precipitated in methanol, separated and collected.

Separately, the acrylonitrile-styrene copolymer latex represented by ABS-2 was salted out with magnesium sulfate, separated and collected to obtain a copolymer. Then, the AES graft copolymer and the copolymer were mixed so that the rubber content was 30%.

Reference Example 3 Production of Oxazoline Modified Copolymer (C) C-1: Intrinsic viscosity of 1 part of 2-vinyl-2oxazoline, 28 parts of acrylonitrile and 71 parts of styrene by solution polymerization method.
56 copolymers were prepared. The intrinsic viscosity was measured at 30 ° C. in dimethylformamide. (Unit 100 ml / g) C-2: In the same manner as C-1, 2-vinyl-2-oxazoline 5
Part, acrylonitrile 30 parts, and styrene 65 parts to prepare a copolymer having an intrinsic viscosity of 0.55.

C-3: In the same manner as C-1, 2-vinyl-2-oxazoline 15
Part, acrylonitrile (26 parts) and styrene (59 parts) having an intrinsic viscosity of 0.53 were produced.

C-4: as in C-1, 2-vinyl-2-oxazoline 25
Part, acrylonitrile (23 parts), and styrene (52 parts) to give a copolymer having an intrinsic viscosity of 0.54.

C-1 to C-4 were separated and recovered after being precipitated in methanol.

Example Engineering plastic (A), rubber-reinforced styrene resin (B) and oxazoline-modified copolymer (C)
Were mixed in the composition shown in Tables 1 to 5, and were melt mixed and granulated using a 40 mm twin-screw extruder. The granulation temperature is 250 ° C except for polyphenylene ether and polyarylate.
The polyphenylene ether and polyarylate were set at 280 ° C.

The physical properties of the obtained resin composition were measured by the following methods, and the results are shown in Tables 1-5.

-Impact strength (Izod with notch): ASTM D-256 (23 ° C) In addition, the test piece for the above quality evaluation uses a 3.5 ounce injection molding machine, and the cylinder temperature is 250 ° C except for polyphenylene ether and polyarylate. In addition, polyphenylene ether and polyarylate were set at 280 ° C.

<Effects of the Invention> The resin composition of the present invention has a characteristic of being excellent in impact strength as compared with the composition of the conventional engineering plastics and the rubber-reinforced styrene resin, and is practical as a material for various industrial parts. Extremely high value.

Claims (1)

[Claims] 1. A rubber-reinforced styrene resin (B) and 10 to 90 parts by weight of one or more engineering plastics (A) selected from the group consisting of polycarbonate, polyamide, saturated polyester, polyphenylene ether and polyarylate. 100 to 100 parts by weight of a composition consisting of 90 to 10 parts by weight, vinyl oxazoline 0.1 to 20% by weight, aromatic vinyl monomer 50 to 89.9% by weight and other copolymerizable vinyl monomer 10 to 49.9% by weight % Of the oxazoline-modified copolymer (C) in an amount of 0.1 to 50 parts by weight, which is a thermoplastic resin composition.