JP2003231802A - Thermoplastic resin composition and molding using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition which provides a molding having excellent impact resistance, heat resistance and appearance and has excellent moldability and the molding obtained by using the thermoplastic resin composition. <P>SOLUTION: The thermoplastic resin composition comprises 100 parts wt. of a resin composition (A) which is composed of (a) 10-90 wt.% of an aromatic polycarbonate resin, (b) 5-60 wt.% of a thermoplastic resin obtained by polymerizing an aromatic vinyl monomer with a vinyl cyanide monomer and another copolymerizable monomer and (c) 5-50 wt.% of a resin obtained by subjecting the aromatic vinyl monomer, the vinyl cyanide monomer and another copolymerizable monomer to graft copolymerization in the presence of a rubber- like substance and 0.1-40 parts wt. of a methyl methacrylate/alkyl acrylate copolymer (B). The molding is obtained by using the thermoplastic resin composition. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition which is excellent in impact resistance, heat resistance and appearance and is excellent in moldability, and a molded product obtained by using the same.

[0002]

2. Description of the Related Art Aromatic polycarbonate resins are widely used as resins having excellent mechanical strength, impact resistance and heat resistance, but have drawbacks such as chemical resistance and fluidity.
On the other hand, AXS resin such as AAS resin, AES resin, ABS resin, etc. (Aromatic vinyl monomer, vinyl cyanide monomer and other copolymerizable monomer are graft-copolymerized in the presence of a rubber-like substance. The resin obtained by polymerization) is excellent in chemical resistance and moldability (fluidity), but has drawbacks in impact resistance, heat resistance and the like. Therefore, an attempt has been made to produce a resin having excellent impact resistance, heat resistance, and chemical resistance by adding a polycarbonate resin to the AXS resin. However, since the compatibility is not sufficient by simply mixing the AXS resin and the polycarbonate resin, streaky unevenness occurs on the surface of the molded product.

[0003]

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted various studies to solve the above problems, and as a result, have found that a specific weight average of a molding material containing an aromatic polycarbonate resin and an AXS resin as a main component can be obtained. It has been found that by blending a methyl methacrylate / alkyl acrylate copolymer having a molecular weight in a predetermined ratio, a thermoplastic resin composition excellent in impact resistance, heat resistance, appearance of a molded article, etc. can be obtained. The present invention provides a resin composition suitable for a molding material containing an aromatic polycarbonate resin and an AXS resin as main components, and particularly a thermoplastic resin composition excellent in impact resistance, heat resistance, appearance of a molded article and the like. To do.

[0004]

The present invention provides (1) (a)
Aromatic polycarbonate resin 10 to 90% by weight, (b)
5-60% by weight of a thermoplastic resin obtained by polymerizing an aromatic vinyl monomer, a vinyl cyanide monomer and other copolymerizable monomers, and (c) an aromatic compound in the presence of a rubber-like substance. Resin 5 obtained by graft-copolymerizing vinyl monomers, vinyl cyanide monomers and other copolymerizable monomers
A thermoplastic resin composition containing 100 parts by weight of a resin composition (A) consisting of 50% by weight and 0.1 to 40 parts by weight of a methyl methacrylate / alkyl acrylate copolymer (B) and a thermoplastic resin composition using the same It relates to the obtained molded product.

[0005]

DETAILED DESCRIPTION OF THE INVENTION The details of the present invention will be described below. The aromatic polycarbonate resin which is the component (a) in the present invention is an aromatic polycarbonate polymer obtained by reacting an aromatic dihydroxy compound or a small amount of this polyhydroxy compound with phosgene or carbonic acid diester.

As the above aromatic dihydroxy compound,
2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (4-hydroxy-)
3,5-Dimethylphenyl) propane (tetramethylbisphenol A), 2,2-bis (4-hydroxy-)
3,5-Dibromophenyl) propane (tetrabromobisphenol A), 2,2-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxyphenyl) sulfone, 2,2-bis (4-hydroxy) Phenyl) sulfide, 2,2-bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ether, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) ) Cyclohexane and the like are exemplified. The preferred bisphenol is 2,2-bis (4-hydroxyphenyl)
It is propane (bisphenol A).

The blending amount of the component (a) in the present invention is
It is necessary to set it to 10 to 90% by weight, preferably 30 to 80% by weight, and more preferably 50 to 70% by weight, based on the total amount of the components (a), (b) and (c). To be done. If the blending amount is less than 10% by weight, heat resistance and mechanical properties are lowered, and if the blending amount exceeds 90% by weight, chemical resistance is lowered. The thermoplastic resin which is the component (b) in the present invention is obtained by polymerizing an aromatic vinyl monomer, a vinyl cyanide monomer and other copolymerizable monomers. As the aromatic vinyl monomer, styrene, α-methylstyrene, p-methylstyrene, p-
Tert-butylstyrene, chlorostyrene, bromostyrene and the like can be used alone or in combination of two or more.

As the vinyl cyanide monomer, acrylonitrile, methacrylonitrile and the like can be used alone or in combination of two or more. Other vinyl monomers include acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate and butyl acrylate, and methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate. , Acrylic acid, methacrylic acid,
Unsaturated fatty acids such as oleic acid, maleic acid and fumaric acid,
Unsaturated fatty acid anhydrides such as acrylic acid anhydride, methacrylic acid anhydride and maleic anhydride, amides of unsaturated fatty acids such as acrylamide, N, N-dimethylacrylamide, methacrylamide, N, N-dimethylmethacrylamide, N-
Methyl maleimide, N-cyclohexyl maleimide, N
Examples include maleimides such as phenylmaleimide, vinyl esters such as vinyl acetate, vinyl butyrate, vinyl benzoate, and the like. These can be used alone or in combination of two or more.

The ratio of each monomer in the thermoplastic resin which is the component (b) in the present invention is such that the aromatic vinyl monomer is 50.
˜95 wt%, vinyl cyanide monomer is 5-40 wt%, and other copolymerizable monomer is preferably 0-30 wt%. The blending amount of the component (b) in the present invention needs to be 5 to 60% by weight, and preferably 10 to 40% by weight based on the total amount of the components (a), (b) and (c). % By weight, more preferably 20
-30% by weight. If the blending amount is less than 10% by weight, the chemical resistance and fluidity tend to be lowered, and if the blending amount exceeds 40% by weight, the impact resistance and the mechanical strength tend to be lowered.

Examples of the AXS resin which is the component (c) in the present invention include AAS resin, AES resin and ABS.
Resins, ACS resins and the like can be mentioned. Considering weather resistance, AAS obtained by polymerizing acrylic rubber particles with aromatic vinyl monomers, vinyl cyanide monomers and other copolymerizable monomers. Resins are preferred. Specific examples of the aromatic vinyl-based monomer, vinyl cyanide-based monomer and other copolymerizable monomer used here are the same as those exemplified in the description of the thermoplastic resin (b). Is mentioned.

In the production of the AXS resin as the component (c), the ratio of the rubber-like polymer to the above-mentioned monomer for graft polymerization is preferably rubber-like polymer / monomer mixture (weight ratio) = 5. ~ 70 / 30-95, more preferably 10-6
5 / 35-90. When the amount of the rubber-like polymer is less than 5, the ratio of the rubber-like polymer in the resin tends to be low and the impact resistance tends to be low, and when it exceeds 70, the graft ratio to the rubber-like polymer tends to be low. However, the dispersion of the rubber-like polymer in the resin becomes insufficient, and the impact resistance tends to decrease.

The blending amount of the component (c) in the present invention is
It is necessary that the amount is 5 to 50% by weight, preferably 5 to 40% by weight, and more preferably 10 to 20% by weight, based on the total amount of the components (a), (b) and (c). To be done. If the blending amount is less than 5% by weight, impact resistance and mechanical strength are lowered, and if the blending amount exceeds 40% by weight, heat resistance tends to be lowered. The component (B) in the present invention is
It is obtained by copolymerizing methyl methacrylate and an alkyl acrylate monomer. Examples of the alkyl acrylate monomer include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate and the like. Can be mentioned. Preferred is ethyl acrylate. The weight average molecular weight of the component (B) is 300,000 to 10
The range of 00000 is preferred.

The copolymerization ratio (methyl methacrylate / alkyl acrylate monomer) of methyl methacrylate and alkyl acrylate monomer of the component (B) in the present invention is from 5 to 5.
It is preferably 9/1 to 5 (molar ratio), more preferably 7 to 9/3 to 1 (molar ratio), and further preferably 8
/ 2 (molar ratio). The blending amount of the component (B) in the present invention is required to be 0.1 to 40 parts by weight with respect to 100 parts by weight of the resin composition comprising the components (a), (b) and (c). It is preferably 1 to 20 parts by weight, more preferably 3 to 7 parts by weight. If the blending amount is less than 1 part by weight, the effect of improving the appearance of the molded product is lowered, and if the blending amount exceeds 20 parts by weight, heat resistance and mechanical strength tend to be lowered.

If desired, the resin composition of the present invention may contain various additives such as stabilizers, pigments, dyes, lubricants, plasticizers, reinforcing agents such as glass fibers and carbon fibers, and glass beads. Fillers and the like can be added. Molded articles obtained using the resin composition according to the present invention are automobile-related parts, O
It is suitable for equipment A, home electric appliances, and sundries.

[0015]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto. <Manufacture of AAS resin> 39 parts by weight of polybutadiene latex (SNX8004 manufactured by A & L Japan) (20 parts by weight of solid content), 200 parts by weight of pure water, 0.8 parts by weight of potassium tallow fatty acid (KS soap manufactured by Kao Corporation), acrylic acid 80 parts by weight of butyl, 0.04 parts by weight of allyl methacrylate, and 0.8 parts by weight of 1,6-hexanediol diacrylate were stirred and mixed, and the temperature was raised to 60 ° C. while substituting with nitrogen. After the temperature was raised, a solution prepared by dissolving 0.16 parts by weight of potassium persulfate in 8 parts by weight of pure water was added, and the mixture was stirred for 3 hours and then cooled. The reaction rate at this time was 97%.

195 parts by weight of the above latex, pure water 16.
5 parts by weight, 0.175 parts by weight of potassium tallow fatty acid, 3 parts by weight of styrene, 1.5 parts by weight of acrylonitrile, 0.1 part by weight of allyl methacrylate, 0.016 part by weight of cumene hydroperoxide were stirred and mixed, and the atmosphere was replaced with nitrogen. While raising the temperature to 70 ° C. After the temperature was raised, sodium pyrophosphate was adjusted to 0.
2 parts by weight and 0.004 parts by weight of iron (II) sulfate were added to pure water 12
The solution dissolved in 1 part by weight was added and stirred for 1 hour. Sequentially, 24 parts by weight of styrene, 9.3 parts by weight of acrylonitrile, 0.16 parts by weight of tert-dodecyl mercaptan,
2 parts of a mixture of 15 parts by weight of pure water, 0.5 part by weight of potassium tallow fatty acid and 0.07 part by weight of cumene hydroperoxide.
It dripped over time. After completion of dropping, the temperature was maintained for 1 hour and then cooled to obtain a graft copolymer latex. The reaction rate at this time was 95%. Aluminum sulfate 0.
The synthesized graft copolymer latex was added dropwise to 200 parts by weight of a 2% by weight aqueous solution to coagulate, and the resulting slurry was dehydrated and dried to obtain an AAS resin powder.

<Ingredients> Aromatic polycarbonate is
Made by Nippon GE Plastics, product name "LS-1" (M
FR = 5 g / 10 min) was used. The thermoplastic resin is manufactured by Electrochemical Co., Ltd., trade name "GR-AT-R" weight average molecular weight 140000, "GR-AT-6S" weight average molecular weight 85000, "MS-NC" weight average molecular weight 1200.
00 (mixture of 30:30:40 by weight in this order) was used. As the AAS resin, the AAS resin powder manufactured by the above manufacturing method was used. The methyl methacrylate / alkyl acrylate copolymer is manufactured by Mitsubishi Rayon Co., Ltd. under the trade name “METABRENE P-501” (weight average molecular weight 540,0).
00) was used. The above components were mixed in the proportions shown in Table 1 and extruded into pellets with a twin-screw vent extruder. After drying the pellets with a hot air dryer at 120 ° C. for 5 hours or more, a test piece for measuring physical properties was prepared by injection molding at a resin temperature of 270 ° C. In the table, the blending amounts of the components (a), (b) and (c) are% by weight, the component (B) is the component (a),
Parts (b) and (c) are parts by weight based on 100 parts by weight.

<Evaluation method> Izod impact strength is ASTM
According to -D256, deflection temperature under load is ASTM-D64
It measured according to 8. The appearance of the molded product is visually evaluated, and is expressed in three grades of good, good, and bad.

[0019]

[Table 1]

[0020]

[Table 2]

[0021]

The resin composition of the present invention has impact resistance,
A molded product having excellent heat resistance and appearance can be provided, and it is suitable as a material for molded products such as automobile-related parts, OA equipment, home electric appliance parts and sundries.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 51/00 C08L 51/00

Claims (2)

[Claims] 1. (a) Aromatic polycarbonate resin 10
To 90% by weight, (b) 5 to 60% by weight of a thermoplastic resin obtained by polymerizing an aromatic vinyl monomer, a vinyl cyanide monomer and other copolymerizable monomers, and (c) rubber. A resin composition comprising 5 to 50% by weight of a resin obtained by graft-copolymerizing an aromatic vinyl monomer, a vinyl cyanide monomer and another copolymerizable monomer in the presence of a particulate substance (A ) 100 parts by weight and methyl methacrylate / alkyl acrylate copolymer (B) 0.1 to 40
A thermoplastic resin composition containing parts by weight. 2. A molded article obtained by using the thermoplastic resin composition according to claim 1.