JP2000265031A - Thermoplastic resin composition and sheet product made therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition having an excellent extrusion moldability. SOLUTION: A resin composition comprises 10 to 50 pts.wt. rubber-reinforced styrene resin (A) and 50 to 90 pts.wt. vinyl cyanide copolymer (B) obtained by copolymerizing a mixture comprising 85 to 45 wt.% aromatic vinyl monomer (1), 15 to 55 wt.% vinyl cyanide monomer (2) and 0 to 40 wt.% other vinyl monomer (3) copolymerizable with these. Against 100 pts.wt. resin composition, a vinyl cyanide copolymer (C) having a weight average molecular weight of 5,000,000 or larger, obtained by copolymerizing 85 to 45 wt.% aromatic vinyl monomer (1) and 15 to 55 wt.% vinyl cyanide monomer (2), and 0.05 to 5 pts.wt. α-olefin oligomer and/or ethylene/α-olefin cooligomer (D), are mixed.

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 having excellent extrusion moldability, vacuum moldability, and surface appearance.

[0002]

2. Description of the Related Art Acrylonitrile is added to a diene rubber component.
A so-called ABS resin containing a graft copolymer obtained by copolymerizing a cyanide compound such as methacrylonitrile and an aromatic vinyl compound component such as styrene and α-methylstyrene has a high impact resistance, a high mechanical strength and a good molding property. OA equipment, home appliances, automotive parts,
It is widely used as an injection molding resin in application fields such as general goods, but in recent years, a technique for obtaining a vacuum molded product by sheet molding has attracted attention. As for ABS resin, a resin composition suitable for sheet molding has been developed.

[0003] In particular, a technique of blending AS resins having different molecular weights to improve vacuum formability (Japanese Patent Laid-Open No. 7-3163).
90) have been proposed. However, by blending AS resins having different molecular weights, extrusion moldability,
And, although the vacuum formability is improved, there is no description of a technique for improving the surface appearance of a sheet molded product or a vacuum molded product.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned drawbacks of the prior art, and to provide a thermoplastic resin composition excellent in extrusion moldability, vacuum moldability and surface appearance of a product, and a thermoplastic resin composition comprising the same. To provide molded products.

[0005]

As a means for solving the problems, as a result of intensive studies on the polymer component to be blended with the rubber-reinforced styrene resin, an aromatic vinyl monomer and a cyanide were added to the rubber-reinforced styrene resin. By blending a vinyl cyanide copolymer having a weight average molecular weight of 5,000,000 or more obtained by copolymerizing a vinyl monomer, and an α-olefin oligomer and / or a co-oligomer of ethylene and an α-olefin, The present inventors have found that the above objects can be efficiently achieved, and have reached the present invention.

That is, according to the present invention, 10 to 50 parts by weight of a rubber-reinforced styrene resin (A), 85 to 45% by weight of an aromatic vinyl monomer (A) and 15 to 45% by weight of a vinyl cyanide monomer (B) (B) a vinyl cyanide copolymer (B) obtained by copolymerizing a mixture consisting of 0 to 55% by weight and 0 to 40% by weight of another vinyl monomer (c) copolymerizable therewith.
85 to 45% by weight of an aromatic vinyl monomer (a) and 15 to 55% by weight of a vinyl cyanide monomer (b) are copolymerized with 100 parts by weight of a resin composition consisting of 50 to 90 parts by weight. 0.1 to 10 parts by weight of a vinyl cyanide-based copolymer (C) having a weight average molecular weight of 5,000,000 or more and α-
The present invention provides a thermoplastic resin composition comprising 0.05 to 5 parts by weight of an olefin oligomer and / or a co-oligomer of ethylene and an α-olefin (D).
More preferably, the weight average particle diameter is 0.1 to 1.5 μm
In the presence of 20 to 80 parts by weight of the rubbery polymer (A-1), 10 to 90% by weight of an aromatic vinyl monomer (A) and 0 to 50% by weight of a vinyl cyanide monomer (B) % And other vinyl monomers (c) copolymerizable therewith with 0 to 90%
Graft copolymer (A) 10 obtained by graft polymerization of 80 to 20 parts by weight of a monomer mixture (A-2) consisting of
To 50 parts by weight, and an aromatic vinyl monomer (a) 85 to 4
A mixture comprising 5% by weight, 15 to 55% by weight of a vinyl cyanide monomer (b) and 0 to 40% by weight of another vinyl monomer (c) copolymerizable therewith is obtained by copolymerization. 85 to 45% by weight of an aromatic vinyl monomer (a) and 100 to 100 parts by weight of a resin composition comprising 50 to 90 parts by weight of a vinyl cyanide copolymer (B) (B) 0.1 to 10 parts by weight of a vinyl cyanide copolymer (C) having a weight average molecular weight of 5.5 million or more, obtained by copolymerizing 15 to 55% by weight, and α-olefin oligomer and / or ethylene And 0.05 to 5 parts by weight of an α-olefin coloolomer (D), and the intrinsic viscosity [η] of the acetone-soluble component (A) + (B) + (C) + (D) Of 0.4 to 1.2 dl / g and the thermoplastic resin composition It relates sheet formed by extrusion molding.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The rubber-reinforced styrene resin (A) in the present invention is not particularly limited,
The rubbery polymer (A-1) is converted from an aromatic vinyl monomer (a), a vinyl cyanide monomer (b), and another vinyl monomer (c) copolymerizable therewith. A monomer mixture comprising at least one or more selected monomers (A
-2) is a graft copolymer obtained by graft polymerization. Examples of the rubbery polymer (A-1) include, in addition to polybutadiene, a styrene-butadiene copolymer, an acrylonitrile-butadiene copolymer, and styrene- Examples thereof include a butadiene block copolymer, a butyl acrylate-butadiene copolymer, and a polyisoprene rubber. Among them, polybutadiene and a styrene-butadiene copolymer rubber are preferable.

In the present invention, the aromatic vinyl monomer (A) of the monomer mixture (A-2) includes styrene, α-
Examples include methylstyrene, p-methylstyrene, vinyltoluene, t-butylstyrene, o-ethylstyrene, o-chlorostyrene, o, p-dichlorostyrene and the like, with styrene and α-methylstyrene being particularly preferred. The content of the aromatic vinyl monomer (a) is 10 to 90% by weight of the monomer mixture (A-2) in the presence of 20 to 80 parts by weight of the rubbery polymer (A-1). preferable. Within this range, the mechanical strength is excellent.

As the vinyl cyanide monomer (b),
Acrylonitrile, methacrylonitrile, ethacrylonitrile and the like can be mentioned, and acrylonitrile is particularly preferable. The content of the vinyl cyanide monomer (b) is preferably 0 to 50% by weight of the monomer mixture (A-2) in the presence of 20 to 80 parts by weight of the rubbery polymer (A-1). . Within this range, the mechanical strength is excellent.

[0010] Other copolymerizable vinyl monomers (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and (meth) acrylic acid. α, β such as n-butyl, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, chloromethyl (meth) acrylate and 2-chloroethyl (meth) acrylate -Unsaturated carboxylic acid esters, N-methylmaleimide, N-cyclohexylmaleimide, maleimide compounds such as N-phenylmaleimide, unsaturated dicarboxylic acids such as maleic acid, unsaturated dicarboxylic anhydrides such as maleic anhydride, and acrylamide. And unsaturated amides. Of these, methyl methacrylate, N-phenylmaleimide and And maleic anhydride are preferred.

The weight-average particle diameter of the rubbery polymer (A-1) is from the viewpoint of impact resistance, moldability, especially fluidity and appearance of the molded article of the thermoplastic resin composition obtained.
It is preferably from 1 to 1.5 μm, more preferably from 0.2 to 1.2 μm.

The content of the rubbery polymer (A-1) is from 20 to 80 parts by weight based on 100 parts by weight of the graft copolymer (A) in view of mechanical strength, heat resistance and moldability. And preferably 35 to 70 parts by weight.

The graft ratio of the graft copolymer (A) is from 15 to 150 in view of mechanical strength and moldability.
%, More preferably 20 to 70%.
%. If the graft ratio is less than 15%, the impact resistance of the obtained thermoplastic resin composition may not be sufficient, and if it exceeds 150%, moldability, particularly fluidity, may be reduced.

The content of the graft copolymer (A) is as follows:
Graft copolymer (A) and vinyl copolymer (B)
It is 10 to 50 parts by weight in 100 parts by weight. The content of the graft copolymer (A) is preferably from 15 to 40 parts by weight from the viewpoint of the balance among impact resistance, rigidity, heat resistance and fluidity. If the content is less than 10 parts by weight, the resulting thermoplastic resin composition has insufficient impact resistance, and if it exceeds 50 parts by weight, the fluidity, heat resistance and rigidity decrease.

The vinyl copolymer (B) in the present invention
Are 85 to 45% by weight of an aromatic vinyl monomer (a) exemplified as a rubber-reinforced styrene resin (A), 15 to 55% by weight of a vinyl cyanide monomer (b), and are copolymerizable therewith. It is obtained by copolymerizing a monomer mixture (B-1) composed of 0 to 40% by weight of other vinyl monomers (c), and has extrudability, chemical resistance and vacuum moldability. From the viewpoint, 80 to 50% by weight / 50 to 20% by weight / 0 to 30%
% By weight, more preferably 70 to 50% by weight /
40 to 30% by weight / 0 to 20% by weight. If the amount of the vinyl cyanide monomer (b) is less than 15%, the resulting resin composition has insufficient chemical resistance. Color tone stability may decrease.

The average molecular weight of the vinyl copolymer (B) is 5
It is preferably from 10,000 to 300,000, and more preferably from 100,000 to 250,000. Within this range, the balance of physical properties is excellent.

The intrinsic viscosity [η] of the acetone-soluble component of the vinyl copolymer (B) is preferably from 0.4 to 1.2 dl / g, more preferably from 0.5 to 0.8 dl / g.
g, and less than 0.4 dl / g, the extrusion moldability and vacuum moldability are insufficient, and if it exceeds 1.2 dl / g, the fluidity decreases.

The content of the vinyl cyanide-based copolymer content (B) is determined from the viewpoint of the balance between extrusion moldability, vacuum moldability, and mechanical properties. 90 to 5 in 100 parts by weight of polymer (B)
It must be 0 parts by weight. If the content exceeds 90 parts by weight, the resulting thermoplastic resin composition will have insufficient impact resistance. If the content is less than 50 parts by weight, the fluidity, heat resistance and rigidity will decrease.

The method for producing the copolymers (A) and (B) may be any of polymerization methods such as emulsion polymerization, suspension polymerization, bulk polymerization, and solution polymerization, and is not particularly limited. There is also no particular limitation on the method of charging the monomer, and the initial batch charging, or while charging a part or all of the charged monomer continuously or divided to suppress the generation of the composition distribution of the copolymer. It may be polymerized.

The vinyl cyanide-based copolymer (C) in the present invention is a copolymer of an aromatic vinyl-based monomer and a vinyl cyanide-based monomer. B) It is obtained by copolymerizing a monomer mixture consisting of 85 to 45% by weight and 15 to 55% by weight of a vinyl cyanide monomer (b), and has an extrusion moldability, a vacuum moldability, and an appearance. 80 to 50% by weight / 50 to 20% by weight, more preferably 75 to 45% by weight / 3 from the viewpoint of properties.
5 to 25% by weight. When the content of the vinyl cyanide monomer (b) is less than 15%, the appearance of the obtained resin composition is not sufficient, and when it exceeds 55% by weight, the extrudability and vacuum moldability deteriorate. There is.

The vinyl cyanide copolymer (C) must have a weight average molecular weight of 5,000,000 or more. 50
If it is less than 0,000, the extrusion moldability, vacuum moldability, and appearance are remarkably deteriorated, which is not preferable. Among them, those having a weight average molecular weight of 5.5 to 9,000,000 are particularly preferable.

The intrinsic viscosity [η] of the acetone-soluble component of the vinyl copolymer (C) is preferably 5.0 to 10.0 dl / g, more preferably 6.0 to 9.0 dl.
If it is less than 5.0 dl / g, extrusion moldability, vacuum moldability, and appearance are insufficient, and 10.0 dl / g
/ G, the above characteristics deteriorate.

In the present invention, the content of the vinyl cyanide-based copolymer (C) is determined from the viewpoints of extrusion moldability, vacuum moldability, and appearance of the product, the graft copolymer (A) and the vinyl copolymer. (B) It must be 0.1 to 10 parts by weight based on 100 parts by weight. When the content exceeds 10 parts by weight, the fluidity of the obtained thermoplastic resin composition decreases,
On the other hand, if the amount is less than 0.1 part by weight, the extrudability, vacuum moldability, and appearance of the product of the obtained thermoplastic resin composition are remarkably reduced, which is not preferable.

The method for producing the vinyl cyanide copolymer is as follows:
Any polymerization method such as emulsion polymerization, suspension polymerization, bulk polymerization, and solution polymerization may be used, and is not particularly limited. There is also no particular limitation on the method of charging the monomer, and the initial batch charging, or while charging a part or all of the charged monomer continuously or divided to suppress the generation of the composition distribution of the copolymer. It may be polymerized.

The monomers used for the α-olefin oligomer and / or the ethylene-α-olefin cololimer (D) used in the present invention include ethylene and α-olefins having 3 to 20 carbon atoms, for example, Propylene, 1-butene, 1-hexene 4-methyl-1-pentene, 1-octene, 1-decene, 1-tetradecene,
Examples thereof include 1-hexesezecene, 1-octazecene, and 1-eicosene.

The α-olefin oligomer and / or the co-oligomer of ethylene and α-olefin (D) used in the present invention have a kinematic viscosity at 100 ° C. of 5 to 500 cS.
It is preferably t.

The α-olefin oligomer and / or the co-oligomer of ethylene and α-olefin (D) used in the present invention are 100 parts by weight of the graft copolymer (A) and the vinyl copolymer (B). Against 0.05
To 5 parts by weight, preferably 0.1 to 4 parts by weight. Within this range, extrudability, especially the reduction of deposits on the die and the screw current value during extrusion are stable,
Discharge unevenness is eliminated. When the amount is less than 0.05 part by weight, the extrusion moldability of the obtained thermoplastic resin composition is not sufficient, and when it exceeds 5 parts by weight, the mechanical properties of the obtained thermoplastic resin composition deteriorate. Further, the thermoplastic resin composition of the present invention is (A) + (B) from the viewpoints of extrusion moldability and vacuum moldability and the fluidity of the obtained thermoplastic resin composition.
+ (C) + (D) intrinsic viscosity [η] of acetone-soluble component
Is preferably 0.4 to 1.2 dl / g.

In the thermoplastic resin composition of the present invention, polyolefins such as vinyl chloride, polyethylene, polypropylene, polyamides such as nylon 6, nylon 66, polyethylene terephthalate, polybutylene terephthalate, polycyclohexane dimethyl terephthalate, etc. Polyester, polycarbonate, and various elastomers can be added to improve the performance as a molding resin. In addition, if necessary, an antioxidant such as a hindered phenol type, a sulfur-containing organic compound type, a phosphorus-containing organic compound type, a heat stabilizer such as a phenol type or an acrylate type, a benzotriazole type, a benzophenone type, a salicylate type, etc. UV stabilizers, various stabilizers such as organic nickel-based, hindered amine-based light stabilizers, etc., lubricants such as metal salts of higher fatty acids, higher fatty acid amides, etc., plasticizers such as phthalate esters and phosphate esters, poly Bromodiphenyl ether, tetrabromobisphenol-A,
Halogen-containing compounds such as brominated epoxy oligomers and brominated polycarbonate oligomers, phosphorus compounds, flame retardants and flame retardants such as antimony trioxide, odor masking agents, carbon black, titanium oxide, pigments, dyes, etc. You can also. Further, reinforcing agents and fillers such as glass fibers, glass flakes, glass beads, carbon fibers, and metal fibers can also be added. Regarding the method for producing the thermoplastic resin composition of the present invention, various methods such as melt kneading with a Banbury mixer, a roll, and a single-screw or multi-screw extruder can be adopted.

The thermoplastic resin composition of the present invention having excellent extrusion moldability is suitable for known extrusion molding, and is particularly excellent in sheet extrusion moldability. In addition, as a secondary processing, the sheet is excellent in vacuum formability using the sheet, and other known methods currently used for molding thermoplastic resins such as injection molding, blow molding, compression molding, and gas assist molding. Can be molded.

A sheet product extruded using the thermoplastic resin composition of the present invention is suitable for appearance and a vacuum formed product using the sheet product, and a product excellent in uneven thickness can be obtained. Particularly when the average thickness is 3.0 mm or less, a remarkable effect can be obtained.

The present invention will be described more specifically with reference to the following Examples and Comparative Examples, but these Examples do not limit the present invention. Here, unless otherwise specified, "%" represents% by weight and "parts" represents parts by weight. A method for analyzing the resin properties of a thermoplastic resin composition excellent in extrusion molding will be described below. For general properties such as mechanical strength and heat resistance, test pieces were molded by injection molding and measured according to the following test methods.

(1) Weight Average Rubber Particle Size “Rubber Age Vol.88 p.484-
490 (1960) by E.I. Schmidt, P .;
H. Sodium alginate method described in "Biddison" (using the fact that the particle size of polybutadiene to be creamed varies depending on the concentration of sodium alginate, the particles having a cumulative weight fraction of 50% based on the cumulative weight fraction of the creamed weight ratio and the sodium alginate concentration) Find the diameter).

(2) Measurement of molecular weight The molecular weight was measured by gel permeation chromatography (GPC). A. Solvent: tetrahydrofuran B. Flow rate: 1.0 ml / min C. Temperature: 23 ° C. D. Sample concentration: 0.1% (injection volume: 0.40 ml) E. Mouth: 0.5 μ filter F. Differential refraction Rate detector (3) Graft rate To a predetermined amount (m) of the graft copolymer, acetone was added, and the mixture was refluxed for 3 hours. p. m. (1000
After centrifugation at 0 G) for 40 minutes, the insoluble matter was filtered, and the insoluble matter was dried under reduced pressure at 60 ° C. for 5 hours, and the weight (n) was measured. The graft ratio was calculated from the following equation. Graft rate (%) = ｛[(n) − (m) × L] /
[(M) × L]｝ × 100 where L is the rubber content of the graft copolymer.

(4) Intrinsic viscosity [η] 200 ml of acetone was added to 1 g of the sample, and the mixture was refluxed for 3 hours. p. m. (10000G)
After centrifugation at for 40 minutes, the insoluble matter is filtered. The filtrate was concentrated with a rotary evaporator, and the precipitate (acetone-soluble matter) was dried under reduced pressure at 60 ° C. for 5 hours. Then, using an Ubbelohde viscometer, a methyl ethyl ketone solution was used.
c was measured, and intrinsic viscosity [η] was calculated.

(5) Measurement of gloss: The surface of the sheet molded product obtained by extrusion molding was measured at an incident angle of 60 ° using a digital variable gloss meter UGV-5D manufactured by Suga Test Instruments Co., Ltd. The surface reflected light of the molded article was measured.

(6) Measurement of sheet thickness: 6
A sheet product of 00 mm x 600 mm was formed. Five thicknesses of the sheet were measured with a dial gauge, and the average value was used.

(7) Vacuum formability: dimension 500 mm × 50
Using a sheet having a thickness of 0 to 1.5 mm and a thickness of 1.5 to 3.0 mm, vacuum molding is performed with a plug-assist type vacuum molding machine, and the thickness of 10 molded products is measured. ,
It was determined as follows. ◎: 0.1 mm or less. ：: More than 0.1 mm and 0.3 mm or less. Δ: More than 0.3 mm and 1 mm or less. X: More than 1 mm.

(8) Flexural modulus: ASTM D790
(23 ° C).

(9) Izod impact strength: ASTM D
256 (23 ° C., with V notch).

(10) MFR (melt flow rate): ISO 113
3 (220 ° C, 98N load).

(11) Kinematic viscosity: JIS K2283 (10
0 ° C).

Reference Example (A) Graft copolymer A1: 120 parts of pure water, 0.5 part of glucose, 0.5 part of sodium pyrophosphate, 0.005 part of ferrous sulfate and A predetermined amount of polybutadiene latex shown in Table 1 was charged, and the temperature in the reactor was raised to 65 ° C. while stirring. When the internal temperature reached 65 ° C., polymerization was started, and a predetermined amount of a mixture of monomers and t-dodecyl mercaptan shown in Table 1 was continuously added over 5 hours. At the same time, an aqueous solution comprising cumene hydroperoxide and potassium oleate shown in Table 1 was continuously added over 7 hours to complete the reaction.

To the obtained latex, 1 part by weight of 2,2′-methylenebis (4-methyl-6-t-butylphenol) was added to 100 parts by weight of the solid content of the latex,
Subsequently, the latex was coagulated with sulfuric acid, neutralized with sodium hydroxide, washed, filtered, and dried to obtain a powdery graft copolymer. The graft ratio of this graft copolymer was 45%.

A2 to A6: Graft copolymers were obtained in the same manner as for A1 at the composition ratios shown in Table 1.

(B) Vinyl copolymer B1: A monomer mixture consisting of 70% by weight of styrene and 30% by weight of acrylonitrile was subjected to bulk polymerization to obtain a pellet-shaped copolymer. The weight average molecular weight of the copolymer was 220,000, and the intrinsic viscosity [η] thereof was 0.60 dl / g.

B2: A monomer mixture consisting of 50% by weight of styrene and 50% by weight of acrylonitrile is subjected to suspension polymerization to form a bead.
Thus, a syrupy copolymer was obtained. The weight average molecular weight of the copolymer was 200,000, and the intrinsic viscosity [η] was 0.55 dl / g.

B3: A monomer mixture consisting of 45% by weight of styrene, 30% by weight of acrylonitrile and 25% by weight of N-phenylmaleimide was emulsion-polymerized to obtain a powdery copolymer. The weight average molecular weight of the copolymer is 200,000,
The intrinsic viscosity [η] was 0.55 dl / g.

B4: A monomer mixture consisting of 45% by weight of styrene, 30% by weight of acrylonitrile and 25% by weight of α-methylstyrene was emulsion-polymerized to obtain a powdery copolymer. The weight average molecular weight of the copolymer was 260,000, and the intrinsic viscosity [η] was 0.75 dl / g.

B5: A monomer mixture consisting of 80% by weight of styrene and 20% by weight of acrylonitrile was subjected to bulk polymerization to obtain a pellet-like copolymer. The weight average molecular weight of the copolymer was 100,000, and the intrinsic viscosity [η] was 0.38 dl / g.

B6: A monomer mixture consisting of 40% by weight of styrene and 60% by weight of acrylonitrile was subjected to bulk polymerization to obtain a pellet-shaped copolymer. The weight average molecular weight of the copolymer is 370,000, and the intrinsic viscosity [η] is 1.30 dl / g.
Met.

(C) Vinyl cyanide copolymer C1: A monomer mixture consisting of 75% by weight of styrene and 25% by weight of acrylonitrile was emulsion-polymerized to obtain a powdery copolymer. The weight average molecular weight of the copolymer was 6.5 million, and the intrinsic viscosity [η] was 6.0 dl / g.

C2: A monomer mixture consisting of 70% by weight of styrene and 30% by weight of acrylonitrile is subjected to suspension polymerization to form a bead.
Thus, a syrupy copolymer was obtained. The weight average molecular weight of the copolymer was 7,000,000, and the intrinsic viscosity [η] was 7.5 dl / g.

C3: 75% by weight of styrene and 25% by weight of acrylonitrile were subjected to bulk polymerization to obtain a pellet-shaped copolymer. The weight average molecular weight of the copolymer was 5.5 million, and the intrinsic viscosity [η] was 6.2 dl / g.

C4: 75% by weight of styrene and 25% by weight of acrylonitrile were emulsion-polymerized to obtain a powdery copolymer. The weight average molecular weight of the copolymer was 4,000,000, and the intrinsic viscosity [η] was 2.5 dl / g.

(D) α-olefin oligomer and / or
Or ethylene and α-olefin colooligomer D1: “Lucant” HC10 manufactured by Mitsui Chemicals, Inc. 100 ° C.
Viscosity at room temperature: 10 cSt D2: "Lucant" HC20 manufactured by Mitsui Chemicals, Inc. 100 ° C
Viscosity at room temperature: 20 cSt D3: "Lucant" HC600 100 manufactured by Mitsui Chemicals, Inc.
Kinematic viscosity at 600C: 600 cSt

[0056]

Examples Examples 1 to 13 and Comparative Examples 1 to 5 (A) Graft copolymer, (B) vinyl copolymer, (C) vinyl copolymer, (D) α described in Reference Examples -Olefin oligomers and / or coloolomers of ethylene and α-olefin were blended at the ratios shown in Tables 2 and 3 and then melt-kneaded with a 40 mmφ single screw extruder to obtain pellet-like resins.

Test pieces were molded from the obtained pellets using an injection molding machine IS-50A manufactured by Toshiba Machine Co., Ltd., and various characteristics were evaluated. The results are shown in Tables 4 to 6.

Examples 1 to 13 show that the thermoplastic resin composition is excellent in extrusion moldability, vacuum moldability, and appearance of the product at the compounding ratio of the present invention.

However, in the comparative example, the vinyl copolymer (C) was used.
In addition, the extrudability, vacuum moldability and appearance of the product are inadequate because any one of the α-olefin oligomer and / or the co-oligomer of ethylene and α-olefin (D) is outside the scope of the present invention. .

[0060]

[Table 1]

[0061]

[Table 2]

[0062]

[Table 3]

[0063]

[Table 4]

[0064]

[Table 5]

[0065]

[Table 6]

[0066]

Industrial Applicability The thermoplastic resin composition of the present invention has excellent extrudability and a good vacuum-molded product can be obtained, whereby material cost can be reduced and productivity can be improved.

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Claims (6)

[Claims] 1. A rubber-reinforced styrenic resin (A) 10 to 50.
Parts by weight, 85 to 45% by weight of an aromatic vinyl monomer (a), 15 to 55% by weight of a vinyl cyanide monomer (b), and another vinyl monomer copolymerizable therewith ( C) 0
A vinyl cyanide-based copolymer (B) obtained by copolymerizing a mixture consisting of 50 to 90% by weight of a resin composition consisting of 50 to 90 parts by weight of an aromatic vinyl-based monomer (A) A vinyl cyanide copolymer (C) having a weight average molecular weight of 5,000,000 or more, obtained by copolymerizing 85 to 45% by weight and 15 to 55% by weight of a vinyl cyanide monomer (b).
0.1 to 10 parts by weight, and α-olefin oligomer
And / or 0.05 to 5 parts by weight of a copolymer of ethylene and an α-olefin (D). 2. An aromatic vinyl-based monomer (i) in the presence of 20 to 80 parts by weight of a rubbery polymer (A-1) having a weight-average particle diameter of 0.1 to 1.5 μm. % Of a vinyl cyanide-based monomer (b), and 0 to 90% by weight of another vinyl-based monomer (c) copolymerizable therewith (A- 2) Graft copolymer (A) 10 to 5 obtained by graft polymerization of 80 to 20 parts by weight
0 parts by weight, 85 to 45% by weight of an aromatic vinyl monomer (A), 15 to 55% by weight of a vinyl cyanide monomer (B), and other vinyl monomers copolymerizable therewith (C) A vinyl cyanide-based copolymer (B) obtained by copolymerizing a mixture of 0 to 40% by weight, and an aromatic vinyl-based monomer per 100 parts by weight of a resin composition of 50 to 90 parts by weight. Body (a) 85
To 45% by weight and a vinyl cyanide monomer (b) 15 to 5
0.1 to 10 parts by weight of a vinyl cyanide copolymer (C) having a weight average molecular weight of 5.5 million or more obtained by copolymerizing 5% by weight, and α-olefin oligomer and / or ethylene and α-olefin Cooligomer (D) 0.0
5-5 parts by weight, and (A) + (B) +
A thermoplastic resin composition wherein the intrinsic viscosity [η] of the acetone-soluble component (C) + (D) is 0.4 to 1.2 dl / g. 3. The thermoplastic resin composition according to claim 1, wherein the intrinsic viscosity [η] of the vinyl cyanide copolymer (C) is 5.0 to 10.0 dl / g. 4. An α-olefin oligomer and / or a co-oligomer of ethylene and α-olefin (D) is 10
The kinematic viscosity at 0C is 5 to 100 cSt.
4. The thermoplastic resin composition according to any one of claims 1 to 3. 5. A sheet product obtained by extruding the thermoplastic resin composition according to claim 1. 6. A sheet product having an average thickness of 3.0 mm or less obtained by extruding the thermoplastic resin composition according to claim 1.