JP3235411B2 - Rubber-modified thermoplastic resin and composition thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to
The present invention relates to a rubber-modified thermoplastic resin suitable for imparting excellent mechanical strength such as tensile strength and bending strength and impact resistance, and a composition comprising the rubber-modified thermoplastic resin and another thermoplastic resin.

[0002]

2. Description of the Related Art ABS resins and AES resins are widely known as rubber-modified thermoplastic resins, and are used in large quantities industrially. As a method for producing an ABS resin, the following two methods are generally known. A method obtained by polymerizing 75 to 95% by weight of a monomer composed of styrene and acrylonitrile in the presence of 5 to 25% by weight of a rubbery polymer. A high rubber content ABS resin (hereinafter referred to as "Rubber-rich AB") obtained by polymerizing 55 to 60% by weight of a monomer composed of styrene and acrylonitrile in the presence of 40 to 45% by weight of a rubbery polymer.
S resin)), separately obtained styrene-
A method of obtaining an ABS resin by blending it with an acrylonitrile copolymer (AS resin) and adjusting the content of the rubbery polymer in the blend to 5 to 25% by weight (A obtained by this method)
The BS resin is hereinafter referred to as “blend type ABS resin”). According to the above-mentioned method, various kinds of ABS resins having different qualities can be produced with high productivity by appropriately selecting the amount of the rubber-rich ABS resin and appropriately selecting the type of the AS resin.

However, in the ABS resin industry, further cost reduction is required. As a countermeasure for this cost reduction, there is a method of further increasing the rubber content of the rubber-rich ABS resin and increasing the blending amount of the low-cost AS resin with excellent productivity to increase the productivity of the blend type ABS resin. Conceivable. However, according to our study, if the rubber content of the rubber-rich ABS resin is increased compared to the conventional product, the blend type ABS resin using the same has the mechanical strength and impact resistance of the molded product which is lower than that of the conventional rubber-rich ABS ( Resin) is inferior to a blend type ABS resin using the same. In addition, the rubber-rich ABS resin is used in combination with other thermoplastic resins in addition to the AS resin. However, when the rubber content of the rubber-rich ABS resin is increased, the same problems as described above were observed. .

[0004]

SUMMARY OF THE INVENTION The present invention is directed to a rubber-rich ABS resin having a high rubber content which solves the above-mentioned problems of a rubber-rich ABS resin having a high rubber content, and a rubber-rich ABS resin having the above-mentioned properties. An object is to provide a thermoplastic resin composition comprising a thermoplastic resin.

[0005]

Means for Solving the Problems The inventors of the present invention have made intensive studies on the solution of the above-mentioned problems caused by the rubber-rich ABS resin, and found that the storage elastic modulus of the acetone-insoluble portion of the rubber-rich ABS resin falls within a specific range. By reforming,
The inventors have found that the above-mentioned problems can be solved, and have reached the present invention.

That is, the present invention relates to a rubbery polymer (a)
It is obtained by polymerizing an aromatic vinyl compound (b) and a vinyl cyanide compound (c) in the presence of the component, wherein the content of the component (a) is 50 to 85% by weight, and the content of the component (b) is 5
And the storage elastic modulus of the acetone-insoluble component measured under the following conditions is 0.5 ×
A rubber-modified thermoplastic resin having a graft ratio of 10 ⁸ to 10 × 10 ⁸ Pa and a graft ratio of 10 % by weight or more; and a rubber-modified thermoplastic resin (A) and another thermoplastic resin (B). Wherein the content of the component (a) in the composition is from 3 to 35% by weight. Measurement conditions for storage elastic modulus of acetone-insoluble matter Preparation of test piece Solvent soluble (sol) other than rubber component and graft resin (gel) in rubber-modified thermoplastic resin dissolved in acetone and removed by centrifugation . The obtained gel component is vacuum-dried to remove acetone, and then melt-pressed to form a sheet having a thickness of 1 mm. This sheet is cut into a strip having a length of 40 mm and a width of 5 mm to obtain a test piece. Measurement of storage elastic modulus Polymer Laborator was used as a measuring device.
Dynamic Mechanical manufactured by ies
The measurement is performed under the following conditions using a Thermal Analysis (DMTA) device. Total sample length: 40 mm Sample thickness: 1 mm Measurement temperature: constant at 30 ° C. Jig shape: Doubly supported beam (Dual Cantil)
ever) Sample length between jigs: 5 mm Angular frequency: 2π rad / s (1 Hz)

Hereinafter, the present invention will be described in detail. The rubber-modified thermoplastic resin (A) of the present invention is obtained by polymerizing an aromatic vinyl compound (b) and a vinyl cyanide compound (c) in the presence of a rubber-like polymer (a) component. The content of the component (a) in the thermoplastic resin (A) is 50
-85% by weight, the content of the component (b) is 5-48% by weight,
A rubber-modified thermoplastic resin having a component (c) having a storage elastic modulus of 2 to 45% by weight, an acetone-insoluble portion of (A) of 0.5 × 10 ⁸ to 10 × 10 ⁸ Pa, and a graft ratio of 10 % by weight or more. is there.

The rubbery polymer of the component (a) used in the present invention includes, for example, polybutadiene, polyisoprene, styrene-butadiene copolymer (styrene content 5 to 5).
60% by weight), styrene-isoprene copolymer, acrylonitrile-butadiene copolymer, ethylene-α-olefin-based copolymer, ethylene-α-olefin-polyene copolymer, acrylic rubber, butadiene-
(Meth) acrylate copolymer, polyisoprene, styrene-butadiene block copolymer, styrene-isoprene block copolymer, hydrogenated styrene-butadiene block copolymer, hydrogenated butadiene-based polymer,
Ethylene ionomers and the like can be mentioned. In addition, the styrene-butadiene block copolymer and the styrene-isoprene block copolymer include those having an AB type, ABA type, a taper type, a radial teleblock type, and the like. Furthermore, the hydrogenated butadiene-based polymer has, in addition to the hydride of the above block copolymer, a styrene block and a styrene-butadiene random copolymer block, a 1,2-vinyl bond content in polybutadiene. A hydride of a polymer comprising a block of not more than 20% by weight and a polybutadiene block having a 1,2-vinyl bond content of more than 20% by weight is included. These rubbery polymers are used alone or in combination of two or more.
The preferred component (a) is at least one conjugated diene rubber selected from polybutadiene and styrene-butadiene (preferably 5 to 60% by weight of styrene) copolymer, and more preferably polybutadiene / styrene-styrene. Butadiene copolymer: 50-99 / 1-50
(% By weight).

As the aromatic vinyl compound as the component (b), for example, styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene,
1,1-diphenylstyrene, N, N-diethyl-p-
Aminoethylstyrene, N, N-diethyl-p-aminomethylstyrene, vinylpyridine, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, fluorostyrene, ethylstyrene, vinylnaphthalene, etc., and particularly styrene, α- Methylstyrene is preferred. These aromatic vinyl compounds may be used alone or in combination of two or more.

Examples of the vinyl cyanide compound (c) include acrylonitrile and methacrylonitrile.

For the purpose of the present invention, other monomers can be used as long as they do not hinder. As other monomers, for example, methyl acrylate, ethyl acrylate,
Acrylates such as propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, benzyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate;
Butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, methacrylic acid esters such as benzyl methacrylate; maleic anhydride, itaconic anhydride, citraconic anhydride and the like Unsaturated acid anhydrides; unsaturated acids such as acrylic acid and methacrylic acid; maleimide, N-methylmaleimide, N-butylmaleimide;
Α- such as N- (p-methylphenyl) maleimide, N-phenylmaleimide and N-cyclohexylmaleimide
Or an imide compound of β-unsaturated dicarboxylic acid (also referred to as a maleimide monomer); glycidyl methacrylate;
Epoxy compounds such as allyl glycidyl ether; unsaturated carboxylic amides such as acrylamide and methacrylamide; acrylamine, aminomethyl methacrylate,
Amino group-containing unsaturated compounds such as aminoethyl methacrylate, aminopropyl methacrylate, aminostyrene,
3-hydroxy-1-propene, 4-hydroxy-1-
Butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3-hydroxy-2-
Examples include a hydroxyl group-containing unsaturated compound such as methyl-1-propene, 2-hydroxyethyl acrylate, and 2-hydroxyethyl methacrylate; and an oxazoline group-containing unsaturated compound such as vinyl oxazoline. These monomers are used alone or in combination of two or more. The content of the other monomer is preferably 20% among the components excluding the component (a).
% By weight, more preferably 10% by weight or less.

The content of the component (a) in the rubber-modified thermoplastic resin (A) is 50 to 85% by weight, preferably 52 to 80%.
%, More preferably 55 to 75% by weight, particularly preferably 56 to 73% by weight. When the content of the component (a) is less than 50% by weight, the effect of improving productivity is not sufficient,
On the other hand, if it exceeds 85% by weight, the mechanical strength and impact resistance decrease. Further, (b) in the rubber-modified thermoplastic resin (A)
The component content is 5 to 48% by weight, preferably 5 to 46% by weight.
%, More preferably 10 to 42% by weight, particularly preferably 12 to 40% by weight. The content of the component (c) is 2 to 45% by weight, preferably 2 to 43% by weight, more preferably 3 to 35% by weight, and particularly preferably 4 to 32% by weight. Either the component (b) is less than 5% by weight, the component (b) exceeds 48% by weight, the component (c) is less than 2% by weight, or the component (c) exceeds 45% by weight. In either case, either the effect of improving the mechanical strength or the effect of improving the impact resistance is not sufficient, and both cannot be maintained at the desired levels.

The storage elastic modulus of the acetone-insoluble portion of the rubber-modified thermoplastic resin (A) is 0.5 × 10 ⁸ to 10 × 10 ⁸ P
a, preferably 0.7 × 10 ⁸ to 8 × 10 ⁸ Pa, more preferably 0.8 × 10 ^{8 to} 5 × 10 ⁸ Pa, particularly preferably 1 × 10 ⁸ to 4 × 10 ⁸ Pa. When the storage elastic modulus is less than 0.5 × 10 ⁸ Pa, the mechanical strength is inferior.
If it exceeds 0 × 10 ⁸ Pa, the impact resistance is not sufficient. The conditions for measuring the storage modulus are as described above.

The graft ratio of the rubber-modified thermoplastic resin (A) is 10% by weight or more. When the graft ratio is less than 10 % by weight, mechanical strength and impact resistance are poor. The graft ratio is
It is measured by the following method. Here, the graft ratio refers to the ratio of the copolymer component directly graft-bonded to the rubber-like polymer with respect to the amount of rubber in the rubber-modified thermoplastic resin. This graft ratio can be controlled by the amount of the polymerization initiator, the polymerization temperature, and the like. A specific method of obtaining the graft ratio is as follows. First, 2 g of the rubber-modified thermoplastic resin (A) of the present invention is charged into acetone at room temperature, and sufficiently stirred to obtain an insoluble matter (w).
Ask for. On the other hand, the amount of the rubbery polymer in the insoluble matter (w) can be calculated based on the polymerization recipe. With the calculated total amount of the rubbery polymer as R, the graft ratio is determined from the following equation. Graft ratio (% by weight) = [(w−R) / R] × 100

The content of the components (a), (b) and (c) in the rubber-modified thermoplastic resin (A) can be appropriately adjusted during polymerization by the charged amounts of these components. Further, the component (a) in the rubber-modified thermoplastic resin (A),
The content of the components (b) and (c) can be determined from the charged amounts of these components and the polymerization conversion. As another method, it can be determined by a known quantitative analysis method. The adjustment of the storage modulus of the rubber-modified thermoplastic resin (A) depends on the type of chain transfer agent and initiator used during polymerization.
A method of appropriately selecting the amount, a method of appropriately selecting the polymerization temperature,
It can be carried out by appropriately selecting the gel content and the molecular weight of the rubbery polymer as the component (a). Examples of the method for producing the rubber-modified thermoplastic resin (A) include a solution polymerization method, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, and a method combining these methods. A preferred polymerization method is an emulsion polymerization method, and generally known polymerization auxiliaries used in the emulsion polymerization method can be used.

Examples of the polymerization initiator used in the production of the rubber-modified thermoplastic resin (A) of the present invention include various organic peroxides such as hydroperoxides, alkyl peresters and percarbonates. Oxide, diisopropylbenzene hydroperoxide, and t-butylperoxyisopropyl carbonate. In particular, when t-butyl peroxyisopropyl carbonate is used, the effect of the present invention can be further improved. The preferred amount of the initiator is 0.1 to 100 parts by weight of the total of the rubber component and the monomer component.
2 parts by weight. Examples of the chain transfer agent include halogenated hydrocarbons (eg, chloroform, bromoform, etc.), mercaptans (eg, n-dodecyl mercaptan, t-dodecyl mercaptan, n-octyl mercaptan, n-hexadecyl mercaptan, etc.), terpenes (For example, dipentene, terpinolene, etc.) and α-methylstyrene dimer.

The intrinsic viscosity (at 30 ° C. in methyl ethyl ketone) of the methyl ethyl ketone-soluble component of the rubber-modified thermoplastic resin (A) is preferably 0.15 to 1.5 dl / g, more preferably 0.2 to 1 dl / g. 0.2 dl / g, more preferably 0.25 to 1 dl / g, particularly preferably 0.3 to 0.8 dl / g.

The other thermoplastic resin (B) according to claim 2 mixed with the rubber-modified thermoplastic resin (A) includes, for example,
ABS resin / A having a rubbery polymer content of less than 50% by weight
ES resins, AAS resins, AS resins, styrene resins such as HIPS, PS; olefin resins such as polyethylene and polypropylene; PA6, PA66, PA46, P
Polyamide resins such as A12; Polyester resins such as polybutylene terephthalate, polyethylene terephthalate, and polyarylate; Polyphenylene ether-based resins such as polycarbonate resin, polyphenylene ether or polyphenylene ether / styrene-based resin; Polyacetal, vinyl chloride resin, polysulfone, PPS,
There are polyether sulfone, ethylene-vinyl acetate copolymer, EVOH and the like, and these can be used alone or in combination of two or more.

Other preferable thermoplastic resins (B) include the following a. , B. Each alone or a. And b.
In combination. a. A monomer comprising at least two groups selected from the group consisting of an aromatic compound, a vinyl cyanide compound, a (meth) acrylate ester and a maleimide monomer in the presence of a rubber-like polymer; And a rubber-modified thermoplastic resin having a rubbery polymer content of less than 50% by weight. Here, the rubbery polymer and the monomer include those described above. Further, the intrinsic viscosity (at 30 ° C. in methyl ethyl ketone) of the methyl ethyl ketone-soluble component of the rubber-modified thermoplastic resin is preferably from 0.2 to 1 dl / g, more preferably from 0.3 to 0.6 dl / g. b. An aromatic vinyl compound, a vinyl cyanide compound,
It is obtained by polymerizing at least two kinds of monomers selected from the group of (meth) acrylic acid esters and maleimide monomers, and has an intrinsic viscosity (measured at 30 ° C. using methyl ethyl ketone as a solvent). Preferably 0.2-1.3d
1 / g, more preferably 0.3 to 1 dl / g, particularly preferably 0.35 to 0.7 dl / g.

The above a. As, for example, ABS resin,
AES resin, AAS resin, MBS resin and the like,
Among them, ABS resin and AES resin are preferred. B. Examples thereof include the following copolymers. I. A copolymer of an aromatic vinyl compound and a vinyl cyanide compound. A preferable composition ratio is such that the former monomer is 50 to 99.
% By weight, the latter being from 1 to 50% by weight. B. Copolymer of aromatic vinyl compound and (meth) acrylate. C. Aromatic vinyl compound, maleimide monomer and, if necessary, vinyl cyanide compound and / or (meth)
A copolymer composed of acrylic acid esters. In addition, an unsaturated acid anhydride monomer is used in place of the maleimide-based monomer, the obtained copolymer is imidized, and the obtained post-imide type copolymer is also included herein. The aromatic vinyl compound, vinyl cyanide compound, (meth) acrylic acid ester, and maleimide-based monomer here are the same as those described above.

The rubber-modified thermoplastic resin (A) is composed of a rubber-modified thermoplastic resin (A) and another thermoplastic resin (B). The respective components are appropriately blended so that the rubbery polymer as the component (a) of A) is preferably contained in the composition at 3 to 35% by weight. More preferably, the content of the component (a) is 5 to 25% by weight. If the content of the component (a) is less than 3% by weight, sufficient impact resistance cannot be obtained. On the other hand, if it exceeds 35% by weight, the molded product becomes soft, which is not preferable. When a rubber-modified thermoplastic resin (C) other than the rubber-modified thermoplastic resin (A) of the present application is used as the other thermoplastic resin (B), the rubber contained in the rubber-modified thermoplastic resin (C) is used. The treatment of the state polymer (hereinafter referred to as “a ′ component”) is as follows. a 'component is also a
It shall be regarded as a component and satisfy the following conditions. (A +
The content of a ′) is 3 to 35% by weight and the content of a is 3 to 35%.
35% by weight. Preferably, the content of (a + a ') is 5 to 25% by weight and the content of a is 5 to 25% by weight.

The thermoplastic resin composition according to claim 2 of the present invention comprises a rubber-modified thermoplastic resin (A) and a thermoplastic resin (B).
It is manufactured by kneading various additives as necessary. As a kneading method, there is a method using an extruder, a roll, a Banbury mixer, a kneader, or the like. A preferable method is a method using an extruder, and examples of the extruder include a single screw extruder and a twin screw extruder. When kneading the various components using the above-described kneading method, all the components may be kneaded all at once, some of the components may be kneaded first, and the remaining components may be mixed or divided and added. It may be kneaded. Further, various additives can be added to the rubber-modified thermoplastic resin (A) as needed. When kneading is required, kneading can be performed by the method described above. As various additives, known colorants, pigments,
Examples include lubricants, weathering agents, antistatic agents, antioxidants, flame retardants, heat aging inhibitors, plasticizers, antibacterial and antifungal agents.
The thermoplastic resin composition according to claim 2 of the present invention comprises injection molding,
Various molded products can be formed by sheet extrusion, vacuum molding, profile extrusion, injection press, foam molding, blow molding, hollow molding, and the like.

[0023]

The present invention will now be described more specifically with reference to examples. In the examples, parts and% are based on weight unless otherwise specified. Various evaluations in the examples are values measured as follows. [Evaluation method] (1) Measurement of storage elastic modulus Method of preparing test piece for measuring storage elastic modulus Solvent soluble components (sol components) other than rubber and graft resin components (gel components) of the graft copolymer were dissolved in acetone. And removed by centrifugation. The obtained gel component was vacuum-dried to remove acetone, and then melt-pressed to a thickness of 1 μm.
mm sheet. This sheet has a length of 40 mm and a width of 5
The test piece was cut out into a strip of mm. Measurement conditions of storage elastic modulus Measurement device: Polymer Laboratories
Dynamic Mechanical Thermo
l Analysis (DMTA) device Total sample length: 40 mm Sample thickness: 1 mm Measurement temperature: 30 ° C. Jig shape: Dual cantilever (Dual Cantil)
ever) Sample length between jigs: 5 mm Angular frequency: 2π rad / s (1 Hz)

(2) Method for Mixing Rubber-Modified Thermoplastic Resin (A) and Thermoplastic Resin (B) The rubber-modified thermoplastic resin (A), the thermoplastic resin (B) and the additive are added in the proportions shown in Table 2. The mixture was mixed using a Henschel mixer, and the mixture was obtained with an extruder having a cylinder set temperature of 200 ° C. to obtain pellets.

(3) Method for Forming Test Piece for Izod Impact Strength Measurement, Tensile Test, and Bending Test A test for measuring Izod impact strength under the following molding conditions using the pellet obtained by the method of (2) above as a molding material. Pieces, test pieces for tensile tests and test pieces for bending tests were formed. Molding machine: 5 oz. In-line screw type molding machine Mold temperature: 50 ° C. ± 5 ° C. Molding machine setting condition: Cylinder set temperature: 200 ° C. Injection pressure: Primary pressure 75 to 95 kg / cm ² G, secondary pressure 5
0 kg / cm ² G Back pressure: 5 kg / cm ² G Molding cycle: injection 15 seconds, loading 10 seconds, curing 40 seconds, cycle start 2 seconds

(4) Measurement of Izod impact strength ASTM D256 (１ ／), with notch, unit = kg
f · cm / cm).

(5) Measurement of Tensile Strength Measurement of tensile strength and elongation strength was performed according to ASTM D638.
Performed according to. Specimen: ASTM Type I Length: 21.6 cm Central width: 1.27 cm Thickness: 0.32 cm Tensile speed: 5.0 cm / min Tensile strength TS (kgf / cm ² ) and elongation E of each specimen (%) Was calculated.

(6) Measurement of Flexural Strength The flexural strength was measured according to ASTM D790. Specimen: Length: 10.0 cm Width: 2.5 cm Thickness: 0.32 cm Bending speed: 1.5 cm / min Flexural strength FS (kgf / cm ² ) and flexural modulus FM (kgf / cm) of each specimen ² ) was calculated.

[Reference Example 1. Method for Producing Rubber-Modified Thermoplastic Resin (A)] In a flask, 54 parts of polybutadiene rubber latex in terms of solid content and 6 parts of styrene-butadiene copolymer rubber latex in terms of solid content are added, and 150 parts of ion-exchanged water is added.
Parts, 7 parts of styrene, 3 parts of acrylonitrile, and 0.2 part of t-dodecyl mercaptan, and the temperature in the flask was raised to 60 ° C.
Parts, a solution of 0.01 part of ferrous sulfate heptahydrate and 0.4 part of glucose dissolved in 20 parts of ion-exchanged water was added, and 0.1 part of cumene hydroperoxide was further added to initiate polymerization, The bath temperature was maintained at 70 ° C. After polymerization for 1 hour, 22 parts of styrene, 8 parts of acrylonitrile, 0.5 part of t-dodecyl mercaptan, and 0.2 part of cumene hydroperoxide were continuously added over 2 hours.
The reaction was completed by polymerizing for an hour. The obtained copolymer latex was coagulated using sulfuric acid, washed with water and dried. Table 1
Was obtained.

[0030]

[Table 1]

ABS-2 and ABS-4 in Table 1 represent A
Polymerization was carried out under the same conditions as ABS-1 and ABS-3 except that t-butylperoxyisopropyl carbonate was used instead of cumene hydroperoxide of BS-1 and ABS-3. ABS-3,5,
6 and 7 are ABS-1 formulations in which the amount of rubber, the amount of t-dodecyl mercaptan, and the amount of initiator are appropriately varied, and the others are ABS.
-1 was performed under the same conditions. (Thermoplastic resin) AS-1; a copolymer of 75% styrene and 25% acrylonitrile; [η] is 0.6 dl / g AS-2; a copolymer of 75% styrene and 25% acrylonitrile; [Η] (intrinsic viscosity of methyl ethyl ketone-soluble component) is 0.4 dl / g Examples 1 to 6 and Comparative Examples 1 to 3 Examples 1 to 6 are rubber-modified thermoplastic resins having a storage modulus within the range of the present invention. Is a thermoplastic resin composition. Table 2 shows the formulation and evaluation results.

[0032]

[Table 2]

Comparative Examples 1 and 3 are thermoplastic resin compositions using a rubber-modified thermoplastic resin having a storage modulus lower than the range of the present invention. Comparative Example 2 has a storage modulus lower than the range of the present invention. This is a thermoplastic resin composition using a rubber-modified thermoplastic resin. Table 2 shows the formulation and evaluation results. Compared with Examples 1-4, Comparative Examples 1 and 3 are inferior in mechanical strength, and Comparative Example 2 is inferior in impact strength. That is, it is apparent that Examples 1 to 4 are excellent in impact resistance and mechanical strength of the molded product.

[0034]

The rubber-modified thermoplastic resin of the present invention (A)
The molded product obtained by blending with another thermoplastic resin (B) has excellent impact resistance and mechanical strength even if it has a high rubber component content. And since it has a high rubber component content, the effect of improving impact resistance and mechanical strength can be obtained with a small amount, so that it is easy to cope with deployability. In addition, since other thermoplastic resins such as AS resin are excellent in productivity and low in cost, by blending with them, it is possible to mass-produce high productivity and low cost ABS resin. .

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-62-48709 (JP, A) JP-A-2-302414 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 279/00 C08L 55/02 C08L 101/02

Claims (2)

(57) [Claims] An aromatic vinyl compound (b) and a vinyl cyanide compound (c) are polymerized in the presence of a rubber-like polymer (a) component, and the content of the component (a) is 50 to 50.
85% by weight, the content of the component (b) is 5 to 48% by weight,
The storage elastic modulus of the component (c) is 2 to 45% by weight and the acetone-insoluble content measured under the following conditions is 0.5 × 10 ⁸ to 10 ×.
A rubber-modified thermoplastic resin having a graft ratio of 10 ⁸ Pa and a graft ratio of 10 % by weight or more. Measurement conditions for storage elastic modulus of acetone-insoluble matter Preparation of test piece Solvent soluble (sol) other than rubber component and graft resin (gel) in rubber-modified thermoplastic resin dissolved in acetone and removed by centrifugation . The obtained gel component is vacuum-dried to remove acetone, and then melt-pressed to form a sheet having a thickness of 1 mm. This sheet is cut into a strip having a length of 40 mm and a width of 5 mm to obtain a test piece. Measurement of storage elastic modulus Polymer Laborator was used as a measuring device.
Dynamic Mechanical manufactured by ies
The measurement is performed under the following conditions using a Thermal Analysis (DMTA) device. Total sample length: 40 mm Sample thickness: 1 mm Measurement temperature: constant at 30 ° C. Jig shape: Doubly supported beam (Dual Cantil)
ever) Sample length between jigs: 5 mm Angular frequency: 2π rad / s (1 Hz) 2. A composition comprising the rubber-modified thermoplastic resin (A) according to claim 1 and another thermoplastic resin (B), wherein the content of the component (a) in the composition is from 3 to 35. A thermoplastic resin composition which is wt%.