JP2001131398A - Thermoplastic resin composition having excellent heat resistance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition excellent in heat resistance, impact resistance and thinner resistance. SOLUTION: This thermoplastic resin composition in which two kinds of specific ABS-based resins are compounded with a polycarbonate resin, contains (I) the polycarbonate resin, (II) a (rubber-modified) thermoplastic resin comprising (i) a specified rubber-modified thermoplastic resin and/or (ii) a specified thermoplastic resin, and (III) a (rubber-modified) thermoplastic resin comprising (iii) a specific rubber-reinforced thermoplastic resin and/or (iv) a specific thermoplastic resin as main components.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a high impact resistance
Further, the present invention relates to a thermoplastic resin composition having excellent impact resistance and thinner resistance.

[0002]

2. Description of the Related Art Polycarbonate resin (PC resin)
Although it has excellent heat resistance and mechanical properties, it has a feature that the notch sensitivity is sensitive and the impact strength is significantly reduced if the molded product is damaged. In addition, since the heat resistance is too high, the molding temperature must be set high, which is not suitable for a large molded product. On the other hand, ABS resin (acrylonitrile-butadiene-styrene resin) is a molding material that is very well-balanced in terms of moldability, impact strength, dimensions, etc., and is widely used in automobiles, home appliances, OA equipment, and the like. And has the disadvantage of low heat resistance. As means for improving the heat resistance, increasing the amount of the PC resin and copolymerizing α-methylstyrene or the like in the ABS resin are generally adopted. There are drawbacks such as inferior properties and reduced impact resistance. In addition, these molded articles are generally subjected to secondary processing such as painting, but there are problems such as poor thinner resistance, and improvement is desired.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and has a heat resistance, an impact resistance,
An object of the present invention is to provide a thermoplastic resin composition which has excellent thinner resistance and can be used for a wide range of applications.

[0004]

According to the present invention, there are provided (I) 45 to 70% by weight of a polycarbonate resin, (II) 40 to 65% by weight of an aromatic vinyl compound in the presence of a rubbery polymer, (b) ) 35 to 50% by weight of a vinyl cyanide compound and (c) 0 to 25% by weight of another copolymerizable vinyl monomer [however, (a) + (b) + (c) = 100% by weight]
Having a graft ratio of 3
A rubber-modified thermoplastic resin (i) having an intrinsic viscosity [η] of 1 to 100% and a dimethylformamide-soluble component at 30 ° C. of 0.2 to 0.8 dl / g; The intrinsic viscosity [η] is 0.3 to
0.6 dl / g thermoplastic resin (ii),
10 to 60% by weight of a (rubber-modified) thermoplastic resin having a (i) / (ii) ratio of 0 to 100/100 to 0% by weight; and (III) a fragrance in the presence of (III) a rubbery polymer. 65 to 100% by weight of a vinyl group compound, 0 to less than 35% by weight of (b) a vinyl cyanide compound, and 0 to 35% by weight of (c) another copolymerizable vinyl monomer [where (a) +
(B) + (c) = 100% by weight] and a graft ratio of 10 to 100% and 3
A rubber-modified thermoplastic resin (iii) having an intrinsic viscosity [η] of 0.2 to 0.8 dl / g at 0 ° C., which is obtained by polymerizing the above monomer component; (Η) is a thermoplastic resin (iv) having a ratio of 0.3 to 0.6 dl / g, and a ratio (iii) / (iv) of 0 to 100/100 to 0% by weight (rubber modified). 0 to 50% by weight of plastic resin [however, (I) + (II) +
(III) = 100% by weight].

[0005]

DETAILED DESCRIPTION OF THE INVENTION (I) Polycarbonate resin; The (I) polycarbonate resin used in the thermoplastic resin composition of the present invention is obtained by reacting various dihydroxyaryl compounds with phosgene (phosgene method). Or a compound obtained by a transesterification reaction between a dihydroxyaryl compound and diphenyl carbonate (a transesterification method). Preferred polycarbonate resins are aromatic polycarbonates.
Typical aromatic polycarbonates include 2,2'-
Bis (4-hydroxyphenyl) propane, a polycarbonate obtained by the reaction of bisphenol A with phosgene.

Here, the dihydroxyaryl compounds used as the raw materials for polycarbonate include bis (4-hydroxyphenyl) methane, 1,1'-bis (4-hydroxyphenyl) ethane, and 2,2'-bis (4-hydroxyphenyl) methane. Phenyl) propane, 2,2'-bis (4-hydroxyphenyl) butane, 2,2'-bis (4-hydroxyphenyl) octane, 2,2'-bis (4-hydroxyphenyl) phenylmethane, 2,2 '-Bis (4-hydroxy-3-methylphenyl) propane, 2,2'-bis (4-hydroxy-3-t-butylphenyl) propane, 2,2'-bis (4-hydroxy-3-bromophenyl ) Propane, 2,2'-bis (4-hydroxy-
3,5-dichlorophenyl) propane, 1,1'-bis (4-hydroxyphenyl) cyclopentane, 1,1 '
-Bis (4-hydroxyphenyl) cyclohexane,
4,4'-dihydroxydiphenyl ether, 4,4 '
-Dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-dihydroxyphenyl sulfide, 4,
4'-dihydroxy-3,3'-dimethylphenylsulfide, 4,4'-dihydroxy-3,3'-dimethylphenylsulfoxide, 4,4'-dihydroxyphenylsulfoxide, 4,4'-dihydroxyphenylsulfone, 4, 4'-dihydroxy-3,3'-dimethylphenylsulfone, 1,1'-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane,
1'-bis (4-hydroxyphenyl) -3,3-dimethylcyclohexane, 1,1'-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclopentane,
Hydroquinone, resorcin, and the like, which are
One or two or more are used. Particularly preferred is 2,2'-bis (4-hydroxyphenyl) propane, or bisphenol A.

The polycarbonate resin (I) preferably has a viscosity average molecular weight of 15,000 to 40,000,
It is more preferably from 16,000 to 30,000, particularly preferably from 17,000 to 28,000. Higher molecular weights provide higher notched impact resistance, but are less fluid. Further, two or more polycarbonates having different molecular weights can be used.

The proportion of the polycarbonate resin (I) in the thermoplastic resin composition of the present invention is 45 to 70% by weight, preferably 50 to 65% by weight. If the amount is less than 45% by weight, heat resistance and thinner resistance are inferior. On the other hand, if it exceeds 70% by weight, fluidity is remarkably reduced, which is not preferable.

(II) (Rubber-Modified) The thermoplastic resin (II) component contains (a) an aromatic vinyl compound, (b) a vinyl cyanide compound and, if necessary, (c) in the presence of a rubbery polymer. A) a rubber-modified thermoplastic resin (i) obtained by polymerizing a monomer component comprising another copolymerizable vinyl monomer, and / or a thermoplastic resin obtained by polymerizing the above monomer component. (Ii).

Rubber-modified thermoplastic resin (i); Here, examples of the rubbery polymer used for the rubber-modified thermoplastic resin (i) include polybutadiene, polyisoprene, butyl rubber, and styrene-butadiene copolymer (styrene). Content is preferably 5 to 60% by weight), styrene-isoprene copolymer, acrylonitrile-butadiene copolymer, ethylene-α-olefin-based copolymer, ethylene-α-olefin-polyene copolymer, silicone rubber, acrylic rubber , Butadiene- (meth) acrylate copolymer, polyisoprene, styrene-butadiene block copolymer, styrene-isoprene block copolymer, hydrogenated styrene-butadiene block copolymer, hydrogenated butadiene-based copolymer, Ethylene ionomers and the like can be mentioned. AB-styrene and styrene-butadiene block copolymers,
Mold, ABA mold, taper mold, radial teleblock mold, and the like. Further, the hydrogenated butadiene-based polymer has, in addition to the hydrogenated product of the block copolymer, a hydrogenated product of a styrene block and a styrene-butadiene random copolymer block, and a 1,2-vinyl bond content in polybutadiene. It includes 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. These rubbery polymers can be used alone or in combination of two or more.

When a rubbery polymer is used, when two or more kinds of graft polymers (rubber-modified thermoplastic resin) having different rubber particle diameters are used, the thermoplastic resin of the present invention which is more excellent in impact resistance and physical property balance is used. A resin composition is obtained. The preferred particle size of the rubbery polymer is 30 to 300 nm and 50 to 300 nm.
It is preferable to use two types of rubbery polymers having different particle sizes of 0 to 1,000 nm. In this case, even if the graft component (rubber-modified thermoplastic resin) is synthesized in the presence of two types of rubbery polymers having different particle diameters, the graft component (rubber-modified thermoplastic resin) cannot be used.
Various kinds of rubber-modified thermoplastic resins can be blended. The molecular weight of the rubbery polymer is preferably 60,000 or more, more preferably 70,000 or more, in terms of polystyrene equivalent weight average molecular weight. If it is less than 60,000, impact resistance is not exhibited, which is not preferable. Further, the rubbery polymer may have a three-dimensional crosslinked structure.

The proportion of the rubbery polymer in the rubber-modified thermoplastic resin (i) is preferably 3 to 70% by weight, more preferably 5 to 65% by weight, and particularly preferably 7 to 60% by weight. , Most preferably 8 to 50% by weight. If the amount is less than 3% by weight, the impact resistance becomes insufficient. On the other hand, if it exceeds 70% by weight, thermal stability and workability are undesirably reduced.

On the other hand, the monomer components used in the rubber-modified thermoplastic resin (i) include (a) an aromatic vinyl compound,
It comprises (b) a vinyl cyanide compound and, if necessary, (c) another copolymerizable vinyl monomer.

Here, (a) the aromatic vinyl compound includes styrene, α-methylstyrene, p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-t -Butylstyrene, ethylstyrene, vinylnaphthalene, etc., and these can be used alone or in combination of two or more. Preferred aromatic vinyl compounds are styrene or those containing 50% by weight or more of styrene in the aromatic vinyl compound. (A) The proportion of the aromatic vinyl compound in the monomer component is 40 to 65% by weight, preferably 50 to 65% by weight. When the content of the (a) aromatic vinyl compound is less than 40% by weight, the impact resistance is significantly reduced. On the other hand, when the content exceeds 65% by weight, heat resistance is reduced.

The vinyl cyanide compound (b) includes acrylonitrile, methacrylonitrile and the like, and is preferably acrylonitrile. (B) The ratio of the vinyl cyanide compound is 35 to 5 in the monomer component.
0% by weight, preferably 35 to 45% by weight. (B)
When the amount of the vinyl cyanide compound is less than 35% by weight, heat resistance and thinner resistance are reduced. On the other hand, if it exceeds 50% by weight, the impact resistance is significantly reduced.

The ratio (a) / (b) of (a) the aromatic vinyl compound to (b) the vinyl cyanide compound in the monomer component is preferably from 50 to 65/50.
35% by weight, more preferably 55-65 / 45-35
% By weight.

Furthermore, (c) other copolymerizable vinyl monomers include (meth) acrylic acid monomers such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl Acrylate, octyl acrylate,
Acrylic esters such as 2-ethylhexyl acrylate, cyclohexyl acrylate and phenyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate,
Methacrylates such as amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, and benzyl methacrylate; unsaturated acid anhydrides such as maleic anhydride;
Itaconic anhydride and the like; unsaturated acids such as acrylic acid,
Methacrylic acid and the like; maleimide monomers such as N-
Examples thereof include α, β-unsaturated dicarboxylic acid imide compounds such as methylmaleimide, N-butylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide. Preferably, methyl methacrylate, N-phenylmaleimide, and N-cyclohexylmaleimide are used. is there. These (c) other copolymerizable vinyl monomers can be used alone or in combination of two or more.
(C) The proportion of the other copolymerizable vinyl monomer is 0 to 25% by weight, preferably 0 to 20% by weight in the monomer component. (C) The other copolymerizable vinyl monomer is 2
If it exceeds 5% by weight, the balance between heat resistance and impact resistance will be poor.

The graft ratio of the rubber-modified thermoplastic resin (i) constituting the component (II) is 10 to 100%, preferably 20 to 80%. If the graft ratio is less than 10% by weight, the impact resistance is inferior.
It is not preferable because the fluidity decreases. The graft ratio can be easily adjusted by changing the types and amounts of the rubbery polymer, the polymerization initiator, the chain transfer agent, the emulsifier, and the like, and further, the polymerization time, the polymerization temperature, and the like. Here, the graft ratio (%) is determined by putting the rubber-modified thermoplastic resin in an organic solvent (dimethylformamide or methyl ethyl ketone) at room temperature, shaking and dissolving it sufficiently, and then centrifuging it to obtain a dissolved component and an insoluble component. After separating and drying, the insoluble matter (W) is determined,
It is a value determined by the following formula from the rubber amount (R) calculated by the polymerization recipe. Graft ratio (%) = [(WR)
/ R] × 100

The molecular weight of the rubber-modified thermoplastic resin (i) constituting the component (II) is determined by the intrinsic viscosity [η] of the dimethylformamide-soluble component as a matrix component (30 ° C.
Measured in dimethylformamide) 0.2-0.8 d
1 / g, preferably 0.2 to 0.7 dl / g. If the intrinsic viscosity [η] is less than 0.2 dl / g, the impact resistance is poor, while if it exceeds 0.8 dl / g, the fluidity is poor. The intrinsic viscosity [η] can be easily controlled by changing the types and amounts of the polymerization initiator, the chain transfer agent, the emulsifier, the solvent, and the like, and further, the polymerization time, the polymerization temperature, and the like.

Thermoplastic resin (ii); The thermoplastic resin (ii) used for the component (II) is obtained by polymerizing the same monomer components as those used for the rubber-modified thermoplastic resin (i). Can be Here, the types of (a) an aromatic vinyl compound, (b) a vinyl cyanide compound, and (c) other copolymerizable vinyl monomers constituting the monomer component of the thermoplastic resin (ii) are described. The ratio is the same as that of the monomer component in the rubber-modified thermoplastic resin (i), and thus the description is omitted. Further, the preferred weight ratio (a) / (b) of (a) the aromatic vinyl compound and (b) the vinyl cyanide compound in the thermoplastic resin (ii) is the same as that of the rubber-modified thermoplastic resin (i). .

In the component (II), the usage ratio of the rubber-modified thermoplastic resin (i) to the thermoplastic resin (ii) (i) /
(Ii) is 0 to 100/100 to 0% by weight, preferably 10 to 80/90 to 20% by weight.

Component (II) is used in an amount of 10 to 60% by weight, preferably 10 to 60% by weight, in the thermoplastic resin composition of the present invention.
It is 50% by weight, more preferably 10 to 40% by weight. If it is less than 10% by weight, heat resistance is poor, while if it exceeds 60% by weight, impact resistance is poor.

(III) (Rubber-Modified) The thermoplastic resin (III) component contains (a) an aromatic vinyl compound, (b) a vinyl cyanide compound and, if necessary, (c) in the presence of a rubbery polymer. A rubber-modified thermoplastic resin obtained by polymerizing a monomer component composed of another copolymerizable vinyl monomer (i
ii) and / or a thermoplastic resin (iv) obtained by polymerizing the above monomer component. Here, the component (III) constitutes a rubbery polymer or a monomer component except that the proportions of the components (a) to (c) in the monomer component are different.
(C) the type of component, the graft ratio and intrinsic viscosity of the rubber-modified thermoplastic resin (iii), the intrinsic viscosity of the thermoplastic resin (iv), and (ii)
Since the weight ratio of i) to (iv) is the same as that used for the component (II), the description of these points will be omitted. The proportion of the rubbery polymer in the rubber-modified thermoplastic resin (iii) is preferably 3 to 70% by weight, more preferably 5 to 65% by weight, and particularly preferably 7 to 60% by weight.

In the component (III), the proportions of (a) to (c) in the monomer components used in the rubber-modified thermoplastic resin (iii) and the thermoplastic resin (iv) are as follows: Compound 65 to 100% by weight, preferably 55 to 100% by weight, (b) 0 to 35% by weight of vinyl cyanide compound
(C) 0 to 35% by weight of another copolymerizable vinyl monomer, preferably 0 to 2% by weight.
0% by weight. If (a) the aromatic vinyl compound is less than 65% by weight, the impact resistance is poor. When the content of the vinyl cyanide compound (b) is 35% by weight or more, the impact resistance is poor. Further, when the amount of the other copolymerizable vinyl monomer (c) exceeds 35% by weight, the balance between heat resistance and impact resistance deteriorates.

Component (III) is used in an amount of 0 to 50% by weight, preferably 0 to 40% by weight, in the thermoplastic resin composition of the present invention.
%, More preferably 0 to 30% by weight. 50
If the content exceeds% by weight, heat resistance will be poor.

As the radical initiator used for the polymerization of the rubber-modified thermoplastic resins (i) and (iii) and the thermoplastic resins (ii) and (iv) used in the present invention, general ones are used. it can. Specific examples include cumene hydroperoxide, diisopropylbenzene hydroperoxide, potassium persulfate, azobisisobutyronitrile, benzoyl peroxide, lauroyl peroxide, t-butylperoxylaurate, t-butylperoxymonocarbonate And the like. The amount of the radical initiator used is usually 0.1 to the above monomer component.
It is from 0.5 to 5% by weight, preferably from 0.1 to 1% by weight.

In order to exhibit the effects of the present invention,
During the graft polymerization, selection of an organic peroxide and a solvent such that the graft reaction proceeds uniformly, and synthesis of the rubbery polymer by emulsion polymerization, and graft polymerization by emulsion polymerization, or uniformization of the rubbery polymer The intended effect can be obtained by devising a polymerization method such as emulsion polymerization or suspension polymerization of a polymer that has been melted and started polymerization or melt-kneaded in advance.

The thermoplastic resin composition of the present invention may contain, if necessary, glass fiber, carbon fiber, glass beads, wollastonite, rock filler, calcium carbonate, talc,
Fillers such as mica, glass flake, milled fiber, barium sulfate, graphite, molybdenum disulfide, magnesium oxide, zinc oxide whiskers, and potassium titanate whiskers can be used alone or in combination of two or more. By blending these fillers, the thermoplastic resin composition of the present invention can be provided with rigidity, high heat distortion temperature, and the like. Further, by blending the above-mentioned talc, calcium carbonate and the like, it is possible to impart a matting property to the thermoplastic resin composition of the present invention. In addition, the preferable shape of the glass fiber or the carbon fiber is one having a fiber diameter of 6 to 60 μm and a fiber length of 30 μm or more.

Further, the thermoplastic resin composition of the present invention comprises:
Known heat stabilizers, weathering agents, lubricants, coloring agents, antistatic agents,
Additives such as silicone oil can be blended. Among them, phosphorus, phenol, sulfur and the like are preferable as the heat stabilizer. As the weathering agent, benzotriazole, triazine, benzophenone and the like are preferable. As the lubricant, ethylene bisstearylamide, hydrogenated castor oil and the like are preferable. As a coloring agent,
Examples include carbon black and red iron. Examples of the antistatic agent include polyethers and sulfonates having an alkyl group.

The thermoplastic resin composition of the present invention can be obtained by kneading the components using various extruders, Banbury mixers, kneaders, rolls and the like. A preferred manufacturing method is a method using a twin screw extruder. Regarding kneading of each component, kneading may be performed at once, or may be performed by a multi-stage addition method.

The thermoplastic resin composition of the present invention can be formed into various molded products by injection molding, sheet extrusion, vacuum molding, profile extrusion, foam molding and the like.
Various molded products obtained by the above molding method utilize the excellent properties of the molded products, such as wheel covers, rear spoilers,
A. Disc and tray materials for home appliances, vehicles, etc.
It can be used for housing materials and the like.

[0032]

The present invention will be further described below with reference to examples and comparative examples. In Examples and Comparative Examples, parts and% are by weight unless otherwise specified. Various evaluations in Examples and Comparative Examples are values measured as follows.

The average particle size of the dispersed particles was confirmed by an electron microscope that the particle size of the latex synthesized in advance in an emulsified state directly indicates the particle size of the dispersed particles in the resin. Was measured by a light scattering method. The measuring equipment is
Otsuka Electronics Co., Ltd., Laser Particle Size Analysis System LPA-
Using 3100, cumulant method with 70 times integration,
The particle size was measured.

Graft ratio As described in the above text. Intrinsic viscosity [η] The sample was dissolved in an organic solvent, and measured with an Ubbelohde viscometer at a temperature of 30 ° C. As the organic solvent, dimethylformamide was used for the component (II), and methyl ethyl ketone was used for the component (III).

Heat resistance (HDT ) Measured according to ASTM D648. The unit is ° C. Thinner resistance was evaluated by a high-speed surface impact test. Evaluation was made based on the retention rate of the absorbed energy before and after the thinner application. The impact punch is φ1
2.7mm, cradle hole diameter 43mm, hitting speed 2.4
m / s. The impact resistance was measured with a notch according to ASTM D256.
The unit is kg · fcm / cm. Specimen; 2.5 x 1/2 x 1/2 inch, notched.

The components used in this example are as follows. (I) Preparation of Polycarbonate Resin A polycarbonate resin manufactured by Mitsubishi Engineering-Plastics Corporation was used. (I) -1; Iupilon H2000 (I) -2; NOVAREX 7022PJ

(II) Preparation of Components ABS resin [(i) -1]; internal volume 7 equipped with a stirrer
100 liters of ion-exchanged water in a liter glass flask
Parts, disproportionated sodium rosinate 1.5 parts, t-dodecyl mercaptan 0.1 parts, polybutadiene [JSR Corporation
# 0700] 40 parts (in terms of solid content) (average particle size: 2
70 nm), 10 parts of styrene and acrylonitrile 1
0 parts were added and the temperature was raised while stirring. When the temperature reaches 45 ° C, sodium ethylenediaminetetraacetate 0.1
, 0.003 part of ferrous sulfate, 0.2 part of formaldehyde sodium sulfoxylate dihydrate and 15 parts of ion-exchanged water, and 0.1 part of diisopropylbenzene hydroperoxide. The reaction was continued for 1 hour. After that, ion-exchanged water 50
Parts, disproportionated sodium rosinate 1 part, t-dodecyl mercaptan 0.1 part, diisopropyl hydroperoxide 0.2 part, styrene 26 parts and acrylonitrile 1
4 parts of an incremental polymerization component was continuously added over 3 hours to continue the polymerization reaction. After the addition was completed, stirring was further continued for 1 hour, and then 2,2-methylene-bis-
0.2 parts of (4-ethylene-6-t-butylphenol) was added, and the reaction product was taken out of the flask. The latex of the reaction product was coagulated with 2 parts of sulfuric acid, and the reaction product was thoroughly washed with water and then dried at 75 ° C. for 24 hours to obtain a white powder. The polymerization conversion rate is 97.2%, and the graft rate is 60.
%, And the intrinsic viscosity was 0.3 dl / g.

ABS resin (i) -2: ABS resin shown in Table 1 in the same manner as in the method for producing ABS resin (i) -1.
A resin was prepared.

[0039]

[Table 1]

Thermoplastic resin (ii) -1-2: 300 parts of ion-exchanged water, 1.5 parts of sodium oleate, 0.1 part of t-dodecyl mercaptan in a 7-liter glass flask equipped with a stirrer. And the monomer components shown in Table 2 were added, and the temperature was raised while stirring. When the temperature reached 45 ° C., 0.8 parts of potassium persulfate and 0.2 parts of sodium acid sulfite were added, and the reaction was continued for 3 hours. further,
After stirring for 1 hour, 2,2-methylene-bis-
0.2 parts of (4-ethylene-6-t-butylphenol) was added, and the reaction product was taken out of the flask. The latex of the reaction product was coagulated with 2 parts of sulfuric acid, and the reaction product was thoroughly washed with water and then dried at 75 ° C. for 24 hours to obtain a white powder.

[0041]

[Table 2]

Preparation of Component (III) ABS resin (iii) -1: ABS resin shown in Table 3 was prepared in the same manner as in the production method of the above ABS resin (i) -1.

[0043]

[Table 3]

Thermoplastic resin (iv) -1 The thermoplastic resin shown in Table 4 was obtained in the same manner as in the above thermoplastic resins (ii) -1 and (2).

[0045]

[Table 4]

Examples 1 to 6 and Comparative Examples 1 to 5 (Preparation of Thermoplastic Resin Compositions) The blending recipes shown in Tables 5 to 6 were melt-kneaded using an extruder at a temperature of 250 ° C. An evaluation sample was obtained by molding. The results are shown in Tables 5-6.

As is clear from the results shown in Table 5, the thermoplastic resin composition of the present invention exhibited remarkably excellent heat resistance and thinner resistance, and also had excellent impact resistance.
On the other hand, as is clear from Table 6, Comparative Example 1 uses a small amount of the component (II) of the present invention outside the range of the present invention, and is inferior in heat resistance and thinner resistance. Comparative Example 2
In addition, the amount of the component (II) used in the present invention is small outside the range of the present invention, and is inferior in heat resistance and thinner resistance. In Comparative Example 3, the amount of the component (I) used in the present invention was small outside the range of the present invention, and the impact resistance was poor. In Comparative Examples 4 and 5, the amount of the component (I) used in the present invention was small outside the range of the present invention, and the heat resistance and the impact resistance were poor.

[0048]

[Table 5]

[0049]

[Table 6]

[0050]

The thermoplastic resin composition of the present invention is excellent in heat resistance, impact resistance and thinner resistance, and the molded product obtained therefrom can be used as a wheel cover, a rear spoiler by utilizing its excellent properties. It is useful for disc / tray materials, housing materials, etc. for OA / home appliances, vehicle applications, etc.

Continuing from the front page (72) Inventor Takashi Kurata 1-18-1 Kyobashi, Chuo-ku, Tokyo Techno Polymer Co., Ltd. F-term (reference) 4J002 BC04Y BC06Y BN14X BN15X BN16X BN21X CG00W CG01W CG02W FD010 FD060 FD090 GC00 GN00 A12A AA17 AA68 AA69 AB44 AC02 AC10 AC11 AC12 AC16 BA05 BA06 BA09 BA27 BA31 BA32 BA38 GA09

Claims (1)

[Claims] (I) Polycarbonate resins 45 to 70
(A) 40 to 65% by weight of an aromatic vinyl compound in the presence of a rubbery polymer, and (b) a vinyl cyanide compound 35
To 50% by weight and (c) 0 to 25% by weight of another copolymerizable vinyl monomer (provided that (a) + (b) + (c)
= 100% by weight], a graft ratio of 10 to 100%, and an intrinsic viscosity [η] of a dimethylformamide-soluble component at 30 ° C of 0.2.
A rubber-modified thermoplastic resin (i) having a viscosity of ~ 0.8 dl / g,
And a thermoplastic resin (ii) obtained by polymerizing the above monomer component and having the intrinsic viscosity [η] of 0.3 to 0.6 dl / g, wherein the ratio of (i) / (ii) is 0-100 / 1
100 to 0% by weight (rubber modified) thermoplastic resin
60% by weight, and (III) 65-100% by weight of an aromatic vinyl compound in the presence of a rubbery polymer, (b)
0% to less than 35% by weight of vinyl cyanide compound and (c) 0 to 35% by weight of another copolymerizable vinyl monomer
[However, (a) + (b) + (c) = 100% by weight] is obtained by polymerizing a monomer component having a graft ratio of 10%.
A rubber-modified thermoplastic resin (iii) having an intrinsic viscosity [η] of 0.2 to 0.8 dl / g at 30 ° C. and a methyl ethyl ketone-soluble component at 30 ° C., and the above monomer component is polymerized. And the intrinsic viscosity [η] is 0.3 to 0.6.
dl / g thermoplastic resin (iv), (iii) /
(Iv) 0 to 100/100 to 0% by weight (rubber-modified) thermoplastic resin 0 to 50% by weight [however, (I)
+ (II) + (III) = 100% by weight].