JPH11199747A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inorganic-filled thermoplastic resin which can give a molding excellent in impact resistance, rigidity, appearance, and weld strength and to provide a molding made therefrom. SOLUTION: There are provided a thermoplastic resin mainly consisting of (A) 10-60 pts.wt. (rubber-modified) thermoplastic resin obtained by polymerizing (b) at least one vinyl monomer selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, (meth)acrylic esters, acid- anhydride-free unsaturated compounds, and maleimide compounds in the presence or absence of (a) a rubbery polymer, (B) 70-10 pts.wt. polycarbonate; (C) 1-20 pts.wt. inorganic filler having a mean particle diameter of 1-15 μm and a pH in the range of 8-10, the total of components A, B, and C being 100 pts.wt., or a composition prepared by mixing 100 pts.wt. above thermoplastic resin with (D) 1-10 pts.wt. thermoplastic resin obtained by grafting a vinyl monomer in the presence of a polycarbonate; and a molding prepared by molding either of the above compositions.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a (rubber-modified) thermoplastic resin, a polycarbonate and an inorganic filler, and, if necessary, a thermoplastic resin obtained by graft-polymerizing a vinyl monomer to a polycarbonate. The present invention relates to a thermoplastic resin composition having excellent impact resistance, rigidity, and weld strength, and a molded product thereof.

[0002]

2. Description of the Related Art Conventionally, an alloy material of ABS resin and polycarbonate has been known as a material having excellent heat resistance, impact resistance, and moldability. In recent years, as the thickness and weight of resin molded products have been reduced, the demand for imparting rigidity to resins has increased. Glass fiber, carbon fiber,
Attempts have been made to blend inorganic fillers and the like. However, in the alloy material of ABS resin and polycarbonate,
When glass fiber, carbon fiber, and the like are blended, appearance is impaired, and impact resistance and weld strength are also poor. Also, when an inorganic filler is blended, there is a problem that impact resistance and weld strength are inferior.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and solves the above-mentioned problems by using an inorganic filler having a certain average particle size and pH. It is an object of the present invention to provide a thermoplastic resin composition containing an inorganic filler excellent in impact resistance, rigidity, molded appearance, and weld strength.

[0004]

According to the present invention, there is provided an aromatic vinyl compound, a vinyl cyanide compound, a (meth) acrylic acid ester, an acid ester, or a compound (A) in the presence or absence of a rubbery polymer (a). 10 to 60 parts by weight of a (rubber-modified) thermoplastic resin obtained by polymerizing at least one vinyl monomer (b) selected from the group consisting of an anhydride group-containing unsaturated compound and a maleimide compound; ) Polycarbonate 70-1
0 parts by weight, and (C) the average particle size is 1 to 15 μm,
And a thermoplastic resin composition containing 1 to 20 parts by weight of an inorganic filler having a pH of 8 to 10 [(A) + (B) + (C) = 100 parts by weight] as a main component (hereinafter referred to as “ A first composition). Further, the present invention relates to a thermoplastic resin obtained by blending 1 to 10 parts by weight of a thermoplastic resin obtained by graft polymerization of a vinyl monomer in the presence of (D) polycarbonate with respect to 100 parts by weight of the first composition. A resin composition (hereinafter also referred to as a “second composition”;
The present invention also provides a molding composition obtained by molding the first composition and / or the second composition. Goods.

[0005]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The component (A) used in the thermoplastic resin composition (first and second compositions) of the present invention comprises the above-mentioned vinyl polymer in the presence or absence of a rubbery polymer (a). It is a (rubber-modified) thermoplastic resin obtained by polymerizing the system monomer (b). Here, as the rubbery polymer (a) used for the component (A), for example, polybutadiene, butadiene-
Styrene copolymer, butadiene-acrylonitrile copolymer, ethylene-propylene- (non-conjugated diene) copolymer, ethylene-butene-1- (non-conjugated diene) copolymer, isobutylene-isoprene copolymer, acrylic rubber, Examples include styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, hydrogenated diene (block, random, or homo) polymers such as SEBS, polyurethane rubber, silicone rubber, and the like. Among them, polybutadiene, butadiene-styrene copolymer, ethylene-propylene- (non-conjugated diene) copolymer, hydrogenated diene polymer, and silicone rubber are preferable. When a silicone rubber is used, a graft crossing agent (for example, one containing a vinyl group or γ-methacryloxypropylmethyldimethoxysilane) in the silicone rubber is used in an amount of from 0.01 to 0.01%.
When a silicone rubber copolymerized at about 10% by weight is used, the thermoplastic resin composition excellent in impact resistance of the present invention can be obtained.

When the rubber-like polymer (a) is used, when two or more (A) rubber-modified thermoplastic resins having different rubber particle diameters are used, the present invention is more excellent in impact resistance and physical property balance. A thermoplastic resin composition is obtained. Preferred particle sizes are 800 to 1,800 angstroms and 1,8
It is preferable to use two kinds of the component (a) having different particle sizes of about 00 to 4,800 angstroms. In this case, even if the component (A) is produced in the presence of two types of rubbery polymers, two types of (A) components having different rubber particle diameters can be used. The above rubbery polymer (a) is used alone or in combination of two or more.

Among the vinyl monomers (b), aromatic vinyl compounds include 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, dibromostyrene, monofluorostyrene, ethylstyrene, Examples thereof include vinyl naphthalene, and styrene, α-methylstyrene, and p-methylstyrene are particularly preferable. Among the vinyl monomers (b), examples of the vinyl cyanide compound include vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, and acrylonitrile is preferable.

Among the vinyl monomers, (meth) acrylates include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate,
Cyclohexyl acrylate, dodecyl acrylate,
Acrylic esters such as octadecyl acrylate, phenyl acrylate and 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 Examples include methacrylates such as methacrylate and benzyl methacrylate, and methyl methacrylate and butyl acrylate are preferred.

Among the vinyl monomers (b), examples of the unsaturated compound containing an acid anhydride group include maleic anhydride, itaconic anhydride and citraconic anhydride, and maleic anhydride is preferred. Among the vinyl monomers (b), examples of the maleimide compound include maleimide, N-methylmaleimide, N-butylmaleimide, N- (p-methylphenyl) maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide. , Α, β-unsaturated dicarboxylic acid maleimide compounds, and N-phenylmaleimide is preferred. Particularly, in the vinyl monomer (b),
By using 20 to 80% by weight of the maleimide-based compound, the heat resistance of the thermoplastic resin composition of the present invention can be improved. The above vinyl monomers (b) can be used alone or as a mixture of two or more.

The (A) (rubber-modified) thermoplastic resin of the present invention may be obtained by graft-polymerizing a vinyl monomer (b) in the presence of a rubber-like polymer (a). A polymer obtained by (co) polymerizing the vinyl monomer (b) in the absence of the polymer (a) may be used, or a mixture of the above (1) and (2) may be used.

The proportion of the rubbery polymer (a) in the (A) (rubber-modified) thermoplastic resin is from 0 to 90% by weight, preferably from 10 to 80% by weight, more preferably from the viewpoint of impact resistance. Is 20 to 70% by weight, while the proportion of the vinyl monomer (b) is 100 to 10% by weight, preferably 90 to 20% by weight, more preferably 80 to 30% by weight [where (a ) + (B) = 100% by weight]. If the amount of the component (a) exceeds 90% by weight, poor appearance and a reduction in molding workability are not preferred.

The (A) (rubber-modified) thermoplastic resin of the present invention can be produced by known polymerization methods such as emulsion polymerization, solution polymerization, suspension polymerization and bulk polymerization. In addition, as a radical initiator at the time of graft polymerization, a general one can be used. Specific examples include cumene hydroperoxide, diisopropylbenzene hydroperoxide, potassium persulfate, azobisisobutyronitrile, benzoyl peroxide, lauroyl peroxide,
t-butyl peroxylaurate, t-butyl peroxy monocarbonate and the like.

[0013] Of the thermoplastic resin (A) (rubber modified) thus obtained, the graft ratio when the rubbery polymer (a) is used is preferably 10 to 150% by weight.
More preferably 30 to 130% by weight, particularly preferably 4% by weight.
0 to 120% by weight. If the graft ratio is less than 10% by weight, the resulting thermoplastic resin composition has poor appearance and reduced impact strength, which is not preferable.
If it exceeds, the moldability will be poor. Here, the graft ratio is determined by the following formula, where x is a rubber component in 1 g of the component (A) and y is a methyl ethyl ketone insoluble component of the component (A). Graft ratio (% by weight) = {(y−x) / x} × 100

The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the methyl ethyl ketone-soluble component (matrix resin) as the component (A) is preferably 0.1 to 0.1.
1.5 dl / g, more preferably 0.3 to 1.0 dl
/ G. When the intrinsic viscosity [η] is within this range, a thermoplastic resin composition of the present invention having excellent impact resistance and moldability (flowability) can be obtained.

(A) (Rubber Modified) Typical examples of thermoplastic resins include ABS resin, AES resin, AS resin, thermoplastic resin obtained by grafting AS resin to silicone rubber, styrene-methyl methacrylate copolymer, and styrene. —N-phenylmaleimide copolymer, polystyrene, polymethyl methacrylate and the like. Above all, ABS resin, AS resin and AES resin are preferable. Of these, AB
As the S resin or the AES resin, the preferable amount of rubber is 5
-65% by weight, more preferably 15-55% by weight, a preferred graft ratio is 40-150% by weight, more preferably 50-120% by weight, and a preferred intrinsic viscosity [η] of the matrix resin is 0.1-1.5dl. / G. As the AS resin, the copolymerization amount of acrylonitrile is preferably 10 to 45% by weight, more preferably 15 to 3% by weight.
It is 5% by weight, particularly preferably 20 to 32% by weight, and the intrinsic viscosity [η] is preferably 0.1 to 1.5 dl / g, more preferably 0.2 to 0.8 dl / g.

The (A) (rubber-modified) thermoplastic resin may be copolymerized with a vinyl monomer having a functional group. Examples of the functional group include an epoxy group, a hydroxyl group, a carboxylic acid group, an amino group, an amide group, and an oxazoline group. Preferable examples of the functional group-containing vinyl monomer include glycidyl methacrylate, glycidyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, acrylamide, acrylic acid, methacrylic acid, and vinyl oxazoline. By copolymerizing these functional group-containing vinyl monomers, the interfacial adhesion (compatibility) with the polycarbonate (B) can be increased. The copolymerization amount of the functional group-containing vinyl monomer in the component (A) is preferably 0.1 to 15% by weight, more preferably 0.5 to 12% by weight.

The (A) (rubber-modified) thermoplastic resin may be blended singly or as a blend of two or more components (A). Preferred combinations are shown below, but are not limited to these combinations. ABS resin ABS resin / AS resin AES resin / AS resin Polyorganosiloxane reinforced resin (silicone rubber grafted with AS resin) / AS resin

Next, the thermoplastic resin composition of the present invention (No. 1)
(B) polycarbonate used in the composition (2).
Examples include those obtained by reacting various dihydroxyaryl compounds with phosgene (phosgene method) and those obtained by transesterification of dihydroxyaryl compounds with diphenyl carbonate (ester exchange method). Preferred polycarbonate resins are
It is an aromatic polycarbonate. A typical aromatic polycarbonate is a polycarbonate obtained by reacting 2,2'-bis (4-hydroxyphenyl) propane with phosgene.

Here, as the dihydroxyaryl compound as a raw material of the polycarbonate, 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, 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'-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-
3,3'-dimethyldiphenyl ether, 4,4'-dihydroxyphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethylphenyl sulfide, 4,4 '
-Dihydroxyphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethylphenyl sulfide, 4,
4'-dihydroxydiphenylsulfoxide, 4,4 '
-Dihydroxy-3,3'-dimethylphenyl sulfide, 4,4'-dihydroxyphenyl sulfoxide,
4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone, hydroquinone, resorcin, and the like. Are used alone or in combination of two or more. Particularly preferred is 2,2'-bis (4-hydroxyphenyl) propane, or bisphenol A.

The weight average molecular weight of the polycarbonate (B) is preferably 15,000 to 40,000, more preferably 17,000 to 30,000, and particularly preferably 18,000 to 28,000. The higher the molecular weight, the higher the impact resistance, but the lower the flowability. Therefore, the most preferable weight average molecular weight is 18,000 to above.
28,000. Further, two or more polycarbonates having different molecular weights can be used.

Next, the thermoplastic resin composition of the present invention (No. 1)
(C) inorganic filler used in the composition
Wollastonite, talc, mica, magnesium oxide,
Examples thereof include zinc oxide whiskers and potassium titanate whiskers, and these can be used alone or as a mixture of two or more. Among these, talc, wollastonite and mica are preferred, and talc is more preferred.

(C) The average particle size of the inorganic filler is from 1 to 15
μm, preferably 1.2 to 6 μm. Average particle size is 1
If it is less than μm, the extrusion processability is poor, while 15 μm
If more, the appearance is inferior. In addition, (C) p of the inorganic filler
H is from 8 to 10, preferably from 8.5 to 9.5. p
If H is out of this range, the thermal stability at the time of melting is inferior, and good impact resistance cannot be obtained. In particular, the molecular weight of the polycarbonate (B) decreases, which is not preferable. (C) When talc is used as the inorganic filler, the preferable whiteness range of talc is 85 to 99%, more preferably 95 to 9%.
9%. If the whiteness of talc is out of this range, a molded article having a good molded appearance cannot be obtained.

Next, the component (D) used in the second composition of the present invention is a thermoplastic resin obtained by graft-polymerizing a vinyl monomer in the presence of polycarbonate.
Here, the polycarbonate used for the component (D) is:
The same as the polycarbonate used for the component (B). The weight average molecular weight of the polycarbonate used for the component (D) is preferably from 20,000 to 40,000.
00, more preferably 22,000 to 36,000,
Particularly preferably, it is 22,000 to 24,000.

The vinyl monomer used for the component (D) is the same as the vinyl monomer (b) used for the (A) (rubber-modified) thermoplastic resin, and is an aromatic vinyl monomer. In addition to at least one selected from the group consisting of compounds, vinyl cyanide compounds, (meth) acrylic acid esters, acid anhydride group-containing unsaturated compounds and maleimide-based compounds, the above-mentioned functional group-containing vinyl monomers can be mentioned. . Of these vinyl monomers, styrene and acrylonitrile are particularly preferred.

(D) As a method for producing a thermoplastic resin,
For example, in the aqueous phase, in the presence of polycarbonate pellets or powder, impregnated with a vinyl monomer containing an aromatic vinyl compound, and added with a monomer peroxide at a temperature of 90 ° C or higher, preferably 105 ° C or higher. Initiate graft polymerization with a radical initiator. (D) As for the ratio of the polycarbonate and the vinyl monomer in the thermoplastic resin, polycarbonate is preferably 90 to 10% by weight, more preferably 70 to 30% by weight, and particularly preferably 60 to 4% by weight.
0% by weight, preferably 10 to 90% by weight, more preferably 30 to 70% by weight, particularly preferably 40 to 60% by weight, of the vinyl monomer. Particularly preferred thermoplastic resin (D) is a thermoplastic resin obtained by graft-polymerizing styrene / acrylonitrile onto a polycarbonate, wherein the amount of acrylonitrile is 20 to 40% by weight, especially 25 to 30% by weight in the vinyl monomer. is there.

(D) The preferred melt flow rate of the thermoplastic resin (measurement conditions: according to ASTM D1238, measurement temperature: 240 ° C., load: 10 kg) is 20 to 60 g.
/ 10 min, more preferably 35 to 50 g / 10 min, particularly preferably 40 to 48 g / 10 min. If the melt flow rate is out of this range, the second composition of the present invention having good molded appearance cannot be obtained. Further, (D) a preferable heat distortion temperature of the thermoplastic resin (measurement condition; ASTM D64)
8-82) is 110 to 150 ° C, more preferably 1 to 150 ° C.
20-140 ° C. When the heat distortion temperature is outside this range, the second composition of the present invention having good heat resistance cannot be obtained.

The mixing ratio of the first composition of the present invention is (A)
Component 10 to 60 parts by weight, preferably 20 to 50 parts by weight,
More preferably 25 to 40 parts by weight, component (B) 70 to
10 parts by weight, preferably 60 to 35 parts by weight, more preferably 48 to 35 parts by weight, 1 to 20 parts by weight of the component (C),
Preferably from 2 to 15 parts by weight, more preferably from 3 to 12 parts by weight.
Parts by weight (however, (A) + (B) + (C) = 100 parts by weight). When the compounding ratio of the component (A) is less than 10 parts by weight, the moldability is poor. On the other hand, when it exceeds 60 parts by weight, the heat resistance is poor. Further, the mixing ratio of the component (B) is 70
If the amount exceeds the weight part, the fluidity and molding processability are inferior.
If the amount is less than 10 parts by weight, heat resistance is poor. Further, if the compounding ratio of the component (C) is less than 1 part by weight, the effect of improving rigidity is not sufficient, while if it exceeds 20 parts by weight, moldability and impact resistance are poor.

Next, the mixing ratio of the second composition of the present invention is as follows:
The component (D) is 1 to 100 parts by weight of the first composition.
It is 10 parts by weight, preferably 2 to 8 parts by weight, more preferably 3 to 7 parts by weight. If the amount of the component (D) is less than 1 part by weight, the effect of improving the impact resistance, rigidity and weld strength by the component (D) is not sufficient, while if it exceeds 10 parts by weight, good fluidity during molding is obtained. Can not be obtained.

In order to improve the fluidity of the thermoplastic resin composition of the present invention, a low molecular weight polyethylene or an organic phosphorus compound can be blended. The amount of these components is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 3 parts by weight based on 100 parts by weight of the total amount of the components (A) to (C) of the thermoplastic resin composition of the present invention. Parts by weight.

Further, the thermoplastic resin composition of the present invention comprises:
Glass fiber, carbon fiber, glass beads,
Rock filler, glass flake, milled fiber,
Other fillers such as graphite and molybdenum disulfide may be used alone or in combination of two or more.
By blending these fillers, the thermoplastic resin composition of the present invention can be further provided with rigidity. Among these fillers, those having a fiber diameter of 6 to 20 μm and a fiber length of 30 μm or more are preferable as the shape of glass fiber and carbon fiber. The compounding amount of these fillers is preferably 1 to 100 parts by weight, more preferably 5 to 80 parts by weight, based on 100 parts by weight of the total amount of the components (A) to (C) of the thermoplastic resin composition of the present invention. Department.

Further, the thermoplastic resin composition of the present invention may be blended with sodium dihydrogen phosphate, disodium monohydrogen phosphate, or a hydrate thereof to impart thermal stability. . By blending these inorganic phosphorus compounds, the thermal stability during molding can be improved. The compounding amount of the inorganic phosphorus compound is (A)
The amount is preferably 0.01 to 2 parts by weight, more preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the total amount of the component (C).

Further, a flame retardant can be added to the thermoplastic resin composition of the present invention in order to impart flame retardancy. As the flame retardant, a halogen compound, an organic phosphorus compound, a nitrogen compound, an antimony compound, or the like can be used alone or in combination. Among them, examples of the halogen-based compound include oligomers of tetrabromobisphenol A (terminals may be sealed with an epoxy group, tribromophenol, etc.), brominated styrene, post-brominated polystyrene, and brominated polycarbonate. Oligomer, tetrabromobisphenol A, decabromodiphenyl ether, chlorinated polystyrene, aliphatic chlorine compound and the like can be mentioned. Among them, oligomers of tetrabromobisphenol A are preferable (preferable molecular weight is about 1,000 to 6,000). When the halogen is bromine in the halogen-based compound, the preferred bromine concentration is 30 to 65% by weight, and more preferably 45 to 60% by weight.

The organic phosphorus compounds include triphenyl phosphate, trixylenyl phosphate, tricresyl phosphate, trixylenyl thiophosphate, hydroquinone bis (diphenyl phosphate), resorcinol bis (diphenyl phosphate), and resorcinol bis (diphenyl phosphate). (Silenyl phosphate), oligomers of triphenyl phosphate, and the like. Of these, triphenyl phosphate, trixylenyl phosphate, and resorcinol bis (xylenyl phosphate) are preferred. The preferred phosphorus concentration of the organic phosphorus compound is 4 to 30% by weight, more preferably 6 to 25% by weight. Further, examples of the nitrogen-based compound include melamine and cyclized products of isocyanate. Further, as the antimony compound, antimony trioxide, antimony pentoxide and the like can be used.

[0034] The compounding amount of these flame retardants is preferably 1 to 50 parts by weight, more preferably 2 to 30 parts by weight, particularly preferably 2 to 30 parts by weight, based on 100 parts by weight of the total of the components (A) to (C) of the present invention. Preferably it is 5 to 25 parts by weight. If the amount of the flame retardant is less than 1 part by weight, the effect of imparting flame retardancy is insufficient, while if it exceeds 50 parts by weight, the slidability is poor.

Further, additives such as known coupling agents, weathering agents, antioxidants, plasticizers, lubricants, coloring agents, antistatic agents, silicone oils and foaming agents are added to the thermoplastic resin composition of the present invention. Can be blended. this house,
As the weathering agent, a phosphorus-based or sulfur-based organic compound, or an organic compound containing a hydroxyl group is preferable. Examples of the antistatic agent include polyether and a sulfonate having an alkyl group. The amount of these additives is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the total of the components (A) to (C) of the present invention. is there.

Further, the thermoplastic resin composition of the present invention may be blended with another polymer such as another thermoplastic resin or a thermosetting resin according to the required use. Other polymers include polypropylene, polyamide,
Polyester, polysulfone, polyethersulfone,
Polyphenylene sulfide, liquid crystal polymer, polyvinylidene fluoride, polytetrafluoroethylene, polyamide elastomer, polyamideimide elastomer, polyester elastomer, polyetheresteramide, phenol resin, epoxy resin, novolak resin, resol resin, etc. are used alone. Thing or 2
Mixtures of more than one species can be used. The compounding amount of these other polymers is determined according to (A) of the thermoplastic resin composition of the present invention.
The amount is preferably 1 to 150 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of the total amount of the components (C). In addition, a permanent antistatic property can be imparted by blending a polyamide elastomer, a polyetheresteramide, or the like among the other polymers. The preferred compounding amount is 1 to 30 parts by weight, more preferably 2 to 20 parts by weight, based on 100 parts by weight of the total of components (A) to (C).
Parts by weight.

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.
When kneading the respective components, the respective components may be kneaded at once, or may be kneaded by a multi-stage addition method. The thermoplastic resin composition of the present invention thus obtained can be used to form various molded products by injection molding, sheet extrusion molding, vacuum molding, profile extrusion molding, foam molding, and the like. Various molded products obtained by the above molding method,
Utilizing its excellent properties, it can be used for disc / tray materials, housing materials, etc. for OA / home electric appliances, vehicle applications, etc. In particular, molded articles obtained from the thermoplastic resin composition of the present invention are most suitable for materials for portable terminals and box materials for portable phones. In particular, since the thermoplastic resin composition of the present invention has excellent impact resistance, it can withstand the use of, for example, a portion (strap) for attaching a string of a mobile phone.

[0038]

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

The graft ratio is described in the text. Dissolve the sample in methyl ethyl ketone, a limiting viscosity solvent,
It was measured with a Ubbelohde viscometer at a temperature of 0 ° C.

The average particle diameter of the dispersed particles was confirmed by an electron microscope that the particle diameter of the latex synthesized in advance in an emulsified state directly indicates the particle diameter 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. The average particle size of the inorganic filler is a weight average particle size. The whiteness was evaluated according to JIS P8123 and Hunter whiteness.

The flexural modulus was measured according to ASTM D790. The Izod impact strength was measured with a notch according to ASTM D256. In accordance with ASTM D638, in a tensile test using a dumbbell-shaped test piece, the tensile strength of a test piece having a weld at the center of a dumbbell was divided by the tensile strength of a test piece having no weld to obtain a weld retention rate. Was. Fluidity (Melt Flow Rate ) Measured according to ASTM D1238. Measurement temperature is 2
At 40 ° C., the load is 10 kg. The appearance of the molded product was visually evaluated. ○; (in a wide molding condition range, sufficient can be used in the design surface.) Good △; (in the normal molding condition range, can be used in the design surface.) Average ×; poor (. The design surface can not be used) combustion test (Flame retardancy ) Complied with UL-94 V test. The thickness is 1.6mm
It is.

The components used in this example are as follows. (A) Preparation of Component (A-1) Preparation of ABS Resin; Internal Volume 7 with Stirrer
100 liters of ion-exchanged water in a liter glass flask
Parts, sodium dodecylbenzenesulfonate 1.5 parts,
0.1 parts of t-dodecyl mercaptan, 40 parts of polybutadiene (a) (in terms of solid content), 15 parts of styrene and 5 parts of acrylonitrile were added, and the mixture was heated while stirring. When the temperature reaches 45 ° C., 0.1 part of sodium ethylenediaminetetraacetate, 0.003 part of ferrous sulfate, 0.2 part of formaldehyde sodium sulfoxylate dihydrate 0.2
And an aqueous solution of an activator consisting of 15 parts of ion-exchanged water and 0.1 part of diisopropylbenzene hydroperoxide, and the reaction was continued for 1 hour.

Thereafter, 50 parts of ion-exchanged water, 1 part of sodium dodecylbenzenesulfonate, 0.1 part of t-dodecylmercaptan, 0.2 parts of diisopropyl hydroperoxide, 30 parts of styrene and 1 part of acrylonitrile
0 parts of an increment polymerization component was continuously added over 3 hours to continue polymerization. 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 is coagulated with 2 parts of calcium chloride,
After thoroughly washing the reaction product with water, it was dried at 75 ° C. for 24 hours to obtain a white powder A-1. The polymerization conversion rate is 97.2.
%, Graft ratio is 100%, intrinsic viscosity is 0.30 dl /
g.

A-2 to A-4 were obtained in the same manner as A-1. A-1: ABS resin (graft rate = 100%, [η] =
A-2; ABS resin (graft ratio = 60%, [η] = 0.3 dl / g)
0.4 dl / g) A-3; AS resin (B'dAN = 24%, [η] = 0.
A-4; AS resin (B'dAN = 29%, [η] = 0.5 dl / g)
4 dl / g)

(B) Preparation of Polycarbonate Polycarbonate manufactured by Teijin Chemicals Ltd. was used. B-1; Panlite (Mw = 23,500) B-2; Panlite (Mw = 21,000)

(C) Preparation of Inorganic Filler As the inorganic filler, talc manufactured by Nippon Talc Co., Ltd. and micromica manufactured by Corp Chemical Co., Ltd. were used. C-1; talc, average particle size = 3 μm, whiteness = 96%,
pH = 8 C-1 ′; talc, average particle size = 6 μm, whiteness = 96
%, PH = 8 C-2; talc, average particle size = 20 μm, whiteness = 96
%, PH = 8 C-3; talc, average particle size = 3 μm, whiteness = 85%,
pH = 8 C-4; talc, average particle size = 3 μm, whiteness = 96%,
pH = 11 C-5; mica, average particle size = 7 μm, whiteness = 96%,
pH = 8

(D) Preparation of Thermoplastic Resin A thermoplastic resin obtained by graft polymerization of a vinyl monomer onto polycarbonate was manufactured by NOF Corporation. D-1; PC-gr-AS (Mw of PC =
35,000) D-2; PC-gr-AS (Mw of PC = 23,000
0)

Preparation of Other Components Flame Retardant; Brominated Epoxy Resin (Terminal Sealed with Tribromophenoxy) Antimony Trioxide Plasticizer; Low Molecular Weight Polyethylene Wax Triphenyl Phosphate

Examples 1 to 8 and Comparative Examples 1 to 5 The components (A) to (C), or the components (A) to (D), other polymers, additives, etc. were formulated as shown in Tables 1 and 2. And 2
The mixture was melt-kneaded using an extruder under a temperature condition of 20 to 250 ° C., and an evaluation sample was obtained by injection molding. The results are shown in Tables 1 and 2. Each of the thermoplastic resin compositions of the present invention (Examples 1 to 8) in Table 1 has good impact resistance, rigidity,
Weld strength and molded appearance were shown. Further, the flame retardancy of UL94-V0 was exhibited by adding a flame retardant. On the other hand, as is clear from Table 2, Comparative Example 1 was a case where the component (C) of the present invention was not blended, and it was found that the rigidity was significantly reduced. Comparative Example 2 is a case where the component (C) is out of the range of the present invention, and it can be seen that the weld strength and the impact resistance are extremely poor. Comparative Example 3 is a case where the component (C) having a pH outside the range specified in the present invention is used, which causes a decrease in the molecular weight of the polycarbonate and poor impact resistance.
Comparative Example 4 is a case where the blending amount of the component (D) is too large, and the fluidity and the molded appearance are inferior. Comparative Example 5 is a case where the compounding amount of the component (A) is too large, the appearance is poor, and the weld retention is low.

[0050]

[Table 1]

* 1) TPP = triphenyl phosphate

[0052]

[Table 2]

[0053]

Industrial Applicability The thermoplastic resin composition of the present invention is excellent in impact resistance, rigidity, molded appearance, and weld strength, and the molded articles obtained are OA products, home appliances, disk tray materials for vehicle use, housings. It is particularly useful as a material for a mobile terminal or a mobile phone box.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 69:00 51:08) (C08L 55/02 69:00 51:08)

Claims (3)

[Claims] 1. An aromatic vinyl compound, a vinyl cyanide compound, a (meth) acrylic acid ester, an acid anhydride group-containing unsaturated compound and a rubbery polymer (a) in the presence or absence of the rubbery polymer (a). (B) 70 to 10 parts by weight of a (rubber-modified) thermoplastic resin obtained by polymerizing at least one vinyl monomer (b) selected from the group of maleimide-based compounds, And (C) an average particle size of 1 to 15 μm and a pH of 8 to 10
1-20 parts by weight of the inorganic filler in the range of
(A) + (B) + (C) = 100 parts by weight]. 2. The thermoplastic resin composition 10 according to claim 1,
A thermoplastic resin composition comprising (D) 1 to 10 parts by weight of a thermoplastic resin obtained by graft polymerization of a vinyl monomer in the presence of polycarbonate with respect to 0 parts by weight. 3. A molded article obtained by molding the thermoplastic resin composition according to claim 1 and / or 2.