JPH10298423A - Thermoplastic resin composition for housing - Google Patents

Abstract

(57) [Problem] To provide a resin composition excellent in impact resistance, heat resistance, molded article surface gloss, and flame retardancy of a housing having a thin portion without using chlorine and bromine compounds. To do. (A) Aromatic polycarbonate 70 to 95
(B) 30 to 2% by weight of a graft copolymer and (C) 0 to 28% by weight of a vinyl copolymer.
(D) 0.01 to 2 parts by weight of a fluororesin and (E) 2 to 30 parts by weight of a specific phosphoric acid ester compound per 100 parts by weight of the total amount of (A), (B) and (C) A thermoplastic resin composition having a minimum thickness of 2 mm or less, wherein the apparent melt viscosity of the resin composition at 260 ° C. is in a specific range.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention has excellent flame retardancy, impact resistance, and moldability, and has a small dependence of the thickness of the molded article on the impact resistance, and has excellent surface gloss of a thin-walled molded article. Accordingly, the present invention relates to a thermoplastic resin composition suitable for a thin-walled housing.

[0002]

2. Description of the Related Art Plastics have excellent mechanical properties,
Due to its moldability and electrical insulation, it is used in a wide range of fields including home electric appliances, OA appliances, automobiles and other parts. However, most plastics are flammable, and various technologies have been devised for flame retardation due to the increasing demand for safety.

[0003] Generally, a method is employed in which a halogen-based flame retardant such as a bromine compound having a high flame-retardant efficiency and antimony oxide are blended with a resin to make the resin flame-retardant.

In recent years, voluntary regulations relating to environmental problems have demanded a flame-retardant resin containing no chlorine or bromine-based flame retardant, such as aromatic polycarbonates, styrene-containing graft polymers such as ABS, and phosphoric acid. Thermoplastic resin composition comprising a monophosphate ester such as triphenyl (EP-A-0 174 493), aromatic polycarbonate, styrene-containing copolymer and / or styrene-containing graft polymer, and oligomer Thermoplastic Resin Composition Containing Reactive Phosphate Ester Flame Retardant
No. 5262) has been proposed.

[0005]

The method using a halogen-based flame retardant contains a large amount of a flame retardant in order to prevent a drop (drop) of a fire during combustion, so that the mechanical properties and heat resistance of the resin composition are reduced. However, there is a problem that toxic gas is generated by decomposition of the halogen compound at the time of molding or burning.

Further, the composition described in EP-A-0 174 493 has poor heat resistance due to the volatility of the monophosphate, and also has a problem of mold contamination during molding. In the composition described in JP-A-2-115262, a flame retardant improves the problem of the composition described in European Patent No. 0174493 and has been put to practical use. However,
This technique is not satisfactory because molding processability is poor, and it is difficult to mold a housing having a thin portion, or even if molded, the mechanical properties and surface gloss of the molded product are inferior.

An object of the present invention is to provide a resin composition which is excellent in impact resistance, heat resistance, surface gloss of a molded article, and flame retardancy of a housing having a thin portion without using chlorine and bromine compounds. Aim.

[0008]

The present invention has been made as a result of intensive studies to solve the above-mentioned problems, and as a result, a mixture of aromatic polycarbonate and ABS resin is blended with a fluorine resin and a specific phosphate ester. The present inventors have found that the above-mentioned object is efficiently achieved by the resin composition having a specific apparent melt viscosity at 260 ° C., and reached the present invention.

That is, the present invention relates to (A) 70 to 95% by weight of an aromatic polycarbonate, (B) 50 to 90% by weight of an aromatic vinyl monomer and 10 to 90% by weight of a vinyl cyanide monomer.
(C) a graft copolymer obtained by graft-copolymerizing 70 to 20 parts by weight of a monomer mixture containing 50% by weight with 30 to 80 parts by weight of a rubbery polymer;
From 0 to 28% by weight of a vinyl copolymer obtained by copolymerizing a monomer mixture containing 50 to 90% by weight of an aromatic vinyl monomer and 10 to 50% by weight of a vinyl cyanide monomer. (D) 0.01 to 2 parts by weight of a fluororesin and (E) 2 to 30 parts by weight of a phosphoric ester compound of the following general formula (I) per 100 parts by weight of the resulting resin composition (a). A thermoplastic resin composition comprising:
The apparent melt viscosity at 60 ° C. is a shear rate of 10 ² sec.
a minimum thickness of 2 mm or less, wherein c- ¹ is 5 × 10 ³ to 1 × 10 ⁵ poise, and a shear rate is 10 ³ sec ^-1 and 1 × 10 ^{3 to} 5 × 10 ⁴ poise. A thermoplastic resin composition for a housing, comprising: ".

[0010]

Embedded image (In the formula, X is an arylene group; R ¹ , R ² , R ³ , and R ⁴ are substituted or unsubstituted phenyl groups.) The present invention will be specifically described below.

In the present invention, the aromatic polycarbonate (A) generally includes 2,2-bis (4-oxyphenyl) alkane, bis (4-oxyphenyl) ether, and bis (4-oxy). (Phenyl) sulfone, sulfide, sulfoxide or other bisphenol-based polymers or copolymers. Aromatic polycarbonate
Bones are manufactured by any method. For example,
For the production of polycarbonate from 4,4'-dihydroxydiphenyl-2,2-propane (commonly known as bisphenol A), a phosgene method in which phosgene is produced by blowing phosgene in the presence of a caustic aqueous solution and a solvent, or 4,4'-
A method in which dihydroxydiphenyl-2,2-propane and a carbonic acid diester are transesterified in the presence of a catalyst can be used.

Although the molecular weight of the aromatic polycarbonate is not particularly limited, the intrinsic viscosity measured at 30 ° C. in a tetrahydrofuran solvent is 0.38 to 0.52 dl / g, particularly 0.40 dl / g.
A thermoplastic resin composition having a range of from about 0.50 dl / g to about 0.50 dl / g is preferably excellent in balance between impact resistance and fluidity during melt molding.

In the present invention, the graft copolymer (B) refers to a rubbery polymer in an amount of 30 to 80 parts by weight and a monomer mixture of an aromatic vinyl monomer and a vinyl cyanide monomer of 70 to 80 parts by weight.
It is a graft copolymer obtained by graft polymerization of 20 parts by weight. The term “(B) graft copolymer” used herein includes not only a material having a structure obtained by graft copolymerization with a rubbery polymer but also a non-grafted copolymer.

As the rubbery polymer, those having a glass transition temperature of 0 ° C. or less are preferred, and diene rubbers are particularly preferably used. Specifically, polybutadiene,
Styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, styrene-butadiene block copolymer, diene rubber such as butyl acrylate-butadiene copolymer, acrylic rubber such as polybutyl acrylate, polyisoprene, An ethylene-propylene-diene-based terpolymer is exemplified. Among them, polybutadiene or butadiene copolymer is preferred.

The rubber particle diameter of the rubbery polymer is not particularly limited, but the average particle diameter of the rubber particles is 0.15 to 0.40 μm.
m, especially 0.18 to 0.35 μm, is preferred because it is excellent in impact resistance and gloss of a thin-walled molded product.

As the aromatic vinyl monomer, styrene,
Examples include α-methylstyrene, vinyltoluene, o-ethylstyrene, pt-butylstyrene, etc., with styrene being particularly preferred.

Examples of the vinyl cyanide-based monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile and the like, and acrylonitrile is particularly preferred.

If necessary, a graft-copolymerizable vinyl monomer, for example, a maleimide monomer such as maleimide, N-methylmaleimide or N-phenylmaleimide, acrylic acid, methacrylic acid, maleic acid, anhydride, Α, β-unsaturated carboxylic acids such as maleic acid, phthalic acid and itaconic acid and their anhydrides, acrylamide, (meth)
For example, 2-hydroxyethyl acrylate can be used.

(B) The monomer mixture used in the graft copolymer contains at least 50% by weight, preferably at least 70% by weight, and at most 90% by weight of an aromatic vinyl monomer.
The content is preferably in the range of 85% by weight or less, and the content of the vinyl cyanide monomer is in the range of 10% by weight or more, preferably 15% by weight or more, and 50% by weight or less, preferably 30% by weight or less. Used. In addition to the aromatic vinyl monomer and the vinyl cyanide monomer, other vinyl monomers copolymerizable therewith can be added, and the amount is 50% by weight or less, and further 30% by weight. % Is preferably used. When the proportion of the aromatic vinyl monomer is out of the range of 50 to 90% by weight, the impact resistance of the resin composition is poor, which is not preferable. When the proportion of the vinyl cyanide monomer exceeds 50% by weight, the moldability of the resin composition is remarkably reduced, and when it is less than 10% by weight, the impact resistance of the resin composition is poor, which is not preferable.

(B) The ratio of the rubbery polymer to the monomer mixture in obtaining the graft copolymer is 30 parts by weight or more, preferably 40 parts by weight, of the rubbery polymer based on 100 parts by weight of the total graft copolymer. Not less than 80 parts by weight, preferably not more than 70 parts by weight, is used. The monomer mixture is 70
It is at most 60 parts by weight, preferably at least 20 parts by weight, preferably at least 30 parts by weight. If the proportion of the rubbery polymer is less than 30 parts by weight, the impact resistance of the resin composition,
If the surface gloss of the molded article is inferior and exceeds 80 parts by weight, the impact resistance of the resin composition and the surface gloss of the molded article are inferior.

(B) The graft copolymer can be obtained by a known polymerization method. For example, it can be obtained by a method in which a mixture of a monomer and a chain transfer agent and a solution of a radical generator dissolved in an emulsifier are continuously supplied to a polymerization vessel in the presence of a rubbery polymer latex to carry out emulsion polymerization.

(B) The graft copolymer contains a non-grafted copolymer in addition to a material having a structure grafted to a rubbery polymer. (B) The graft ratio of the graft copolymer is not particularly limited, but is preferably 20 to 70% by weight, especially 25 to 70% by weight in order to obtain a resin composition excellent in impact resistance and gloss of a molded product having a thin portion. 45% by weight is preferred. Here, the graft ratio is calculated by the following equation.

Graft ratio (%) = <amount of vinyl copolymer graft-polymerized on rubbery polymer> / <rubber content of graft copolymer> × 100.

The properties of the ungrafted copolymer are not particularly limited, but the intrinsic viscosity [η] (measured at 30 ° C.) of the methyl ethyl ketone-soluble component of the graft copolymer (B) is 0.15 to 0. 0.6 dl / g, especially 0.20
The range of 0.40 dl / g is preferably used because an impact-resistant resin composition is obtained.

In the resin composition of the present invention, if necessary, a vinyl copolymer (C) having a polymerized structure derived from an aromatic vinyl monomer and a vinyl cyanide monomer is blended. . Styrene as an aromatic vinyl monomer,
α-Methylstyrene, p-methylstyrene, t-butylstyrene, vinyltoluene, o-ethylstyrene and the like can be mentioned, but styrene is particularly preferred. One or more of these can be used.

Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, and ethacrylonitrile, and acrylonitrile is particularly preferable.

If necessary, other vinyl monomers,
For example, maleimide monomers such as maleimide, N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, ester compounds of methyl (meth) acrylic acid such as methyl, ethyl, propyl and n-butyl, acrylic acid, methacrylic acid , Maleic acid, maleic anhydride,
Vinyl monomers containing a carboxyl group such as phthalic acid and itaconic acid, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, allyl glycidyl ether, styrene-p-glycidyl ether, p-glycidyl styrene, etc. A vinyl monomer containing an epoxy group, aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, ethylaminopropyl methacrylate, phenylaminoethyl methacrylate, cyclohexylaminoethyl methacrylate, N-vinyl Diethylamine, N-acetylvinylamine, allylamine, methallylamine, N-methylallylamine, acrylamide, methacrylamide, N-methylacrylamide, butoxymethylac Ruamido, N- methacrylamide, vinyl monomers having an amino group having an amino group or a substituted amino group such as styrene bonded to the benzene ring, 2-hydroxyethyl acrylate, methacrylic acid 2
-Hydroxyethyl, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2,3,4,5,6-pentahydroxyhexyl acrylate, 2,3,4,5,6-pentahydroxyhexyl methacrylate, 2,3,4,5-tetrahydroxypentyl acrylate, 2,3,4,5-tetrahydroxypentyl methacrylate, 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy- 2-butene, trans-4-hydroxy-2-butene, 3-hydroxy-2-methyl-1-propene, cis-5-hydroxy-2-pentene, trans-5-hydroxy-2-
A polymer structure derived from a vinyl monomer having a hydroxyl group such as pentene and 1,4-dihydroxy-2-butene can be contained.

Here, the ratio of each component derived from the monomer mixture of the aromatic vinyl monomer is 50% by weight or more, preferably 60% by weight or more, and 90% by weight or less.
The content is preferably 80% by weight or less, and the content of the vinyl cyanide monomer is 10% by weight or more, preferably 20% by weight or more, and 50% by weight or less, preferably 40% by weight or less. The content of other vinyl monomers is 40% by weight or less, preferably 20% by weight or less.

In the vinyl copolymer (C), if the amount of the aromatic vinyl monomer is out of the range of 50 to 90% by weight, the impact resistance of the resin composition deteriorates, which is not preferable. The molecular weight of the vinyl copolymer (C) is not particularly limited, but the intrinsic viscosity [η] (methyl ethyl ketone solvent, measured at 30 ° C.) is 0.35 to 0.60 dl /.
g, especially those in the range of 0.4 to 0.55 dl / g are preferably used because a resin composition having excellent impact resistance and moldability can be obtained.

The method for producing the vinyl copolymer (C) is not particularly limited, and may be any of ordinary methods such as bulk polymerization, suspension polymerization, emulsion polymerization, bulk-suspension polymerization, and solution-bulk polymerization. Can be used.

In the resin composition (A) of the present invention, the aromatic polycarbonate (A) contains 70% by weight or more, preferably 75% by weight or more, and 95% by weight or less, preferably 9% by weight or less.
It is blended in a range of 0% by weight or less. The graft copolymer (B) is blended in an amount of 30% by weight or less, preferably 20% by weight or less, and 2% by weight or more, preferably 4% by weight or more. The vinyl copolymer (C) is blended as required, and the content of (C) is 28% by weight or less, preferably 20% by weight or less, 0% or more, preferably 1% by weight or more, and more preferably 5% by weight. It is blended so as to be in the above range.

When the content of the aromatic polycarbonate (A) is less than 70% by weight, the flame retardancy and heat resistance are deteriorated. When the content is more than 95% by weight, the molding processability and the surface gloss of the molded product are deteriorated. Absent.

The resin composition (A) of the present invention is obtained by combining the specific (A) aromatic polycarbonate and the specific graft copolymer (B) described above to obtain a molded article having a thickness dependency on impact resistance. Demonstrates small characteristics of

The fluororesin (D) used in the present invention is a polymer having a tetrafluoroethylene structure, preferably having a fluorine content of 65 to 76% by weight, more preferably 70 to 76% by weight. It is. Examples thereof include a tetrafluoroethylene polymer, a tetrafluoroethylene-hexafluoropropylene copolymer, and a copolymer of tetrafluoroethylene and an ethylenically unsaturated monomer containing no fluorine.

(D) The method for producing the fluororesin is not particularly limited. For example, the method may be carried out in an aqueous medium using a catalyst such as sodium, potassium or ammonium peroxydisulfate.
Known methods such as polymerization of tetrafluoroethylene or the like under a pressure of 71 kg / cm @ 2 at a temperature of 0 to 200 DEG C. can be used.

(D) The fluorine-based resin having a number average molecular weight in the range of 1 × 10 ^{6 to} 5 × 10 ⁸ determined by the following formula (II) is preferable because it greatly improves the flame retardancy.

D = −0.0579 log Mn + 2.6113 (II) (In the formula (II), Mn is a number average molecular weight, and d is ASTM.
D1457-56T).

The thermoplastic resin composition of the present invention contains (E) a phosphate compound represented by the following general formula (I).

[0039]

Embedded image In the formula (I), X represents an arylene group, and R ¹ , R ² , R ³ , and R ^{4 each} represent a substituted or unsubstituted phenyl group.

Examples of the arylene group include an o-phenylene group, an m-phenylene group, a p-phenylene group, a biphenylene group and a phenyleneoxyphenylene group.
Among them, an m-phenylene group and a p-phenylene group are preferably used.

R ¹ , R ² , R ³ , and R ⁴ are substituted or unsubstituted phenyl groups, provided that at least one of R ¹ , R ² , R ³ , and R ⁴ has 1 to 6 carbon atoms. Alkyl-substituted phenyl group "and" R ¹ , R ² , R ³ and R ^{4 each} have 1 to 1 carbon atoms
6 having an alkyl-substituted phenyl group ", and further having a structure wherein" R ¹ , R ² , R ³ , and R ⁴ are a di-substituted phenyl group having 1 to 6 carbon atoms ". The alkyl group having 1 to 3 carbon atoms is preferably used.

Specifically, resorcinol-bis (di-
2,6-dimethylphenyl phosphate), resorcinol-bis (di-3,5-dimethylphenyl phosphate), resorcinol-bis (di-2,6-diethylphenyl phosphate), resorcinol-bis (di-
3,5-diethylphenyl phosphate), resorcinol-bis (di-2,6-dipropylphenylphosphate), resorcinol bis (di-3,5-dipropylphenylphosphate), hydroquinone-bis (di-2,6 -Dimethylphenyl phosphate), hydroquinone-bis (di-3,5-dimethylphenyl phosphate), hydroquinone-bis (di-2,6-diethylphenyl phosphate), resorcinol-bis (di-
3,5-diethylphenylphosphate), hydroquinone-bis (di-2,6-dipropylphenylphosphate), hydroquinone-bis (di-3,5-dipropylphenylphosphate), 4,4'-biphenylene-
Bis (di-2,6-dimethylphenyl phosphate),
4,4'-biphenylene-bis (di-3,5-dimethylphenyl phosphate), 4,4'-biphenylene-bis (di-2,6-diethylphenyl phosphate),
4,4'-biphenylene-bis (di-3,5-diethylphenyl phosphate), 4,4'-biphenylene-bis (di-2,6-dipropylphenyl phosphate),
4,4'-biphenylin-bis (di-3,5-dipropylphenylphosphate), resorcinol-bis (di-2-methylphenylphosphate), resorcinol-bis (di-3-methylphenylphosphate), resorcinol-bis (Di-4-methylphenyl phosphate), resorcinol-bis (di-5-methylphenyl phosphate), resorcinol-bis (di-6-methylphenyl phosphate), hydroquinone-bis (di-2-methylphenyl phosphate), Hydroquinone-bis (di-3-methylphenyl phosphate),
Hydroquinone-bis (di-4-methylphenyl phosphate), hydroquinone-bis (di-5-methylphenyl phosphate), hydroquinone-bis (di-6
Methylphenyl phosphate), 4,4′-biphenylene-bis (di-2-methylphenyl phosphate),
4,4'-biphenylene-bis (di-3-methylphenyl phosphate), 4,4'-biphenylene-bis (di-4-methylphenyl phosphate), 4,4'-biphenylene-bis (di-5-methyl) Phenyl phosphate), 4,4'-biphenylene-bis (di-5-methylphenyl phosphate), resorcinol-bis (diphenyl phosphate), hydroquinone-bis (diphenyl phosphate), 4,4'-biphenylene-bis (diphenyl phosphate) And resorcinol-bis (di-2,6-dimethylphenyl phosphate), hydroquinone-bis (di-2,6-dimethylphenyl phosphate), and 4,4′-biphenylene-bis (di-2,6). -Dimethylphenyl phosphate), resorcinol-bis ( 4-methyl-phenyl phosphate), hydroquinone - bis (di-4-methylphenyl phosphate), resorcinol - bis (diphenyl phosphate) is rigid, molded article surface gloss, preferably excellent in flame retardancy.

(E) The method for producing the phosphate compound is not particularly limited. For example, after reacting phosphorus oxychloride and hydroquinone in a solvent at a substantially 2: 1 molar ratio,
Hydroquinone-bis (2,6-dimethylphenyl) phosphate can be obtained by adding an appropriate amount of 2,6-dimethylphenol for reaction.

In the present invention, the compounding amount of (D) the fluorine-based resin is as follows: (A) a resin composition comprising an aromatic polycarbonate, (B) a graft copolymer, and (C) a vinyl copolymer. B) 0.01 to 2 parts by weight with respect to 100 parts by weight,
Preferably it is 0.05 to 1.0 part by weight.

(D) If the compounding amount of the fluororesin is less than 0.01 part by weight, the flame retardancy of the thermoplastic resin composition becomes poor,
If the amount exceeds 2 parts by weight, the impact resistance of the thermoplastic resin composition deteriorates, which is not preferable.

In the present invention, the compounding amount of the (E) phosphate compound is a resin composition comprising (A) an aromatic polycarbonate, (B) a graft copolymer and (C) a vinyl copolymer. B) 2 to 30 parts by weight, preferably 4 to 25 parts by weight, per 100 parts by weight. If the amount of the (E) phosphate compound is less than 2 parts by weight, the flame retardancy becomes poor, and if it exceeds 30 parts by weight, the impact resistance and heat resistance of the thermoplastic resin composition become poor. (E) other than the phosphate compound, derived from the compound,
Oligomers such as dimers and trimers may be contained in the resin composition (a).

In order to achieve the object efficiently, the resin composition of the present invention has an apparent melt viscosity at 260 ° C. of 5 × 10 ³ to 1 × 10 ⁵ poise at a shear rate of 10 ² sec ^-1 .
Preferably 7 × 10 ^{3 to} 5 × 10 ⁴ poise, shear rate 10
^{In 3} sec ^−1, it is 1 × 10 ^{3 to} 5 × 10 ⁴ poise, preferably 2 × 10 ^{3 to} 3 × 10 ⁴ poise.

When the apparent melt viscosity is within the above range, the thickness dependency of the molded article on the impact resistance is small, and the surface gloss of the thin molded article is extremely excellent.

The resin composition of the present invention has an average burning time of 5 specimens of 1/16 inch × 1/2 inch × 5 inch in accordance with UL94 standard.
Seconds or less are preferred, and more preferably 2 seconds or less.

When the average burning time is 3 seconds or less, the flame retardancy of the resin composition is more stable, and the reliability of the thin-walled housing with respect to the flame retardancy is further enhanced.

Further, in order to achieve the above-described flame retardancy more efficiently, 1/16 inch × 1/2 according to UL94 standard is used.
In the flammability of the inch × 5 inch test piece, the test piece shrinkage rate in the first combustion test is preferably in the range of 5 to 20%, and higher flame retardancy is exhibited.

The method for producing the resin composition of the present invention is not particularly limited. For example, (A) aromatic polycarbonate
And a mixture of (B) a graft copolymer, (C) a vinyl copolymer, (D) a fluororesin, and (E) a phosphate compound is melt-kneaded with a Banbury mixer, a roll, an extruder, a kneader, or the like. It is commercialized by

The thermoplastic resin composition of the present invention may contain another thermoplastic resin compatible with the composition.
For example, polyphenylene ether, polyglutarimide,
Improve impact resistance and heat resistance by mixing polycyclohexane dimethylene terephthalate, etc., and improve chemical resistance by mixing polyolefin, polybutylene terephthalate, polyethylene terephthalate, polyamide, etc. To improve rigidity and heat resistance. Further, if necessary, various stabilizers such as antioxidants and ultraviolet absorbers, pigments, dyes, lubricants, plasticizers and the like can be added.

The thermoplastic resin composition of the present invention is melt molded and used as a resin molded product. This resin molded product is useful for a housing because of its excellent surface gloss and flame retardancy even in a portion of 2 mm or less. Specific examples of the housing include a printer, a personal computer, a display, and a CR.
T display, fax, copy, word processor, notebook computer, DVD drive, PD drive, floppy disk drive housing, DVD drive, P
Housings for storage devices such as D drives and floppy disk drives, printers, cassettes for copying, housings for mobile phones, televisions, telephones and receivers, housings for air conditioners for home and automobiles, housings for oil fan heaters.

[0055]

EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples. In addition, the number of parts and% in an Example show a weight part and weight%, respectively. The methods for measuring and evaluating each property are as follows.

Average particle size of rubber particles: "Rubber
Age Vol. 88 p. 484-490 (196
0) byE. Schmidt, P .; H. Biddiso
sodium alginate method described in "n" (using the fact that the particle size of polybutadiene to be creamed varies depending on the concentration of sodium alginate, the particles having a cumulative weight fraction of 50% from the cumulative weight fraction of the creamed weight ratio and the sodium alginate concentration) The diameter was determined).

Graft ratio: Acetone was added to a predetermined amount (m) of the graft copolymer and refluxed for 4 hours. Add this solution to 8
After centrifugation at 000 rpm (10,000 G) for 30 minutes, insoluble matter was filtered. This insoluble matter was dried under reduced pressure at 70 ° C. for 5 hours, and the weight (n) was measured.

Graft ratio = [(n)-(m) × L] /
[(M) × L] × 100 Here, L means the rubber content of the graft copolymer.

Number average molecular weight: d = −0.0579 log Mn + 2.6113 (II) (in the formula (II), Mn is the number average molecular weight, d is ASTM)
D1457-56T).

Intrinsic viscosity [η]: (1) In the case of polycarbonate 0.8 g, 0.4 g, 0.2 g, 0.1 g of polycarbonate.
The solution viscosity η of each sample of 1 g / dl and tetrahydrofuran solvent was measured at 30 ° C. Further, the solvent viscosity η ₀ of the tetrahydrofuran solvent was measured at 30 ° C.

[0061]

(2) In the case of vinyl copolymer In the above (1), the same method was used except that the polycarbonate was changed to the vinyl copolymer and the tetrahydrofuran solvent was changed to the methyl ethyl ketone solvent.

1/4 inch Izod impact strength: AS
TM D256-56A.

1/8 inch Izod impact strength: AS
TM D256-56A.

Apparent melt viscosity: The resin composition dried under reduced pressure at 80 ° C. for 7 hours was measured for melt viscosity under the following conditions.

(1) Equipment name: Shimadzu Flotter CFT
-500 (Shimadzu Corporation) (2) Nozzle: 0.5 mmφ × 5 mmL (3) Temperature: 260 ° C. (4) Preheating: 8 minutes (5) Load: 10 to 200 kg From the above, the melt viscosity and shear rate The relationship was plotted, and the apparent melt viscosity at a shear rate of 10 ² sec ^-1 and a shear rate of 10 ³ sec ^-1 was determined.

Molding workability: The minimum filling pressure of a molded product having a thickness of 1.5 mm × 30 mm × 200 mm having a gate beside one end was measured. The smaller the value, the better the moldability.

Surface gloss of molded article: A 1.5 mm thick x 30 mm width x 200 mm length molded article obtained for evaluation of molding workability was measured using a digital variable angle gloss meter UGV-5D (Suga Test Instruments Co., Ltd.). Was measured at an incident angle of 60 °.

Flame retardancy: According to the UL94 standard, a vertical combustion test was performed on a 1/16 inch × 片 inch × 5 inch combustion test piece.

Reference Example 1 (A) Preparation of Aromatic Polycarbonate <A-1> Bisphenol A type aromatic polycarbonate having an intrinsic viscosity of 0.44 dl / g measured at 30 ° C. in a tetrahydrofuran solvent. (A-1) was used.

<A-2> 30
A bisphenol A type aromatic polycarbonate (A-2) having an intrinsic viscosity of 0.48 dl / g measured at ° C was used.

<A-3> 30% with tetrahydrofuran solvent
A bisphenol A type aromatic polycarbonate (A-3) having an intrinsic viscosity of 0.35 dl / g measured at ° C was used.

<A-4> 30
A bisphenol A type aromatic polycarbonate (A-3) having an intrinsic viscosity of 0.55 dl / g measured at ° C was used.

Reference Example 2 (B) Preparation of Graft Copolymer The method for preparing the graft copolymer is described below.

<B-1> Acrylonitrile-butadiene copolymer rubber latex copolymerized with 5% by weight of acrylonitrile (average rubber particle diameter 0.22 μm, gel content 80%)
In the presence of 50 parts (in terms of solid content), 50 parts of a monomer mixture composed of 79% of styrene and 21% of acrylonitrile were emulsion-polymerized. The obtained graft copolymer is coagulated with sulfuric acid,
Neutralized with sodium hydroxide, washed, filtered and dried to prepare a powdery graft copolymer (B-1).

The obtained graft copolymer had a graft ratio of 35%. Further, this graft copolymer has a styrene structural unit of 79% and an acrylonitrile structural unit of 2%.
It contained 32% of a 1% non-graftable copolymer. The intrinsic viscosity of the soluble portion of methyl ethyl ketone was 0.38 dl / g.

<B-2> A monomer mixture 30 composed of 70% styrene and 30% acrylonitrile in the presence of 70 parts (in terms of solids) of polybutadiene latex (average rubber particle diameter 0.30 μm, gel content 87%) Parts were emulsion polymerized.
The obtained graft copolymer was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered, and dried to prepare a powdery graft copolymer (B-2).

The resulting graft copolymer had a graft ratio of 28%. This graft copolymer contained 10% of a non-graft copolymer composed of 70% of styrene structural units and 30% of acrylonitrile structural units. The intrinsic viscosity of the soluble portion of methyl ethyl ketone was 0.20 dl / g.

Reference Example 3 (C) Preparation of Vinyl Copolymer <C-1> A copolymer (C-1) was prepared by subjecting a monomer mixture of 70% styrene and 30% acrylonitrile to suspension polymerization. . The intrinsic viscosity of the resulting copolymer was 0.50 dl / g.

Reference Example 4 (D) Fluorine Resin <D-1> Polytetrafluoroethylene having a number average molecular weight of 1 × 10 ⁷ was used.

<D-2> Reference Example 5 using polytetrafluoroethylene having a number average molecular weight of 8 × 10 ⁷ (E) Phosphate ester compound <E-1> Resorcinol-bis (di-2,6- PX200 (manufactured by Daihachi Chemical Industry Co., Ltd.) which is dimethylphenyl phosphate) was used.

<E-2> Hydroquinone-bis (di-
PX2 which is 2,6-dimethylphenyl phosphate)
01 (manufactured by Daihachi Chemical Industry Co., Ltd.) was used.

<E-3> CR733S (manufactured by Daihachi Chemical Industry Co., Ltd.), which is resorcinol-bis (diphenyl phosphate), was used.

Examples 1 to 11 (A) Aromatic polycarbonate and (B) shown in Reference Examples
The graft copolymer, (C) vinyl-based copolymer, (D) fluorine-based resin, and (E) phosphate ester were mixed at the compounding ratio shown in Table 1, and the resin temperature was 240 using a vented 30 mmφ twin-screw extruder. A pellet-shaped polymer was produced by performing melt-kneading and extrusion at a temperature of ° C. Next, a test piece was molded by an injection molding machine at a cylinder temperature of 260 ° C. and a mold temperature of 60 ° C., and each physical property was measured under the above conditions.

The measurement results of the obtained test pieces are shown in Tables 2 and 3.

[0086]

[Table 1]

[Table 2]

[Table 3]

Comparative Examples 1 to 10 (A) Aromatic polycarbonate prepared in Reference Examples,
(B) a graft copolymer, (C) a vinyl copolymer,
(D) The fluorine-based resin and (E) the phosphate ester were mixed at the compounding ratio shown in Table 1, and each physical property was measured in the same manner as in the examples. The measurement results are shown in Tables 2 and 3.

The following is clear from the results of Tables 2 and 3. In the resin compositions of the present invention (Examples 1 to 11), the dependency of the thickness of the molded article on the impact resistance is small, and the moldability, the surface gloss and the flame retardancy of the molded article having a thickness of 2 mm or less are balanced. It excels.

On the other hand, when the blending amount of the aromatic polycarbonate (A) exceeds 98% by weight (Comparative Example 1), the impact resistance and the moldability are poor, and when it is less than 70% by weight (Comparative Example). (2) and (3) are inferior in flame retardancy and are not preferred.

When the amount of the fluororesin (D) is less than 0.01 part by weight (Comparative Example 5), the flame retardancy is poor, and when it exceeds 2 parts by weight (Comparative Example 4), the impact resistance is poor. Is not preferred.

When the amount of the phosphate compound (E) is 2
When the amount is less than part by weight (Comparative Example 6), the flame retardancy is inferior. When the amount exceeds 30 parts by weight (Comparative Example 7), the impact resistance becomes poor, which is not preferable.

When the apparent melt viscosity of the thermoplastic resin composition is out of the specified range (Comparative Examples 8 and 9), the impact resistance is deteriorated, the moldability and the surface gloss are deteriorated. Not preferred.

[0093]

Industrial Applicability The thermoplastic resin composition of the present invention does not contain bromine and chlorine compounds and has excellent flame retardancy, impact resistance, and moldability. The molded article having a small thickness dependency and a thickness of 2 mm or less has excellent gloss.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 27:12)

Claims (6)

[Claims] (A) Aromatic polycarbonate 70 to 95
% By weight, (B) 50 to 90% by weight of an aromatic vinyl monomer
70 to 20 parts by weight of a monomer mixture containing 10 to 50% by weight of a vinyl cyanide monomer
30 to 2% by weight of a graft copolymer obtained by graft copolymerization to about 80 parts by weight, and (C) 50 to 90% by weight of an aromatic vinyl monomer and 10 to 50% of a vinyl cyanide monomer
Resin composition consisting of 0 to 28% by weight of a vinyl copolymer obtained by copolymerizing a monomer mixture containing
(D) Fluororesin 0.01 to 2 parts per 100 parts by weight
A thermoplastic resin composition comprising 2 parts by weight and (E) 2 to 30 parts by weight of a phosphoric ester compound of the following general formula (I), wherein the apparent melt viscosity of the resin composition at 260 ° C. is shear 5 × 10 ^{3 -1} × at a speed of 10 ² sec ^-1
10 ⁵ poises and a shear rate of 10 ³ sec ^-1
2 m, characterized in that it is from 10 ^{3 to} 5 10 ⁴ poise.
m thermoplastic resin composition having a minimum thickness of not more than m (In the formula, X is an arylene group; R ¹ , R ² , R ³ , and R ⁴ are substituted or unsubstituted phenyl groups.) 2. A 1/16 inch × 1 according to UL94 standard.
In the flammability of a 1/2 inch x 5 inch test piece, the first average burn time was 3 seconds or less and the flammability of a 1/16 inch x 1/2 inch x 5 inch test piece according to UL94 standard 2. The thermoplastic resin composition for a housing according to claim 1, wherein the test piece shrinkage rate in the first combustion test is 5 to 20%. 3. The phosphoric ester compound (E) has the general formula (I) and at least one of R ¹ , R ² , R ³ and R ^4.
3. The thermoplastic resin composition according to claim 1, wherein the one is an alkyl-substituted phenyl group having 1 to 6 carbon atoms. 4. 4. The phosphoric ester compound (E) has the general formula (I), wherein R ¹ , R ² , R ³ and R ⁴ have 1 to 6 carbon atoms.
The thermoplastic resin composition according to claim 1, wherein the phenyl group is an alkyl-substituted phenyl group. 5. The phosphoric ester compound (E) has the general formula (I) and R ¹ , R ² , R ³ and R ⁴ have 1 to 6 carbon atoms.
The thermoplastic resin composition according to claim 1 or 2, wherein the alkyl group is a disubstituted phenyl group. 6. The (D) fluororesin has a number average molecular weight of 1 ×.
The number is 10 ^{6 to} 5 × 10 ⁸ .
5. The thermoplastic resin composition according to any one of 5.