JPH0812868A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic composition excellent in flame retardancy, resistance to shock and heat and moldability by formulating a fluororesin, a silicone and a specific a phosphoric ester to a composition of an aromatic polycarbonate and a specific copolymer. CONSTITUTION:A pre-composition of this resin pre-composition comprises (A) an aromatic polycarbonate, (B) a graft copolymer prepared by grafting 70-20 pts.wt. of a monomer mixture of (i) 40-90wt.% of an aromatic vlinyl monomer with (ii) 10-60wt.% of a vinyl cyanide monomer to 30-80 pts.wt. of a rubber polymer and/or (C) a vinyl copolymer prepared by copolymerization of a monomer mixture of 40-90wt.% of ingredient (i) with 10-60wt.% of ingredient (ii) wherein the amount of the ingredient (A) is adjusted to 50-98wt.%, while the total of ingredients (B) and (C) is to 50-2wt.%. Further, (D) 0.01-5 pts.wt. of a fluororesin and/or silicone and (E) 1-40 pts.wt. of a phosphoric ester of the formula (X is a difunctional aromatic group; R<1>-R<4> are each phenyl which may be substituted) are formulated to 100 pts.wt. of the resin pre-composition to give this composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition containing no chlorine and bromine compounds, which is excellent in flame retardancy and has a good balance of impact resistance, heat resistance and moldability.

[0002]

2. Description of the Related Art Plastics have excellent mechanical properties,
It is used in a wide range of fields including home electric appliances, office automation equipment, automobiles and other parts due to its moldability and electrical insulation. However, most plastics are flammable, and various techniques have been devised to resist flame retardation due to safety issues.

In general, a method has been adopted in which a halogen-based flame retardant such as a bromine compound having a high flame retarding efficiency and antimony oxide are blended with a resin to make the flame retardant.

Further, in connection with recent environmental problems, flame-retardant resins containing no chlorine and bromine flame retardants have been sought, and aromatic polycarbonate, styrene-containing graft polymers such as ABS, and triphosphate. Thermoplastic resin composition consisting of monophosphate ester such as phenyl (European Patent Publication No. 0174493), aromatic polycarbonate,
Thermoplastic resin composition comprising styrene-containing copolymer and / or styrene-containing graft polymer and oligomeric phosphoric acid ester flame retardant (JP-A-2-115262), and aromatic polycarbonate and hydroquinone -Bis (2,6-dimethylphenyl) phosphate and a thermoplastic resin composition (US Pat. No. 5,122,55)
No. 6) has been proposed.

[0005]

The method using a halogen-based flame retardant contains a large amount of the flame retardant for the purpose of preventing the drop (drip) of the fire species at the time of 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 due to decomposition of halogen compounds during molding or combustion.

Further, the composition described in European Patent Publication No. 01744493 has a problem that the monophosphate ester is easily volatilized, so that the heat resistance is inferior and the mold is contaminated during molding. The composition described in Japanese Patent Application Laid-Open No. 2-115262 has a liquid flame retardant and contains a large amount of it, so that it has poor heat resistance, and the composition described in US Pat. No. 5,122,556 is flame retardant. However, the impact resistance was inferior, and these were not able to satisfy various characteristics.

The present invention provides a resin composition which is excellent in impact resistance, heat resistance, fluidity at the time of molding, and flame retardancy without using chlorine and bromine compounds while utilizing the original characteristics of the resin. With the goal.

[0008]

DISCLOSURE OF THE INVENTION The present invention has been made as a result of extensive studies to solve the above-mentioned problems, and as a result, an aromatic polycarbonate,
The present inventors have found that the above object can be efficiently achieved by blending a fluororesin and a specific phosphoric acid ester in a mixture of a resin with ABS resin and have reached the present invention.

That is, the present invention provides (1) "(A) aromatic polycarbonate, and (B) aromatic vinyl monomer 40.
Graft copolymer obtained by graft-copolymerizing 70 to 20 parts by weight of a monomer mixture containing 90 to 90% by weight and 10 to 60% by weight of a vinyl cyanide monomer with 30 to 80 parts by weight of a rubbery polymer. Polymer and / or (C) 40-90% by weight of aromatic vinyl monomer and vinyl cyanide monomer 10-6
Resin composition (a) consisting of a vinyl-based copolymer obtained by copolymerizing a monomer mixture containing 0% by weight (provided that (A)
Ingredients: 50 to 98% by weight, (B) component and (C) component being 50 to 2% by weight) 100 parts by weight) (D) Fluorine resin and / or silicone 0.01 to 5 parts by weight And (E) a phosphoric acid ester compound 1 represented by the following general formula (I)
A thermoplastic resin composition containing about 40 parts by weight.

Embedded image (In the formula, X is a divalent aromatic group. R ¹ , R ² , R ³ , R ⁴
Is a substituted or unsubstituted phenyl group. ) ”, (2)“ The thermoplastic resin composition of (1) above, wherein the component (C) in the resin composition (a) is 2 to 50% by weight. And (3) "in the thermoplastic resin composition according to (1), the component (B) in the resin composition (a) is 2 to 50% by weight, (C)
A thermoplastic resin composition, wherein the component is 0 to 48% by weight. It consists of.

The present invention will be described in detail below.

(A) Aromatic polycarbonate in the present invention
The bisphenol is generally a 2,2-bis (4-oxyphenyl) alkane type, a bis (4-oxyphenyl) ether type, a bis (4-oxyphenyl) sulfone, a sulfide or a sulfoxide type. It is a polymer or a copolymer of the same type. The aromatic polycarbonate is manufactured by any method. For example, 4,
For the production of polycarbonate from 4'-dihydroxydiphenyl-2,2-propane (commonly called bisphenol A), a phosgene method in which phosgene is blown in the presence of a caustic aqueous solution and a solvent, or 4, A method in which 4'-dihydroxydiphenyl-2,2-propane and carbonic acid diester are transesterified in the presence of a catalyst to produce them can be used.

The molecular weight of the aromatic polycarbonate is not particularly limited, but the intrinsic viscosity measured at 30 ° C. in a tetrahydrofuran solvent is 0.35 to 0.55 dl / g, especially 0.40.
It is preferable that the thermoplastic resin composition having a range of from 0.50 dl / g to be obtained has an excellent balance between impact resistance and fluidity during melt molding.

The (B) graft copolymer in the present invention means 30 to 80 parts by weight of a rubbery polymer and 70 to 70 parts by weight of a monomer mixture of an aromatic vinyl monomer and a vinyl cyanide monomer.
It is a graft copolymer obtained by graft-polymerizing 20 parts by weight. The term (B) graft copolymer as used herein includes a material having a structure obtained by graft-copolymerizing a rubber-like polymer, as well as a non-grafted copolymer.

The rubbery polymer preferably has a glass transition temperature of 0 ° C. or lower, and a diene rubber is preferably used. Specifically, polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, styrene-butadiene block copolymer,
Examples thereof include butyl acrylate-butadiene copolymer and other diene rubbers, polybutyl acrylate and other acrylic rubbers, polyisoprene, ethylene-propylene-diene terpolymers and the like. Among them, polybutadiene or butadiene copolymer is preferable.

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 0.60 μm.
m, particularly 0.18 to 0.40 μm is preferable because of excellent impact resistance and color tone.

Aromatic vinyl monomers are styrene,
Examples thereof include α-methylstyrene, vinyltoluene, o-ethylstyrene, pt-butylstyrene and the like, but styrene is particularly preferable.

Examples of vinyl cyanide-based monomers include acrylonitrile, methacrylonitrile and ethacrylonitrile, with acrylonitrile being 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, or anhydride. Α, β-unsaturated carboxylic acids such as maleic acid, phthalic acid and itaconic acid and their anhydrides, acrylamide, (meth)
2-Hydroxyethyl acrylate or the like can be used.

(B) The monomer mixture used in the graft copolymer contains 40% by weight or more of the aromatic vinyl monomer,
The range is preferably 50% by weight or more and 90% by weight or less, preferably 80% by weight or less, and the vinyl cyanide monomer is 10% by weight or more, preferably 20% by weight or more and 60% by weight or less, preferably Is used in the range of 50% by weight or less. In addition to the aromatic vinyl-based monomer and the vinyl cyanide-based monomer, other vinyl-based monomers copolymerizable therewith can be added, and the amount thereof is 50% by weight or less, further 30% by weight. % Or less is preferably used. Aromatic vinyl monomer ratio is 40
When the amount is out of the range of 90% by weight, the impact resistance of the resin composition is poor, which is not preferable. When the proportion of the vinyl cyanide-based monomer is more than 60% by weight, the thermal stability of the graft copolymer is remarkably lowered, resulting in a resin composition having a poor color tone.

(B) The ratio of the rubber-like polymer and the monomer mixture in obtaining the graft copolymer is such that the total graft copolymer 1
30 parts by weight or more, preferably 40 parts by weight or more, and 80 parts by weight or less, preferably 7 parts by weight of the rubbery polymer.
0 parts by weight or less is used. The amount of the monomer mixture is 70 parts by weight or less, preferably 60 parts by weight or less, and 20 parts by weight or more, preferably 30 parts by weight or more. When the proportion of the rubbery polymer is less than 30 parts by weight, the impact resistance of the resin composition is inferior, and when it exceeds 80 parts by weight, the rubbery polymer becomes poorly dispersed and the appearance of the molded product of the resin composition is impaired, which is preferable. Absent.

The (B) 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 in the presence of a rubbery polymer latex is continuously supplied to a polymerization container to carry out emulsion polymerization.

The (B) graft copolymer contains a non-grafted copolymer in addition to a material having a structure grafted to a rubbery polymer. The graft ratio of the (B) graft copolymer is not particularly limited, but is preferably 20 to 120% by weight, particularly preferably 30 to 70% by weight in order to obtain a resin composition excellent in balance of impact resistance and gloss. Here, the graft ratio is calculated by the following equation. Graft ratio (%) = <amount of vinyl copolymer graft-polymerized on rubber polymer> / <rubber content of graft copolymer> × 100

The characteristics of the non-grafted copolymer are not particularly limited, but the intrinsic viscosity [η] (measured at 30 ° C.) of the (B) graft copolymer-soluble component of methyl ethyl ketone.
Is 0.25 to 0.6 dl / g, especially 0.30 to 0.5
A range of 5 dl / g is preferably used because a resin composition having excellent impact resistance can be obtained.

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

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

If necessary, other vinyl-based monomer,
For example, maleimide-based monomers such as maleimide, N-methylmaleimide, N-cyclohexylmaleimide, and N-phenylmaleimide, ester compounds of (meth) acrylic acid methyl, ethyl, propyl, n-butyl, acrylic acid, methacrylic acid. , Maleic acid, maleic anhydride,
Vinyl-based monomers containing carboxyl groups such as phthalic acid and itaconic acid, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylic acid, glycidyl itaconic acid, allyl glycidyl ether, styrene-p-glycidyl ether, p-glycidyl styrene, etc. Vinyl monomers containing epoxy groups, 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, butoxymethylacte 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-based 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 is 40% by weight or more, preferably 50% by weight or more, and 90% by weight or less of the aromatic vinyl monomer.
It is preferably 80% by weight or less, and the content of vinyl cyanide monomer is 10% by weight or more, preferably 20% by weight or more, and 60% by weight or less, preferably 50% by weight or less. The content of the other vinyl-based monomer is 50% by weight or less, preferably 30% by weight or less.

(C) In the vinyl-based copolymer, when the content of the aromatic vinyl-based monomer is out of the range of 40 to 90% by weight, the impact resistance of the resin composition is deteriorated, which is not preferable. The molecular weight of the vinyl copolymer (C) is not particularly limited, but the intrinsic viscosity [η] (N, N-dimethylformamide solvent, measured at 30 ° C) is 0.35 to 0.85.
dl / g, especially those in the range of 0.4 to 0.6 dl / g are preferably used because a resin composition having excellent impact resistance and moldability can be obtained.

(C) The method for producing the vinyl-based copolymer is not particularly limited, and the bulk polymerization method, suspension polymerization method, emulsion polymerization method, bulk-polymerization method
A usual method such as a suspension polymerization method or a solution-bulk polymerization method can be used.

The resin composition (a) defined in the present invention is
It comprises the aromatic polycarbonate (A), the graft copolymer (B) and the vinyl copolymer (C) described above. Aromatic polycarbonate (A) is 50% by weight or more, preferably 60% by weight or more, and 98% by weight.
Below, it is preferably mixed in a range of 95% by weight or less.
Graft copolymer (B) and vinyl copolymer (C)
Of at least one type of copolymer, the total amount of component (B) and component (C) is 2% by weight or more, preferably 5% by weight or more and 50% by weight or less in the resin composition (a), It is mixed in a proportion of 40% by weight or less.

There are two more preferable blending amounts, and one is 2 to 50% by weight of the component (C) in the resin composition (a) together with the above blending amount. As another preferable blending amount, in the resin composition (a), the component (B) is 2 to 50.
% By weight, and component (C) is 0 to 48% by weight.

In the latter case, the graft copolymer (B)
Is 50% by weight or less, preferably 40% by weight or less, and 2
It is mixed in an amount of not less than 5% by weight, preferably not less than 5% by weight. The vinyl copolymer (C) is 48% by weight or less, preferably 35% by weight or less, and 0% or more, preferably 1%.
It is blended in a range of not less than 5% by weight, and more preferably not less than 5% by weight.

If the aromatic polycarbonate (A) is less than 50% by weight with respect to the resin composition (A), the flame retardancy and heat resistance are poor, and if it exceeds 98% by weight, the impact resistance, Molding processability deteriorates, which is not preferable.

In the present invention, (D) a fluorine resin or silicone is blended. A combination of these is also possible here. The fluororesin is a polymer containing a tetrafluoroethylene structure, and preferably has a fluorine content of 65 to 7
6% by weight, more preferably 70 to 76% by weight. Examples thereof include a tetrafluoroethylene polymer, a tetrafluoroethylene-hexafluoropropylene copolymer, and a copolymer of tetrafluoroethylene and a fluorine-free ethylenically unsaturated monomer.

The method for producing the fluororesin is not particularly limited, and may be 7 to 71 using, for example, the catalyst sodium peroxydisulfate, potassium or ammonium in an aqueous medium.
At a temperature of 0 to 200 ° C. under a pressure of kg / cm ² ,
A known method such as polymerization of tetrafluoroethylene or the like can be used.

The fluorocarbon resin usually has a specific gravity of 2.0 to 2.5.
A powdery material having g / cm ³ and a melting point of 310 to 350 ° C. is used, but is not particularly limited. The shape of the fluororesin is arbitrary, but preferably, a powdery one having a particle diameter (secondary) of 10 to 600 μm measured by ASTM D1457 is used.

The other component (D), silicone, is an organopolysiloxane, which is a polymer of dimethylsiloxane, a polymer of phenylmethylsiloxane, a polymer of diphenylsiloxane, a polymer of methylethylsiloxane, or methylpropylsiloxane. Examples thereof include polymers of siloxane and copolymers thereof. Further, a modified silicone in which the terminal or side chain of the molecular structure is substituted by an epoxy group, a hydroxyl group, a carboxyl group, a mercapto group, an amino group, an organic group having an ether bond, or the like is also useful. The number average molecular weight of the silicone is not particularly limited, but the lower limit thereof is preferably 200, more preferably 1000, and the upper limit thereof is 5,000,00.
A range of 0 is preferred. Any shape such as oil, gum, varnish, powder, and pellet can be used as the silicone.

The (E) phosphate ester compound represented by the following general formula (I) is blended in the thermoplastic resin composition of the present invention.

Embedded image In formula (I), X is a divalent aromatic group, R ¹ , R ² , R ³ ,
R ⁴ means a substituted or unsubstituted phenyl group.

Examples of the divalent aromatic group, that is, the arylene group, include o-phenylene group, m-phenylene group, p-phenylene group, biphenylene group, phenyleneoxyphenylene group and the like. Among them, m-phenylene group, p
-Phenylene group and biphenylene group are preferably used.

Although R ¹ , R ² , R ³ and R ⁴ are substituted or unsubstituted phenyl groups, "R ¹ , R ² , R ³ and R 4
^At least one of ⁴ is an alkyl group-substituted phenyl group having 1 to 6 carbon atoms, and "R ¹ , R ² , R ³ , R ⁴
Is a phenyl group substituted with an alkyl group having 1 to 6 carbon atoms, and "R ¹ , R ² , R ³ and R ⁴ are phenyl groups substituted with an alkyl group having 1 to 6 carbon atoms". It is preferably used, and the carbon number of the alkyl group is 1 to 3
Those of are preferably used.

Specifically, 1,4-phenylene-tetrakis (2,6-dimethylphenyl) phosphate ester,
1,4-phenylene-tetrakis (3,5-dimethylphenyl) phosphate ester, 1,4-phenylene-tetrakis (2,6-diethylphenyl) phosphate ester,
1,4-phenylene-tetrakis (3,5-diethylphenyl) phosphate ester, 1,4-phenylene-tetrakis (2,6-dipropylphenyl) phosphate ester,
1,4-phenylene-tetrakis (3,5-dipropylphenyl) phosphate ester, 1,3-phenylene-tetrakis (2,6-dimethylphenyl) phosphate ester,
1,3-phenylene-tetrakis (3,5-dimethylphenyl) phosphate ester, 1,3-phenylene-tetrakis (2,6-diethylphenyl) phosphate ester,
1,3-phenylene-tetrakis (3,5-diethylphenyl) phosphate ester, 1,3-phenylene-tetrakis (2,6-dipropylphenyl) phosphate ester,
1,3-phenylene-tetrakis (3,5-dipropylphenyl) phosphate ester, 4,4'-biphenylene-
Tetrakis (2,6-dimethylphenyl) phosphoric acid ester, 4,4′-biphenylene-tetrakis (3,5-dimethylphenyl) phosphoric acid ester, 4,4′-biphenylene-tetrakis (2,6-diethylphenyl) phosphorus Acid ester, 4,4′-biphenylene-tetrakis (3,3
5-diethylphenyl) phosphoric acid ester, 4,4'-biphenylene-tetrakis (2,6-dipropylphenyl) phosphoric acid ester, 4,4'-biphenylene-tetrakis (3,5-dipropylphenyl) phosphoric acid ester ,
1,4-phenylene-tetrakis (2-methylphenyl) phosphoric acid ester, 1,4-phenylene-tetrakis (3-methylphenyl) phosphoric acid ester, 1,4-phenylene-tetrakis (4-methylphenyl) phosphoric acid ester 1,4-phenylene-tetrakis (5-methylphenyl) phosphate ester, 1,4-phenylene-tetrakis (6-methylphenyl) phosphate ester, 1,3-
Phenylene-tetrakis (2-methylphenyl) phosphate, 1,3-phenylene-tetrakis (3-methylphenyl) phosphate, 1,3-phenylene-tetrakis (4-methylphenyl) phosphate, 1,
3-phenylene-tetrakis (5-methylphenyl) phosphate ester, 1,3-phenylene-tetrakis (6-
Methylphenyl) phosphoric acid ester, 4,4′-biphenylene-tetrakis (2-methylphenyl) phosphoric acid ester, 4,4′-biphenylene-tetrakis (3-methylphenyl) phosphoric acid ester, 4,4′-biphenylene-
Tetrakis (4-methylphenyl) phosphate ester,
4,4'-biphenylene-tetrakis (5-methylphenyl) phosphoric acid ester, 4,4'-biphenylene-tetrakis (6-methylphenyl) phosphoric acid ester, and the like, and particularly 1,4-phenylene-tetrakis ( Two
6-dimethylphenyl) phosphoric acid ester, 1,3-phenylene-tetrakis (2,6-dimethylphenyl) phosphoric acid ester, 4,4′-biphenylene-tetrakis (2,6-dimethylphenyl) phosphoric acid ester, 1, Four
-Phenylene-tetrakis (3-methylphenyl) phosphate, 1,3-phenylene-tetrakis (3-methylphenyl) phosphate, 4,4'-biphenylene-tetrakis (3-methylphenyl) phosphate are rigid Excellent in flame retardancy, which is preferable.

The method for producing the (E) phosphoric acid ester compound is not particularly limited, and 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 and reacting 2,6-dimethylphenol in an appropriate amount.

The blending amount of the (D) fluororesin in the present invention is such that the resin composition ((A) aromatic polycarbonate, (B) graft copolymer and (C) vinyl copolymer ( A) 0.01 to 5 parts by weight, preferably 0.05 to 2.0 parts by weight, based on 100 parts by weight.

If the amount of the (D) fluororesin compounded is less than 0.01 parts by weight, the flame retardancy of the thermoplastic resin composition deteriorates, and
When it exceeds the weight part, the impact resistance of the thermoplastic resin composition is deteriorated, which is not preferable.

The compounding amount of the (E) phosphate ester compound in the present invention is a resin composition comprising (A) an aromatic polycarbonate and (B) a graft copolymer and / or (C) a vinyl copolymer. 1 to 40 for 100 parts by weight of the item (a)
Parts by weight, preferably 4 to 30 parts by weight. If the compounding amount of the (E) phosphoric acid ester compound is less than 1 part by weight, the flame retardancy deteriorates, and if it exceeds 40 parts by weight, the impact resistance and heat resistance of the thermoplastic resin composition deteriorate, which is not preferable. (E) In addition to the phosphate ester compound, derived from the compound,
The resin composition (a) may contain oligomers such as dimers and trimers.

No particular limitation is imposed on the method for producing the resin composition of the present invention. For example, (A) aromatic polycarbonate,
(B) a graft copolymer, (C) a vinyl-based copolymer, (D) a fluororesin and (E) a mixture of a phosphoric ester compound by melt kneading with a Banbury mixer, roll, extruder, kneader, etc. Be commercialized.

The thermoplastic resin composition of the present invention may be blended with another thermoplastic resin compatible with it.
For example, polyphenylene ether, polyglutarimide,
Impact resistance and heat resistance can be improved by mixing with polycyclohexane dimethylene terephthalate, and chemical resistance can be improved by mixing with polyolefin, polybutylene terephthalate, polyethylene terephthalate, polyamide and the like. If necessary, glass fiber,
Fillers such as talc and potassium whisker titanate, various stabilizers such as antioxidants and ultraviolet absorbers, pigments, dyes, lubricants and plasticizers may also 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 housings of OA equipment, home electric appliances and the like and parts thereof because of its features such as flame retardancy.

[0049]

EXAMPLES In order to more specifically describe the present invention, examples and comparative examples will be described below. In addition, the part number and% in an Example show a weight part and weight%, respectively.

Reference Example 1 (Preparation of (A) Aromatic Polycarbonate) <A-1>4,4'-Dihydroxydiphenyl-2,2
Aromatic polycarbonate (A-1) was prepared by blowing phosgene with propane in the presence of a caustic aqueous solution and a solvent. The polymer obtained had an intrinsic viscosity of 0.45 dl / g measured at 30 ° C. in a tetrahydrofuran solvent.
Met. <A-2> An aromatic polycarbonate (A-2) having an intrinsic viscosity of 0.49 dl / g measured at 30 ° C. in a tetrahydrofuran solvent was prepared in the same manner as in A-1.

Reference Example 2 (Preparation of (B) Graft Copolymer) The preparation method of the graft copolymer is shown below. The graft ratio is obtained by the following method. Acetone was added to a predetermined amount (m) of the graft copolymer, and the mixture was refluxed for 4 hours. The solution was centrifuged at 8000 rpm (10,000 G) for 30 minutes, and the insoluble matter was filtered. The 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.

<B-1> Monobutadiene mixture 55 consisting of 79% styrene and 21% acrylonitrile in the presence of 45 parts (solid content) of polybutadiene latex (average rubber particle diameter 0.21 μ, gel content 80%). Part was 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-1).

The graft ratio of the obtained graft copolymer was 41%. The graft copolymer also contained styrene structural units 79% and acrylonitrile structural units 2
It contained 36% of a 1% non-graftable copolymer. The intrinsic viscosity of the soluble portion of methyl ethyl ketone was 0.43 dl / g. <B-2> Polybutadiene latex (average rubber particle size: 0.32 μ, gel content: 88%) Emulsified 40 parts of a monomer mixture consisting of 70% styrene and 30% acrylonitrile in the presence of 60 parts (as solid content). Polymerized. The resulting graft copolymer is coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered and dried to obtain a powdery graft copolymer (B
-2) was prepared. The resulting graft copolymer is B-1
The graft ratio was 38% as measured by the same method. This graft copolymer contained 17% of a non-grafting copolymer consisting of 70% styrene structural units and 30% acrylonitrile structural units. The intrinsic viscosity of the methyl ethyl ketone soluble component was 0.37 dl / g.

Reference Example 3 (C) Preparation of Vinyl Copolymer <C-1> A copolymer (C-1) was prepared by suspension polymerization of a monomer mixture of 70% styrene and 30% acrylonitrile. . The obtained copolymer had an intrinsic viscosity of 0.65 dl / g in the N, N-dimethylformamide-soluble component. <C-2> Styrene 50%, N-phenylmaleimide 3
A monomer mixture of 0% and acrylonitrile 20% was emulsion-polymerized to prepare a copolymer (C-2).

The copolymer obtained had an intrinsic viscosity of 0.56 dl / g of the N, N-dimethylformamide-soluble component.

Reference Example 4 (D) Fluorine resin or silicone <D-1> Polytetrafluoroethylene, Polyflon F104 (manufactured by Daikin Industries, Ltd.) (ASTM D1
Particle diameter (secondary) measured at 457 is 0.5 mm, melting point 34
0 ° C) was used. <D-2> Polyflon F201 which is polytetrafluoroethylene (manufactured by Daikin Industries, Ltd.) (ASTM D1
Particle diameter (secondary) measured at 457 is 0.5 mm, melting point 34
0 ° C) was used. <D-3> “Trefil” E-601 (manufactured by Toray Dow Corning Silicone Co., Ltd.) which is an epoxy group-modified silicone was used.

Reference Example 5 (E) Phosphoric Acid Ester <E-1> 1,4-phenylenetetrakis (2,6-dimethylphenyl) phosphoric acid ester PX201 (manufactured by Daihachi Chemical Industry Co., Ltd.) was used. .

<E-2> 1,3-phenylene-tetrakis (2,6-dimethylphenyl) phosphate <E-3>4,4'-biphenylenetetrakis (2,6)
-Dimethylphenyl) phosphate was used.

<E-4> Resorcinol-bis (phenyl) phosphate oligomer (CR733S, manufactured by Daihachi Chemical Industry Co., Ltd.) was used. (Used for comparative examples)

Examples 1 to 13 (A) Aromatic polycarbonate, (B) Graft copolymer, (C) Vinyl copolymer, (D) Fluorine resin, and ( E) Phosphoric acid ester was mixed in the compounding ratio shown in Table 1, and the resin temperature was set to 240 by using a vented 30 mmφ twin-screw extruder.
Melt kneading and extrusion were carried out at 0 ° C. to produce a pelletized polymer. Then, using an injection molding machine, test pieces are molded at a cylinder temperature of 260 ° C. and a mold temperature of 60 ° C.,
The physical properties were measured under the following conditions. 1/4 "Izod Impact Strength: ASTM D256-5
6A 1/8 "Izod Impact Strength: ASTM D256-5
6A Heat resistance: ASTM D648 (Test piece thickness: 1/4 ",
18.56kg / cm ² load) MFR (melt flow rate value): JIS K7207
(250 ° C., 2160 g). A larger value means better fluidity during molding. Flame resistance: 1 / vertical combustion test according to UL94 standard
The test was performed on a 16 ″ × 1/2 ″ × 5 ″ combustion test piece. The measurement results of the obtained test piece are shown in Table 2.

[0061]

[Table 1]

[0062]

[Table 2]

Comparative Examples 1 to 9 (A) Aromatic polycarbonate prepared in Reference Example, (B) Graft copolymer, (C) Vinyl copolymer, (D) Fluorine resin, and ( E) Phosphoric acid esters were mixed at the compounding ratios shown in Table 1, and the respective physical properties were measured by the same methods as in the examples. The measurement results are shown in Table 2. The following is clear from the results in Table 2. All of the resin compositions of the present invention (Examples 1 to 13) are excellent in impact resistance, heat resistance, fluidity (MFR value) and flame retardancy. On the other hand, aromatic polycarbonate
When the compounding amount of the (A) exceeds 98% by weight (Comparative Example 1,
8 and 9) are inferior in impact resistance and fluidity, and when less than 50% by weight (Comparative Example 2), inferior in heat resistance and flame retardancy, which is not preferable. If the compounding amount of the component (D) is less than 0.01 parts by weight (Comparative Example 3), the flame retardancy is poor, and if it exceeds 5 parts by weight (Comparative Example 4), the impact resistance and fluidity are poor. Not preferable. When the compounding amount of the phosphate ester compound (E) is less than 1 part by weight (Comparative Example 5), the flame retardancy is poor, and when it exceeds 40 parts by weight (Comparative Example 6), the impact resistance becomes poor, which is not preferable. Further, when a phosphoric acid ester compound other than the present invention is used (Comparative Example 7), the heat resistance deteriorates, which is not preferable.

[0064]

The thermoplastic resin composition of the present invention does not require bromine and chlorine compounds and has excellent flame retardancy, impact resistance, heat resistance and fluidity during molding.

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Claims (10)

[Claims] 1. (A) Aromatic polycarbonate, and
(B) 70 to 20 parts by weight of a monomer mixture containing 40 to 90% by weight of an aromatic vinyl-based monomer and 10 to 60% by weight of a vinyl cyanide-based monomer is added to a rubbery polymer 30 to 80% by weight. Graft copolymer formed by graft copolymerization in parts by weight, and /
Or (C) a vinyl copolymer obtained by copolymerizing a monomer mixture containing 40 to 90% by weight of an aromatic vinyl monomer and 10 to 60% by weight of a vinyl cyanide monomer. For 100 parts by weight of the resin composition (a) (however, the component (A): 50 to 98% by weight, the sum of the components (B) and (C) is 50 to 2% by weight), (D) the fluororesin And / or 0.01 to 5 parts by weight of silicone and (E) 1 to 40 parts by weight of a phosphoric acid ester compound represented by the following general formula (I) are mixed. Embedded image (In the formula, X is a divalent aromatic group. R ¹ , R ² , R ³ , R ⁴
Is a substituted or unsubstituted phenyl group. ) 2. The component (C) in the resin composition (a) is 2
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is about 50% by weight. 3. The component (B) in the resin composition (a) is 2
The thermoplastic resin composition according to claim 1, wherein the content of the component (C) is 0 to 48% by weight, and the amount of the component (C) is 0 to 48% by weight. 4. The phosphoric acid ester compound (E) is represented by the general formula (I), and at least one of R ¹ , R ² , R ³ and R ⁴ is phenyl substituted with an alkyl group having 1 to 6 carbon atoms. It is a group, The thermoplastic resin composition in any one of Claims 1-3 characterized by the above-mentioned. 5. The phosphoric acid ester compound (E) has the general formula (I), and R ¹ , R ² , R ³ and R ⁴ have 1 to 6 carbon atoms.
4. The thermoplastic resin composition according to claim 1, which is a phenyl group substituted with an alkyl group. 6. The phosphoric acid 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 any one of claims 1 to 3, wherein the phenyl group is an alkyl group-disubstituted phenyl group. 7. The rubbery polymer (B) which gives the graft copolymer is a diene rubber.
3. The thermoplastic resin composition according to any one of 3 above. 8. The thermoplastic according to any one of claims 1 to 3, wherein the rubbery polymer (B) which gives the graft copolymer has a number average particle size of 0.15 to 0.6 μm. Resin composition. 9. The graft ratio of the (B) graft copolymer is 20.
To 120% by weight, the thermoplastic resin composition according to any one of claims 1 to 3. 10. (D) The fluororesin has a secondary particle diameter of 10 to 6
The thermoplastic resin composition according to any one of claims 1 to 3, which has a size of 00 µm.