JPH0812864A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition comprising a specific composition, excellent in flame retardancy, balanced and excellent in impact resistance, toughness and moldability, and free from bromine and chlorine. CONSTITUTION:This composition is obtained by adding (C) 0.01-5 pts.wt. of a fluoro resin and/or a silicone and (D) 1-40 pts.wt. of a phosphate ester of the formula [X is divalent aromatic group; R<1>-R<4> are (substututed)phenyl] [preferably 1,4-phenyl enetetrakis(2,6-dimethylphenyl) phosphate ester] to 100 pts.wt. of a resin composition obtained by compounding (A) 50-90wt.% of the resin mixture of (i) 10-95wt.% of an aromatic polycarbonate with (ii) 90-5wt.% of an aromatic polyester (preferably polybutyrene terephthalate) with (B) 50-0wt.% of a graft copolymer produced by graft-copolymerizing 70-20 pts.wt. of a monomer mixture containing 20-90wt.% of an aromatic monomer (preferably styrene) to 30-80 pts.wt. of a rubbery polymer (preferably polybutadiene, a butadiene copolymer).

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 excellent in impact resistance, rigidity 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 for 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 relation to recent environmental problems, as a flame-retardant resin containing no chlorine and bromine flame retardant, aromatic polycarbonate, styrene-containing graft polymer such as ABS, triphenyl phosphate, etc. The method of blending the monophosphate ester (European Patent Publication No. 0174493), aromatic polycarbonate, styrene-containing copolymer and / or styrene-containing graft polymer and oligomeric phosphate ester flame retardant. A compounding method (Japanese Patent Laid-Open No. 2-115262), a method of compounding 1,4-phenylene-tetrakis (2,6-dimethylphenyl) phosphoric acid ester with an aromatic polycarbonate (US Pat.
No. 122,556) and a method of blending an aromatic polycarbonate with a resorcin polyphosphate flame retardant (JP-A-59-45351).

[0005]

However, in the method of using a halogen-based flame retardant, since the flame retardant is added in an increased amount to prevent the drop (drip) of the fire species during combustion, 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 of mold contamination during molding because the monophosphate ester is easily volatile. Japanese Patent Laid-Open No. 2-11
The composition described in US Pat. No. 5,262,556 has a liquid flame retardant and contains a large amount of it, and therefore has poor heat resistance. The composition described in US Pat. No. 5,122,556 has flame retardancy and impact resistance. The composition described in JP-A-59-45351 is inferior in impact resistance and molding processability. As described above, these materials were not able to satisfy various characteristics.

The present invention has excellent flame retardancy, impact resistance, and
It is an object of the present invention to provide a resin composition containing no chlorine and bromine compounds, which is excellent in balance of rigidity and moldability.

[0008]

DISCLOSURE OF THE INVENTION In the present invention, as a result of extensive studies to solve the above problems, a resin composition of an ABS resin and a resin mixture obtained by mixing an aromatic polycarbonate and an aromatic polyester in a specific ratio. The inventors have found that the above object can be efficiently achieved by adding polytetrafluoroethylene and a specific phosphoric acid ester to the product, and have reached the present invention.

That is, the present invention provides (1) "(A) (a) 10 to 95% by weight of aromatic polycarbonate.
(b) 50 to 100% by weight of a resin mixture consisting of 90 to 5% by weight of aromatic polyester, and (B) 70 to 20 parts by weight of a monomer mixture containing 20 to 90% by weight of an aromatic vinyl monomer. , Rubbery polymer 30-
(C) Fluorine-based resin and / or silicone from 0.01 to 100 parts by weight of the resin composition (a) consisting of 50 to 0% by weight of a graft copolymer obtained by graft copolymerizing 80 parts by weight.
A thermoplastic resin composition comprising 5 parts by weight and (D) 1 to 40 parts by weight of a phosphoric acid ester compound represented by the following general formula (I).

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. ) '' And (2)
“(A) the resin composition of the thermoplastic resin composition of (1)
50-95 resin mixture comprising (A) (a) aromatic polycarbonate and (b) 90-5% by weight of aromatic polyester.
%, And (B) the graft copolymer is 50 to 5% by weight, a thermoplastic resin composition. It consists of.

Hereinafter, the present invention will be described specifically. (A) Aromatic polycarbonate constituting the resin mixture (A) in the present invention
As the binder, generally, a bispheno such as 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 is used. It is a polymer or a copolymer composed of The aromatic polycarbonate is manufactured by any method. For example, in the production of polycarbonate of 4,4'-dihydroxydiphenyl-2,2-propane (commonly called bisphenol A), 4,4'-dihydroxydiphenyl-2,2-propane is used as a dioxy compound. A phosgene method in which phosgene is blown in the presence of a caustic aqueous solution and a solvent, or a method of transesterifying 4,4′-dihydroxydiphenyl-2,2-propane with a carbonic acid diester in the presence of a catalyst. Can be used.

Although the molecular weight of the aromatic polycarbonate is not particularly limited, it has an intrinsic viscosity of 0.35 to 0.55 dl / g, especially 0.40 measured at 30 ° C. in a tetrahydrofuran solvent.
It is preferably in the range of 0.50 dl / g because of excellent balance between impact resistance and fluidity of the resulting thermoplastic resin composition.

The (b) aromatic polyester, which is another constituent of the resin mixture (A), is a polyester having an aromatic ring in the chain unit of the polymer, and the aromatic dicarboxylic acid and diol (or ester formation thereof) are formed. A polymer or a copolymer obtained by a condensation reaction containing a functional derivative) as a main component.

Examples of the aromatic dicarboxylic acid as used herein include terephthalic acid, isophthalic acid, orthophthalic acid, and 1,5-
Naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-
Biphenyl ether dicarboxylic acid, 4,4'-biphenyl methane dicarboxylic acid, 4,4'-biphenyl sulfone dicarboxylic acid, 4,4'-biphenyl isopropylidene dicarboxylic acid, 1,2-bis (phenoxy) ethane-
4,4'-dicarboxylic acid, 2,5-anthracene dicarboxylic acid, 2,6-anthracene dicarboxylic acid, 4,4 '
There are -p-ta-phenylenedicarboxylic acid, 2,5-pyridinedicarboxylic acid and the like, and terephthalic acid is particularly preferably used.

These aromatic dicarboxylic acids may be used as a mixture of two or more kinds. In addition, if it is a small amount, adipic acid, azelaic acid, sebacic acid, aliphatic dicarboxylic acids such as dodecanediacid, and one or more alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid can be used together with these aromatic dicarboxylic acids. .

As the diol component, ethylene glycol, propylene glycol, butylene glycol,
Hexylene glycol, neopentyl glycol, 2-
Aliphatic diols such as methyl-1,3-propanediol, diethylene glycol and triethylene glycol,
Examples thereof include alicyclic diole such as 1,4-cyclohexane dimethanol, and a mixture thereof. If it is a small amount, a long-chain geo-molecule having a molecular weight of 400 to 6000
One or more of polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol and the like may be copolymerized.

Specific aromatic polyesters include polyethylene terephthalate and polypropylene terephthalate.
, Polybutylene terephthalate, polyhexylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene-1,2-bis (phenoxy) ethane-4,4'-dicarboxylate In addition to the above, copolymerized polyesters such as polyethylene isophthalate / terephthalate, polybutylene terephthalate / isophthalate, polybutylene terephthalate / decane dicarboxylate and the like can be mentioned. Of these, polybutylene terephthalate and polyethylene terephthalate, which are well-balanced in mechanical properties and moldability, are preferably used. The method for producing the aromatic polyester (b) is not particularly limited, and a known production method can be used.

The molecular weight of the aromatic polyester (b) is not particularly limited, but it is 0.5 g in an ortho-chlorophenol solvent.
/ Dl solution has a specific viscosity of 1.2 to 2.5 at 25 ° C,
In particular, those in the range of 1.5 to 2.0 are preferable because they are excellent in impact resistance and toughness.

In the resin mixture (A), (a) 10 to 95% by weight of aromatic polycarbonate, preferably 30 to 90% by weight.
The amount of the aromatic polyester (b) is 90 to 5% by weight, preferably 70 to 10% by weight. If the content of the aromatic polycarbonate (a) is less than 10% by weight, the flame retardancy becomes poor, and if it exceeds 95% by weight, the rigidity becomes poor, which is not preferable.

In the present invention, the (B) graft copolymer is preferably blended. The (B) graft copolymer is a graft copolymer obtained by graft polymerizing a monomer mixture containing an aromatic vinyl monomer in 30 to 80 parts by weight of a rubbery polymer. The term (B) graft copolymer as used herein includes a material having a structure grafted to a rubbery polymer and a copolymer not grafted.

As the rubbery polymer, those having a glass transition temperature of 0 ° C. or lower are suitable, and 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 rubber-like 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.

As a monomer other than the aromatic vinyl type monomer, for the purpose of improving toughness and color tone, a (meth) acrylic acid ester type monomer and / or for the purpose of further improving impact resistance, Vinyl cyanide-based monomers are preferably used.
(Meth) acrylic acid ester-based monomers include acrylic acid and methacrylic acid methyl, ethyl, propyl, and n.
Examples thereof include esterified products with -butyl and i-butyl, and methyl methacrylate is particularly preferable. 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 and N-phenylmaleimide, acrylic acid,
Α, β-unsaturated carboxylic acids such as methacrylic acid, maleic acid, maleic anhydride, phthalic acid, and itaconic acid and their anhydrides, acrylamide, (meth) acrylic acid-2
-Hydroxyethyl, (meth) acrylic acid glycidyl ester and the like can also be used.

(B) The monomer mixture used in the graft copolymer must contain 20 to 90% by weight of the aromatic vinyl monomer, preferably 20 to 80% by weight. . When a (meth) acrylic acid ester-based monomer is mixed, it is preferably 80% by weight or less,
Furthermore, 75% by weight or less is preferably used. When a vinyl cyanide-based monomer is mixed, it is preferably used in an amount of 60% by weight or less, more preferably 50% by weight or less. Further, the aromatic vinyl-based monomer in the monomer mixture, (meth)
It is preferable that the total amount of the acrylic acid ester-based monomer and the vinyl cyanide-based monomer is 50% by weight or more, and further 60% by weight.

The ratio of the aromatic vinyl monomer is 20 to 90.
If the amount is out of the range, the impact resistance of the resin composition is poor, which is not preferable. If the amount of the (meth) acrylic acid ester-based monomer exceeds 80% by weight, the toughness deteriorates, 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 reduced, 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, more preferably 30 to 70% by weight in order to obtain a resin composition having excellent impact resistance and gloss in balance. 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] of the (B) graft copolymer-soluble component of methyl ethyl ketone (measured at 30 ° C.)
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.

The resin composition of the present invention may contain another type of polymer obtained from a vinyl-based monomer in order to control the target physical properties. Among them, those which essentially require an aromatic vinyl monomer are preferably used.

Aromatic vinyl monomers are styrene,
Examples thereof include α-methylstyrene, p-methylstyrene, t-butylstyrene, vinyltoluene, o-ethylstyrene, and the like, with styrene being particularly preferable. One or more of these can be used.

Concretely, polystyrene, styrene-acrylonitrile copolymer, styrene-methyl methacrylate copolymer, styrene-methyl methacrylate-acrylonitrile copolymer, α-methylstyrene-acrylonitrile copolymer. , Α-methylstyrene-methylmethacrylate copolymer, α-methylstyrene-methylmethacrylate-acrylonitrile copolymer, styrene-N-
Examples thereof include a phenylimaleimide copolymer, a styrene-methylmethacrylate-N-phenylimaleimide copolymer, and a styrene-acrylonitrile-N-phenylimaleimide copolymer. It is preferable that the structure obtained from the blended aromatic vinyl monomer is 20 to 90% by weight of the polymer, because the resulting resin composition has excellent impact resistance.

There is no limitation on the properties of the polymer, but the intrinsic viscosity [η] (N, N-dimethylformamide solvent, 30 ° C.)
Measurement) is 0.35 to 0.85 dl / g, especially 0.45
In the range of up to 0.70 dl / g, excellent impact resistance,
A resin composition having moldability is obtained, which is preferable.

In the present invention, the resin mixture (A) comprising (a) aromatic polycarbonate and (b) aromatic polyester is 50 to 100% by weight, preferably 50 to 95%.
%, More preferably 55 to 90% by weight, graft copolymer (B) 50 to 0% by weight, preferably 50 to 5% by weight, more preferably 45 to 10% by weight. It is necessary to say (a). If the resin mixture (A) is less than 50% by weight, the flame retardancy deteriorates,
If it exceeds 95% by weight, impact resistance is deteriorated, which is not preferable. By blending the graft copolymer (B), an effect of improving molding fluidity is imparted.

In the present invention, a fluororesin or silicone is blended as the component (C). Also, both can be used together. The fluororesin is a polymer containing a tetrafluoroethylene structure, and preferably has a fluorine content of 6
5 to 76% 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 (C) fluororesin is not particularly limited, and may be 7 to 7 using, for example, the catalyst sodium peroxydisulfate, potassium or ammonium in an aqueous medium.
A known method such as polymerizing tetrafluoroethylene or the like at a temperature of 0 to 200 ° C. under a pressure of 1 kg / cm ² can be used.

(C) The fluororesin usually has a specific gravity of 2.0 to
A powdery material having 2.5 g / cm ³ and a melting point of 310 to 350 ° C. is used, but it is not particularly limited. The shape of the fluororesin is arbitrary, but preferably ASTM D14
A powdery material having a particle size (secondary) of 10 to 600 μm measured in 57 is used.

The other component (C), silicone, is an organopolysiloxane, and examples thereof include dimethylsiloxane polymers, phenylmethylsiloxane polymers, and copolymers thereof. Furthermore, the terminal or side chain of the molecular structure is an epoxy group, a hydroxyl group, a carboxyl group,
Modified silicones substituted with mercapto groups, amino groups, ethers, etc. are 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 preferably in the range of 5,000,000. Any shape such as oil, gum, varnish, powder, and pellet can be used as the silicone.

Next, the (D) phosphate ester compound used in the present invention is represented by the following general formula (I).

Embedded image (In the formula (I), X is a divalent aromatic group, R ¹ , R ² ,
R ³ and R ⁴ mean 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 (D) phosphoric acid ester compound is not particularly limited, and for example, after reacting phosphorus oxychloride and hydroquinone in a solvent in a substantially 2: 1 molar ratio,
1,4-phenylene-tetrakis (2,6-dimethylphenyl) phosphoric acid ester can be obtained by adding and reacting 2,6-dimethylphenol in an appropriate amount.

(C) Fluorine-based resin and / or
Alternatively, the silicone content is (A) (a) an aromatic polycarbonate and (b) a resin mixture consisting of an aromatic polyester.
(B) Based on 100 parts by weight of the total amount of the graft copolymer,
It is 0.01 to 5 parts by weight, preferably 0.05 to 2.0 parts by weight. If the compounding amount of the (C) fluorine-based resin is less than 0.01 parts by weight, the flame retardancy of the resin composition deteriorates, and if it exceeds 5% by weight, the impact resistance of the resin composition deteriorates, which is not preferable.

The blending amount of the (D) phosphate ester compound in the present invention is "(A) (a) a resin mixture comprising an aromatic polycarbonate and (b) an aromatic polyester" and (B) a graft copolymer. The amount is 1 to 40 parts by weight, preferably 4 to 30 parts by weight, based on 100 parts by weight of the resin composition (a) composed of the combined material. If the compounding amount of the (D) phosphate ester compound is less than 1 part by weight, the flame retardancy deteriorates, and if it exceeds 40% by weight, the impact resistance of the resin composition deteriorates, which is not preferable.

No particular limitation is imposed on the method for producing the resin composition of the present invention. For example, (a) an aromatic polycarbonate,
(b) Aromatic polyester, (B) Graft copolymer, (C)
The fluororesin and the (D) phosphate ester compound are mixed and melt-kneaded with a Banbury mixer, a roll, an extruder, a kneader or the like to obtain a product.

The thermoplastic resin composition of the present invention may be blended with another thermoplastic resin compatible with it.
For example, polyphenylene ether, polyglutarimide, etc. can be mixed to improve impact resistance and heat resistance, and polyolefin, polyamide, etc. can be mixed to improve chemical resistance. Further, if necessary, glass fiber, metal salt of borate, talc, filler such as potassium titanate, antioxidants, various stabilizers such as ultraviolet absorbers, pigments, dyes, lubricants and plasticizers may be added. it can.

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.

[0050]

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 (a) Preparation of Aromatic Polycarbonate Using 4,4'-dihydroxydiphenyl-2,2-propane, phosgene was blown in the presence of an aqueous solution of caustic alkali and a solvent for aromatic polycarbonate. -Bonet was prepared.
The polymer obtained had an intrinsic viscosity of 0.48 dl / g measured at 30 ° C. in a tetrahydrofuran solvent.

Reference Example 2 (b) Preparation of Aromatic Polyester Polybutylene terephthalate (PBT-1200S manufactured by Toray Industries, Inc.) having a specific viscosity of 1.58 measured at 25 ° C. in an orthochlorophenol solvent was used. used.

Reference Example 3 (B) Preparation of Graft Copolymer The method for preparing 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> 40 parts of a monomer mixture consisting of 70% styrene and 30% acrylonitrile was added in the presence of 60 parts (average rubber particle size: 0.32 µ, gel content: 88%) (converted to a solid content) of polybutadiene latex. 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 38%. This graft copolymer comprises 17% of a non-grafting copolymer consisting of 70% styrene structural units and 30% acrylonitrile structural units.
It was contained. The intrinsic viscosity of the methyl ethyl ketone soluble component was 0.36 dl / g. <B-2> Polybutadiene latex (average rubber particle diameter 0.24 μ, gel content 80%) in the presence of 45 parts (solid content conversion), styrene 24%, methyl methacrylate 72
% And acrylonitrile 4% monomer mixture 5
Emulsion polymerization was carried out by adding 5 parts. A powdery graft copolymer (B-2) was prepared from the obtained graft copolymer in the same manner as in B-1. The graft ratio of the obtained graft copolymer was 45%. This graft copolymer is
It contained 34% of a non-grafting copolymer consisting of 24% styrene structural unit, 72% methylmethacrylate structural unit and 4% acrylonitrile structural unit. Methyl ethyl ketone soluble component has an intrinsic viscosity of 0.26d
It was 1 / g.

Reference Example 4 <C-1> Fluorine-based resin Polytetrafluoroethylene polyflon F104
(Manufactured by Daikin Industries, Ltd.) (particle diameter (secondary) measured by ASTM D1457: 0.5 mm, melting point: 340 ° C.) was used. <C-2> Silicone “Trefil” E-6 which is an epoxy group-modified silicone
01 (manufactured by Toray Dow Corning Silicone Co., Ltd.) was used.

Reference Example 5 (D) Phosphoric Acid Ester D-1: 1,4-phenylene-tetrakis (2,6-dimethylphenyl) phosphoric acid ester (PX201, manufactured by Daihachi Chemical Industry Co., Ltd.) was used. D-2: 1,3-ferrene-tetrakis (2,6-dimethylphenyl) phosphate ester was used. D-3: 4,4'-biphenylene-tetrakis (2,6
-Dimethylphenyl) phosphate was used. D-4: Resorcinol-bis (phenyl) phosphate oligomer (CR733S, manufactured by Daihachi Chemical Industry) was used. (Used for comparative examples)

Examples 1 to 11 (a) Aromatic polycarbonate, (b) Aromatic polyester, (B) Graft copolymer, (C) Polytetrafluoroethylene, and (D) prepared in Reference Examples. ) Phosphate ester was mixed in the compounding ratio shown in Table 1 and melt-kneaded and extruded at a resin temperature of 240 ° C. in a vented 30 mmφ twin-screw extruder to produce a pelletized polymer. Then, using an injection molding machine, the cylinder temperature is 260 ° C and the mold temperature is 60 ° C.
The test piece was molded by and 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 Flexural modulus: ASTM D790 Heat resistance: ASTM D648 (Test piece thickness 1/4 ", 1
8.56 kg / cm ² load) MFR: JIS K7207 (250 ° C, load: 21
60 g) A larger value means better fluidity during molding. Flame resistance: 1 / vertical combustion test according to UL94 standard
A 16 ″ × 1/2 ″ × 5 ″ combustion test piece was used.

The measurement results are shown in Table 2.

[0058]

[Table 1]

[0059]

[Table 2]

Comparative Examples 1 to 11 (a) Aromatic Polycarbonate, (b) Aromatic Polyester, (B) Graft Copolymer, (C) Polytetrafluoroethylene, and (D) ) 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.

From the results of Table 2, the following is clear.
All of the resin compositions of the present invention (Examples 1 to 11) are excellent in impact resistance, rigidity, fluidity (MFR value) and flame retardancy.

On the other hand, the aromatic polycarbonate in the resin mixture (A)
When the blending amount of the binder (a) exceeds 95% by weight (Comparative Examples 1 and 9), the rigidity is poor, and when it is less than 10% by weight (Comparative Examples 2 and 10), the impact resistance and flame retardancy are low. Inferior and not preferable.
When the content of the graft copolymer (B) exceeds 50% by weight (Comparative Example 4), the flame retardancy is poor, and when it is less than 5% by weight (Comparative Example 3), the impact resistance is poor, which is not preferable. When the amount of the fluorine-based resin (C) is less than 0.01 parts by weight (Comparative Example 5), the flame retardancy is poor, and when it exceeds 5 parts by weight (Comparative Example 6), the impact resistance and the fluidity are poor. Therefore, it is not preferable.
When the compounding amount of the phosphate ester compound (D) is less than 1 part by weight (Comparative Example 7), the flame retardancy is poor, and when it exceeds 40 parts by weight (Comparative Example 8), the impact resistance is poor, which is not preferable. When an oligomer is used as a phosphate ester (Comparative Example 1)
1) is inferior in bending elastic modulus and heat resistance as compared with Example 2 using the phosphoric acid ester of the present invention.

Examples 12 to 22 Table 3 shows (a) aromatic polycarbonate, (b) aromatic polyester, (C) polytetrafluoroethylene or silicone, and (D) phosphoric acid ester prepared in Reference Examples. A pellet-shaped polymer was produced by mixing at a compounding ratio and performing melt-kneading and extrusion at a resin temperature of 250 ° C. with a vented 30 mmφ twin-screw extruder. Then, using an injection molding machine, the cylinder temperature is 260 ° C. and the mold temperature is 60.
A test piece was molded at ℃, and the physical properties were measured under the same conditions as in Example 1. Table 4 shows the measurement results of the obtained test pieces.

Comparative Examples 12 to 18 (a) Aromatic polycarbonate, (b) Aromatic polyester, (C) Polytetrafluoroethylene and (D) Phosphoric acid ester prepared in Reference Examples were used in the compounding ratios shown in Table 3. After mixing, a test piece was prepared in the same manner as in Example 11, and the physical properties of the obtained test piece were measured. The measurement results are shown in Table 4.

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[Table 3]

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[Table 4]

From the results of Table 4, the following is clear.
All of the resin compositions 12 to 22 of the present invention are excellent in impact resistance and rigidity balance and flame retardancy.

On the other hand, when the blending amount of the aromatic polycarbonate (A) exceeds 95% by weight (Comparative Example 12), the rigidity is poor, and when it is less than 10% by weight (Comparative Example 13), the impact resistance, the rigidity and the hardness are poor. Inflammability is poor and not preferable. Fluorine resin (C)
If the compounding amount is less than 0.01 parts by weight (Comparative Example 14), the flame retardancy is poor, and if it exceeds 5 parts by weight (Comparative Example 15), the impact resistance becomes poor, which is not preferable. When the compounding amount of the phosphoric acid ester compound (D) is less than 1 part by weight (Comparative Example 1
6) is inferior in flame retardancy, and when it exceeds 40 parts by weight (Comparative Example 17), the impact resistance is poor and is not preferable. Further, when a phosphoric acid ester compound not specified in the present invention is used (Comparative Example 18), the heat resistance is deteriorated, which is not preferable. When an oligomer is used as a phosphate ester (Comparative Example 1)
8) is inferior in bending elastic modulus and heat resistance to Example 14 using the phosphoric acid ester of the present invention.

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

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[Procedure amendment]

[Submission date] June 23, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0059

[Correction method] Change

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[Table 2]

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Claims (15)

[Claims] 1. A) (a) Aromatic polycarbonate 10 to 9
50 to 100% by weight of a resin mixture consisting of 5% by weight and (b) 90 to 5% by weight of an aromatic polyester, and (B) a monomer mixture 70 containing 20 to 90% by weight of an aromatic vinyl monomer. 20 parts by weight of the rubbery polymer 30 to
(C) Fluorine-based resin and / or silicone from 0.01 to 100 parts by weight of the resin composition (a) consisting of 50 to 0% by weight of a graft copolymer obtained by graft copolymerizing 80 parts by weight.
A thermoplastic resin composition comprising 5 parts by weight and (D) 1 to 40 parts by weight of a phosphoric acid ester compound represented by the following general formula (I). 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. A resin composition comprising (A) a resin mixture comprising (A) (a) an aromatic polycarbonate and (b) an aromatic polyester in an amount of 50 to 95% by weight, and (B) a graft copolymer. 5 polymer
The thermoplastic resin composition according to claim 1, which is 0 to 5% by weight. 3. The phosphoric acid ester compound (D) is represented by the general formula (I), and at least one of R ¹ , R ² , R ³ and R ⁴ is an alkyl group-substituted phenyl group having 1 to 6 carbon atoms. It is a group, The thermoplastic resin composition of Claim 1 or 2 characterized by the above-mentioned. 4. The phosphoric acid ester compound (D) has the general formula (I), and R ¹ , R ² , R ³ and R ⁴ have 1 to 6 carbon atoms.
3. The thermoplastic resin composition according to claim 1, which is a phenyl group substituted with an alkyl group. 5. The phosphoric acid ester compound (D) has the general formula (I), and R ¹ , R ² , R ³ and R ⁴ have 1 to 6 carbon atoms.
3. The thermoplastic resin composition according to claim 1 or 2, wherein the phenyl group is an alkyl group-disubstituted phenyl group. 6. The thermoplastic resin composition according to claim 1 or 2, wherein the rubbery polymer (B) which gives the graft copolymer is a diene rubber. 7. The thermoplastic resin composition according to claim 1, wherein (B) the rubber-like polymer which gives the graft copolymer has a number average particle diameter of 0.15 to 0.6 μm. . 8. The monomer other than the aromatic vinyl-based monomer in the monomer mixture (B) giving the graft copolymer is a (meth) acrylic acid ester-based monomer or a vinyl cyanide-based monomer. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is at least one kind of monomer in the body. 9. (B) The (meth) acrylic acid ester-based monomer in the monomer mixture which gives the graft copolymer is 80
The thermoplastic resin composition according to claim 8, characterized in that it is contained in an amount of not more than wt%. 10. The thermoplastic resin composition according to claim 8, wherein the vinyl cyanide-based monomer in the monomer mixture which gives the (B) graft copolymer is 50% by weight or less. 11. A total of the blending amounts of the aromatic vinyl-based monomer, the (meth) acrylic acid ester-based monomer and the vinyl cyanide-based monomer in the monomer mixture (B) which gives the graft copolymer. Is 50% by weight or more, and the thermoplastic resin composition according to any one of claims 8 to 10. 12. The graft ratio of (B) graft copolymer is 2
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is 0 to 120% by weight. 13. (C) Fluorine-based resin having a secondary particle diameter of 10 to 6
The thermoplastic resin composition according to claim 1, which has a size of 00 μm. 14. (a) The polycarbonate has an intrinsic viscosity of 0.35 to 0.5 measured at 30 ° C. in a tetrahydrofuran solvent.
It is 5 dl / g, The thermoplastic resin composition of Claim 1 or 2 characterized by the above-mentioned. 15. The method according to claim 1 or 2, wherein (b) the aromatic polyester has a specific viscosity of 1.2 to 2.5 in a 0.5 ° C. o-chlorophenol solvent at 0.5 g / dl solution. The thermoplastic resin composition.