JPH11246721A - Thermoplastic resin composition and production thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a material that largely enhances the compatibility of an aromatic polycarbonate and a styrene resin in order to improve the physical balance of rigidity and impact resistance of an aromatic polycarbonate/styrene resin and the flame retardancy thereof. SOLUTION: A thermoplastic resin composition comprises, per 100 pts.wt. of the total of the components (A) and (B), the components (C)-(E), respectively, in a predetermined amount as given below: (A) 95-5 pts.wt. aromatic polycarbonate; (B) 5-95 pts.wt. styrene resin; (C) 5-50 pts.wt. melt kneaded resin composition comprising a polyphenylene ether, a saturated polyester and a phosphorus flame retardant; (D) 0-100 pts.wt. phosphorus flame retardant; and (E) 0-5 pts.wt. polytetrafluoroethylene.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel thermoplastic resin composition comprising an aromatic polycarbonate and a styrene-based resin, which is excellent in balance of physical properties such as rigidity and impact resistance and flame retardancy. It relates to the manufacturing method.

[0002]

2. Description of the Related Art Conventionally, aromatic polycarbonate / ABS
Aromatic polycarbonate / styrene resin compositions represented by alloys are widely used in the market as materials having both fluidity and impact resistance. The flame retardant composition is also OA
Widely used in the field. This flame-retardant composition, particularly a material using a phosphorus-based flame retardant, is disclosed in JP-A-2-115.
262 and JP-A-2-32154 disclose typical compositions. Further, in the OA field, particularly in applications such as housings, thin wall, high rigidity and high fluidity are required,
Numerous materials are on the market.

[0003]

DISCLOSURE OF THE INVENTION The present invention aims at improving the balance between the physical properties of the rigidity and impact resistance of an aromatic polycarbonate / styrene resin and improving the flame retardancy of the aromatic polycarbonate / styrene resin. The purpose of the present invention is to provide a material having a significantly higher quality.

[0004]

Means for Solving the Problems The present inventors have found that a very good melt kneading resin composition containing a polyphenylene ether, a saturated polyester and a phosphorus-based flame retardant is mixed with an aromatic polycarbonate and a styrene resin. The present inventors have found that a composition having compatibility, desirable physical properties and flame retardancy can be obtained, and completed the present invention.

That is, the gist of the present invention is as follows.
The thermoplastic resin composition contains a predetermined amount of the following components (C) to (E) based on 100 parts by weight of the total of the following components (A) and (B). (A) 95 to 5 parts by weight of an aromatic polycarbonate (B) 5 to 95 parts by weight of a styrene-based resin (C) 5 to 50 parts by weight of a melt-kneaded resin composition containing polyphenylene ether, a saturated polyester and a phosphorus-based flame retardant (D) Phosphorus flame retardant 0 to 100 parts by weight (E) Polytetrafluoroethylene 0 to 5 parts by weight

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. (A) Aromatic polycarbonate The aromatic polycarbonate used for the component (A) in the present invention can be obtained by reacting an aromatic hydroxy compound or a small amount thereof with a phosgene or carbonic acid diester. , A polycarbonate polymer or copolymer which may be branched. Further, two or more of these polycarbonate polymers or copolymers may be used as a mixture.

As aromatic dihydroxy compounds, 2,
2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -p-diisopropylbenzene, hydroquinone, resorcinol, 4,4′-dihydroxydiphenyl, and the like, Preferably, bisphenol A is used.

In order to obtain a branched aromatic polycarbonate, phloroglucin, 4,6-dimethyl-2,4,6-
Tri (4-hydroxyphenyl) heptene-2,4,6
-Dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3,1,3,5
-Tri (4-hydroxyphenyl) benzene, 1,1,
Polyhydroxy compounds such as 1-tri (4-hydroxyphenyl) ethane, 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol),
5-chlorisatin, 5,7-dichlorisatin, 5-
A polyfunctional compound such as bromoisatin may be used as a part of the aromatic dihydroxy compound.
It is 0.01 to 10 mol%, preferably 0.1 to 2 mol%.

The aromatic polycarbonate is preferably a polycarbonate polymer derived from 2,2-bis (4-hydroxyphenyl) propane,
Examples include polycarbonate copolymers derived from 2-bis (4-hydroxyphenyl) propane and other aromatic dihydroxy compounds.

[0010] The molecular weight of the aromatic polycarbonate is a viscosity average molecular weight of 16.0, calculated from a solution viscosity measured at a temperature of 25 ° C using methylene chloride as a solvent.
00 to 30,000, preferably 18,000 to 23,
000. In order to control the molecular weight, a monovalent aromatic hydroxy compound may be used, and m- or p-methylphenol, m- or p-propylphenol, pt
tert-butylphenol and p-long-chain alkyl-substituted phenols.

(B) Styrene Resin The styrene resin used as the component (B) in the present invention is a polymer containing a styrene monomer as a main component. Examples include a copolymer with a polymerizable monomer, and a styrene-based graft copolymer obtained by copolymerizing a monomer containing a styrene-based monomer in the presence of a rubber component. Examples of the copolymer of a styrene-based monomer and another copolymerizable monomer include an AS resin, and examples of the styrene-based graft copolymer include H
IPS resin, ABS resin, AES resin, AAS resin, and the like. Examples of the method for producing the styrene resin include known methods such as an emulsion polymerization method, a solution polymerization method, a suspension polymerization method, and a bulk polymerization method.

The styrene monomer includes, for example, styrene, α-methylstyrene, p-methylstyrene and the like, preferably styrene. Examples of the monomer copolymerizable with the styrene-based monomer include, for example, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, methyl acrylate, ethyl acrylate, propyl acrylate, methyl methacrylate, and methacrylic acid. Examples include alkyl (meth) acrylates such as ethyl, maleimide, and N-phenylmaleimide, and preferably include vinyl cyanide monomers and alkyl (meth) acrylates.

The rubber component used to obtain the styrene-based graft copolymer includes diene rubber, acrylic rubber, ethylene / propylene rubber, silicone rubber, and the like, and preferably, diene rubber and acrylic rubber. And the like.

Examples of the diene rubber include polybutadiene, butadiene / styrene copolymer, polyisoprene, lower alkyl ester copolymer of butadiene / (meth) acrylic acid, and lower alkyl of butadiene / styrene / (meth) acrylic acid. Ester copolymers and the like,
As lower alkyl esters of (meth) acrylic acid,
For example, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate and the like can be mentioned. (Meth) in lower alkyl ester copolymer of butadiene / (meth) acrylic acid or lower alkyl ester copolymer of butadiene / styrene / (meth) acrylic acid
The ratio of the lower alkyl ester of acrylic acid is preferably 30% by weight or less of the rubber weight.

Examples of the acrylic rubber include an alkyl acrylate rubber, and the alkyl group preferably has 1 to 8 carbon atoms. Specific examples of the alkyl acrylate rubber include ethyl acrylate, butyl acrylate, ethylhexyl acrylate, and the like. A crosslinkable ethylenically unsaturated monomer may optionally be used in the alkyl acrylate rubber, and examples of the crosslinker include alkylene diol, di (meth) acrylate, and polyester di (meth) acrylate. , Divinylbenzene, trivinylbenzene, triallyl cyanurate, allyl (meth) acrylate, butadiene, isoprene and the like. The acrylic rubber further includes a core-shell polymer having a crosslinked diene rubber as a core.

(C) Melt-kneaded resin composition containing polyphenylene ether, saturated polyester and phosphorus-based flame retardant (a) Polyphenylene ether The polyphenylene ether constituting the component (C) in the present invention is represented by the following formula (1). It is a homopolymer or a copolymer having a structure.

[0017]

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Wherein Q ¹ represents a halogen atom, a primary or secondary alkyl group, a phenyl group, an aminoalkyl group, a hydrocarbonoxy group or a halohydrocarbonoxy group, and Q ² represents Each represents a hydrogen atom, a halogen atom, a primary or secondary alkyl group, a phenyl group, a haloalkyl group, a hydrocarbonoxy group or a halohydrocarbonoxy group, and m represents a number of 10 or more. ]

Preferred examples of Q ¹ and Q ² primary alkyl groups are methyl, ethyl, n-propyl, n-butyl,
n-amyl, isoamyl, 2-methylbutyl, n-hexyl, 2,3-dimethylbutyl, 2-, 3- or 4
-Methylpentyl or heptyl. Suitable examples of secondary alkyl groups are isopropyl, sec-butyl or 1-ethylpropyl. In most cases, Q1 is an alkyl group or a phenyl group, particularly an alkyl group having 1 to 4 carbon atoms, and Q2 is a hydrogen atom.

Suitable homopolymers of polyphenylene ether include, for example, those comprising 2,6-dimethyl-1,4-phenylene ether units. Suitable copolymers include the above units and 2,3,6-trimethyl-1,
It is a random copolymer comprising a combination with 4-phenylene ether units.

The polyphenylene ether used here preferably has an intrinsic viscosity of 0.2 to 0.8 dl / g measured at 30 ° C. in chloroform. More preferably, the intrinsic viscosity is 0.25 to 0.7 dl / g, particularly preferably, the intrinsic viscosity is 0.3 to 0.7 dl / g.
0.6 dl / g. Intrinsic viscosity 0.2 dl /
If the amount is less than 0.1 g, the impact resistance of the composition is insufficient, and 0.8 dl / g is obtained.
Above, the gel content is large and the appearance of the molded article is difficult.

(B) Saturated polyester The saturated polyester used in the present invention has a -CO-O- bond in the polymer main chain and can be melted by heating. Various polyesters can be used.

For example, a dicarboxylic acid or a lower alkyl ester, an acid halide or an acid anhydride derivative thereof;
There is a polyester obtained by polycondensing a glycol or a dihydric phenol. Here, specific examples of dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, aliphatic dicarboxylic acids such as sebacic acid, terephthalic acid, isophthalic acid, p , P'-dicarboxydiphenyl sulfone, p
-Carboxyphenoxyacetic acid, p-carboxyphenoxypropionic acid, p-carboxyphenoxybutyric acid, p-
Examples include aromatic dicarboxylic acids such as carboxyphenoxyvaleric acid, 2,6-naphthalene dicarboxylic acid, and 2,7-naphthalene dicarboxylic acid, and mixtures of these carboxylic acids. On the other hand, as glycols,
12 linear alkylene glycols such as ethylene glycol, 1,3-propylene glycol, 1,4-butene glycol, 1,6-hexene glycol, 1,12
In addition to aliphatic glycols such as -dodecamethylene glycol, alicyclic glycols such as 1,4-cyclohexanedimethanol and aromatic glycols such as p-xylylene glycol can be mentioned. Also, as the dihydric phenol,
Pyrocatechol, resorcinol, hydroquinone or alkyl-substituted derivatives of these compounds.

In addition, polyesters obtained by ring-opening polymerization of lactones such as polypivalolactone and poly (ε-caprolactone) can also be used. Further, a polymer that forms a liquid crystal in a molten state (Thermotropi)
c Liquid Crystal Polymer;
Polyesters (TLCP) can also be used. Typical examples of the liquid crystalline polyester include X7G manufactured by Eastman Kodak Company, Xydar (Zyder) manufactured by Dartco, Econol manufactured by Sumitomo Chemical Co., and Vectra manufactured by Celanese Corporation.

Preferred saturated polyesters are polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PE)
N), poly (1,4-cyclohexane dimethylene terephthalate) (PCT) or the above-mentioned liquid crystalline polyester. Further, the viscosity of the saturated polyester is such that the intrinsic viscosity measured at 20 ° C. in a mixed solution of phenol / 1,1,2,2-tetrachloroethane = 60/40% by weight is 0.5 to
A range of 5.0 dl / g is preferred. More preferably,
1.0 to 4.0 dl / g, particularly preferably 2.0 to 4.0 dl / g
3.5 dl / g. When the intrinsic viscosity is less than 0.5 dl / g, the impact resistance is insufficient, and when the intrinsic viscosity is 5.0 dl / g or more, the moldability is difficult. is there.

(D) Phosphite Compound The phosphite compound of the present invention is a phosphite triester compound, and any known phosphite ester compound can be used. As the phosphite triester, for example, the following formula (2):
There are compounds represented by (3).

[0027]

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[R ¹ is an alkyl group having 1 to 20 carbon atoms,
It represents an aromatic group having 6 to 30 carbon atoms or a substituted aromatic group.
The substituent of R ¹ may be a substituent containing an oxygen atom, a nitrogen atom, a sulfur atom or a halogen atom. Also, R ¹
May be different from each other. ]

[0029]

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[Wherein, R ² represents an alkyl group having 1 to 20 carbon atoms, an aromatic group or a substituted aromatic group having 6 to 30 carbon atoms, and n represents a number of 1 or 2. R represents an alkylene group or an arylene group having 2 to 18 carbon atoms when n is 1, and represents an alkyltetrayl group having 4 to 18 carbon atoms when n is 2. R ² may be the same or different, and the substituent of R ² and R may be a substituent containing an oxygen atom, a nitrogen atom, a sulfur atom or a halogen atom. ].

In the above formulas (2) and (3), R
^{As 1} or R ² , for example, a methyl group, an ethyl group,
Aliphatic groups such as propyl group, octyl group, isooctyl group, isodecyl group, decyl group, stearyl group and lauryl group; aromatic groups such as phenyl group, biphenyl group and naphthyl group; 2-, 3- or 4-methylphenyl Group, 2,4-
Or a 2,6-dimethylphenyl group, a 2,3,6-trimethylphenyl group, a 2-, 3- or 4-ethylphenyl group, a 2,4- or 2,6-diethylphenyl group,
2,3,6-triethylphenyl group, 2-, 3- or 4-tert-butylphenyl group, 2,4- or 2,
6-di-tert-butylphenyl group, 2,6-di-t
tert-butyl-4-methylphenyl group, 2,6-di-
There are substituted aromatic groups such as a tert-butyl-4-ethylphenyl group, an octylphenyl group, an isooctylphenyl group, a 2-, 3- or 4-nonylphenyl group, and a 2,4-dinonylphenyl group. Aromatic groups and substituted aromatic groups are particularly preferred.

When n is 1 in the formula (3), examples of R include 1,2-phenylene group, ethylene group, propylene group, trimethylene group, tetramethylene group, hexamethylene group and the like. , N is 2, a tetrayl group having a pentaerythrityl structure and represented by the following formula (4).

[0033]

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[In the formula, Q represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ]

Specific examples of the phosphite compound represented by the above formula (2) include trioctyl phosphite,
Tridecyl phosphite, trilauryl phosphite,
Tristearyl phosphite, triisooctyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-dinonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, triphenyl Phosphite, tris (octylphenyl) phosphite, diphenylisooctylphosphite, diphenylisodecylphosphite, octyldiphenylphosphite, dilaurylphenylphosphite, diisodecylphenylphosphite, bis (nonylphenyl) phenylphosphite, diiso Octylphenyl phosphite and the like.

As a specific example of the phosphite compound represented by the formula (3), R2 such as diisodecylpentaerythritol diphosphite, dilaurylpentaerythritol diphosphite, distearylpentaerythritol diphosphite, etc. Although there is also a phosphite ester which is an aliphatic group, a phosphite represented by the following formula, which is an aromatic group or a substituted aromatic group, is preferred.

[0037]

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[Wherein, Ar represents an aromatic group having 6 to 30 carbon atoms or a substituted aromatic group, and n represents a number of 1 or 2. R represents an alkylene group or an arylene group having 2 to 18 carbon atoms when n is 1, and represents an alkyltetrayl group having 4 to 18 carbon atoms when n is 2. Ar may be the same or different, and Ar and R
May be a substituent containing an oxygen atom, a nitrogen atom, a sulfur atom or a halogen atom. ]

A preferred specific example of the phosphite compound represented by the above formula is that when n is 1, (phenyl)
(1,3-propanediol) phosphite, (4-methylphenyl) (1,3-propanediol) phosphite, (2,6-dimethylphenyl) (1,3-propanediol) phosphite, (4- tert-butylphenyl) (1,3-propanediol) phosphite,
(2,4-di-tert-butylphenyl) (1,3-
Propanediol) phosphite, (2,6-di-te)
rt-butylphenyl) (1,3-propanediol)
Phosphite, (2,6-di-tert-butyl-4-
(Methylphenyl) (1,3-propanediol) phosphite, (phenyl) (1,2-ethanediol) phosphite, (4-methylphenyl) (1,2-ethanediol) phosphite, (2,6- Dimethylphenyl)
(1,2-ethanediol) phosphite, (4-te
rt-butylphenyl) (1,2-ethanediol) phosphite, (2,4-di-tert-butylphenyl) (1,2-ethanediol) phosphite,
6-di-tert-butylphenyl) (1,2-ethanediol) phosphite, (2,6-di-tert-butyl-4-methylphenyl) (1,2-ethanediol) phosphite, 6-di-tert-butyl-
4-methylphenyl) (1,4-butanediol) phosphite and the like.

When n is 2, preferred examples of the phosphite compound include diphenylpentaerythritol diphosphite, bis (2-methylphenyl) pentaerythritol diphosphite, and bis (3-methylphenyl). Pentaerythritol diphosphite, bis (4-methylphenyl) pentaerythritol diphosphite, bis (2,4-dimethylphenyl) pentaerythritol diphosphite, bis (2,6-dimethylphenyl) pentaerythritol diphosphite, bis (2,3,6-trimethylphenyl) pentaerythritol diphosphite, bis (2-tert-butylphenyl) pentaerythritol diphosphite, bis (3
-Tert-butylphenyl) pentaerythritol diphosphite, bis (4-tert-butylphenyl)
Pentaerythritol diphosphite, bis (2,4-
Di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) penta Erythritol diphosphite, bis (2,
6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (biphenyl) pentaerythritol diphosphite, dinaphthylpentaerythritol diphosphite and the like. Can be

Further, more preferred phosphite compounds include bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite,
Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite; The composition of the present invention may contain a compound generated by the decomposition (hydrolysis, thermal decomposition, or the like) of the phosphite compound.

(D), (c) Phosphorus Flame Retardant In the present invention, the phosphorus flame retardant used for the component (D) or the component (c) is a compound containing phosphorus in the molecule, usually a pentavalent phosphorus compound. And preferably a phosphate compound represented by the following formula (5) or (6).
The phosphorus-based flame retardant may be used in combination of two or more compounds.

[0043]

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Wherein R ³ is an alkyl group having 1 to 6 carbon atoms or 6 carbon atoms which may be alkyl-substituted.
-20 represents an aryl group, and p represents a number of 0 or 1. R ³ and p may be the same or different. ]

Specific examples of the phosphate compound represented by the above formula (5) include triphenyl phosphate, tricresyl phosphate, diphenyl 2-ethylcrisyl phosphate, tri (isopropylphenyl) phosphate, diphenyl methylphosphonate, and diethyl phenylphosphonate. Esters, diphenylcresyl phosphate, tributyl phosphate and the like. These compounds can be produced from phosphorus oxychloride or the like by a known method.

[0046]

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Wherein R ⁴ is an alkyl group having 1 to 6 carbon atoms or 6 carbon atoms which may be alkyl-substituted.
Represents an aryl group of ２０20, q represents a number of 0 or 1, respectively, r represents an integer of 1 to 5, and X represents an arylene group. R ⁴ , q and X may be the same or different. ]

The phosphoric ester compound represented by the above formula (6) is a condensed phosphoric ester, and an arylene group (X) interposed between pentavalent phosphorus atoms is, for example, a dihydroxy group such as resorcinol, hydroquinone, and bisphenol A. A group derived from a compound. Further, as a specific example of the above condensed phosphate ester, when X is a group derived from resorcinol, phenyl resorcinol polyphosphate, cresyl resorcinol polyphosphate, phenyl cresyl resorcinol polyphosphate, xylyl resorcinol. Polyphosphate, phenyl-p
-Tert-butylphenyl resorcinol polyphosphate, phenyl isopropylphenyl resorcinol polyphosphate, cresyl xylyl resorcinol polyphosphate, phenyl isopropylphenyl diisopropylphenyl resorcinol polyphosphate, and the like.

The phosphorus-based flame retardant can be blended as component (D), but if possible, as component (c), ie, together with the polyphenylene ether of component (a) and the saturated polyester of component (b), Further, it is preferable that the phosphite compound of the component (d) is also present and melt-kneaded to obtain a melt-kneaded resin composition (C) before blending. However, when it is difficult to sufficiently melt and knead due to a large amount of the phosphorus-based flame retardant, for example, it may be blended as the component (D).

(E) Polytetrafluoroethylene Examples of the polytetrafluoroethylene used as the component (E) in the present invention include polytetrafluoroethylene having a fibril-forming ability, which is easily dispersed in a polymer. In addition, it shows a tendency to form a fibrous structure by bonding polymers. Polytetrafluoroethylene having a fibril-forming ability is based on ASTM standard (D329
4-81). As polytetrafluoroethylene having a fibril-forming ability, for example, Teflon 6 from Mitsui-DuPont Fluorochemicals Co., Ltd.
J or Teflon 30J or as polyflon from Daikin Industries, Ltd.

<Composition ratio of components> Component (A) of the present invention
The composition ratio of (E) to (E) is 100% of the total amount of (A) + (B).
Parts by weight are as follows. The aromatic polycarbonate of the component (A) is 5 to 95% by weight, preferably 15 to 90% by weight, and more preferably 30 to 80% by weight. The styrene resin of the component (B) is 95 to 5
%, Preferably 85 to 10% by weight, more preferably 20 to 70% by weight. In the resin composition,
If the proportion of the component (A) is less than 5% by weight, the impact resistance will be unsatisfactory, and if it exceeds 95% by weight, the moldability will be unsatisfactory. If the proportion of the component (B) is less than 5% by weight, the moldability will be unsatisfactory, and if it exceeds 95% by weight, the impact resistance will be unsatisfactory.

The melt-kneaded resin composition of the component (C) is used in an amount of 5 to 5 based on 100 parts by weight of the total amount of the components (A) and (B).
0 parts by weight, preferably 7 to 20 parts by weight. 5
When the amount is less than parts by weight, the effect of adding the compatibilizing agent to (A) and (B) is small, and the effect of improving the physical properties of the composition is insufficient. On the other hand, if it exceeds 50 parts by weight, there may be a problem in appearance of the molded product, which is not preferable.

The composition ratio of (a) to (d) constituting component (C) is such that the total amount of (a) + (b) is 100 parts by weight,
It is as follows. The polyphenylene ether of component (a) is 15 to 97% by weight, preferably 20 to 95%.
%, More preferably 55 to 85% by weight. 85 to 3% by weight of the saturated polyester of the component (b)
, Preferably 80 to 5% by weight, more preferably 45 to 15% by weight. If the proportion of the component (a) in the resin composition is less than 15% by weight, impact resistance, heat resistance and flame retardancy are unsatisfactory, and if it exceeds 97% by weight, impact resistance and fluidity are unsatisfactory. If the proportion of the component (b) is less than 3% by weight, impact resistance and fluidity are unsatisfactory, and if it exceeds 85% by weight, impact resistance, heat resistance and flame retardancy are unsatisfactory.

The phosphorus-based flame retardant of the component (c) is used in an amount of 5 to 200 parts by weight, preferably 10 to 50 parts by weight, per 100 parts by weight of the total of the components (a) and (b). 200
If the amount is more than the weight part, there may be a case where a problem occurs in the appearance of the molded product, which is not preferable.

The phosphite compound of the component (d) is
It is 0.05 to 20 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total amount of the components (a) and (b).
Parts by weight. If it is 0.05 part by weight or less, the effect of adding the compatibilizing agent to (a) and (b) is small, and the effect of improving the physical properties of the composition is insufficient. On the other hand, if the amount exceeds 20 parts by weight, there may be a case where a problem occurs in the appearance of the molded product, which is not preferable.

The phosphorus flame retardant of the component (D) is used in an amount of 0 to 100 parts by weight, preferably 5 to 20 parts by weight, based on 100 parts by weight of the total of the components (A) and (B). If the amount exceeds 100 parts by weight, there may be a case where a problem occurs in the appearance of the molded product, which is not preferable.

The blending amount of the polytetrafluoroethylene of the component (E) is 0 to 5 parts by weight based on 100 parts by weight of the total of the components (A) and (B). When the amount of the polyfluoroethylene resin exceeds 5 parts by weight, the appearance of a molded article is deteriorated, which is not preferable.

<Additional Components> The thermoplastic resin composition of the present invention may contain various additional components in addition to the components (A) to (E) as long as the effects of the present invention are not impaired. A typical additional component is a plasticizer,
Specifically, it is not particularly limited as long as it has a plasticizing effect on the aromatic polycarbonate. For example, benzene, toluene, aromatic hydrocarbons such as xylene, heptane, chain and cyclic aliphatic hydrocarbons such as cyclohexane, chlorobenzene, dichlorobenzene, trichlorobenzene, halogenated hydrocarbons such as dichloromethane, dioxane, diethyl ether and the like Ethers, cyclohexanone, ketones such as acetophenone, ethyl acetate, esters such as propiolactone, nitriles such as acetonitrile, benzonitrile, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol and the like Alcohols, nitrobenzene, sulfolane and the like can be mentioned. These may be used alone or as a mixture. Preferably, the compound has a solubility parameter in the range of 7 to 11.5.

Further, the compounding amount of the additional component is usually 100 parts by weight of the total amount of the components (A) and (B), and the impact modifier, antioxidant, weather resistance modifier, alkali 0.01 for soap, metal soap and hydrotalcite
-5 parts by weight, a plasticizer and a fluidity improver are 5-30 parts by weight,
The nucleating agent is 0.5 to 2 parts by weight, the flame retardant is 5 to 50 parts by weight,
0.1 to 10 parts by weight of the anti-dripping agent can be used. In addition, the compounding of 5 to 50 parts by weight of organic filler, inorganic filler, reinforcing agent, especially glass fiber, mica, talc, wollastonite, potassium titanate, calcium carbonate, silica, etc., has rigidity, heat resistance, and dimensions. This is effective for improving accuracy and the like. Further, a colorant and a dispersant thereof may be added in an amount of 0.5 to 5 parts by weight. In addition, if necessary, polyethylene,
Other thermoplastic resins such as polypropylene and polyamide resins may be blended. Particularly, by adding 2 to 10 parts by weight of polyethylene, impact resistance can be improved.

<Production Method of Composition> The production of the resin composition of the present invention is not limited to a specific method, but is preferably by melt-kneading. In this regard, kneading methods generally used for thermoplastic resins can be applied.
However, as the component (C), it is necessary to prepare a predetermined component as a melt-kneading composition in advance. That is, component (A)
And component (B) cause macroscopic phase separation, thereby preventing the molded product from separating into a skin layer and a core layer.

For example, the component (C) is previously formed by a melt-kneading method or the like, and after pelletizing or powdering, each of the components (A) to (E) may be added, if necessary, to the above-mentioned additional component. After uniformly mixing with the described substances using a Henschel mixer, a ribbon blender, a V-type blender, or the like, the mixture can be kneaded using a single-screw or multi-screw kneading extruder, a roll, a Banbury mixer, a Labo Plastomill (Bravender), or the like.

Each component, including the substances described in the section of the additional component described above, may be fed to the kneader at once or sequentially. Further, a mixture obtained by previously mixing two or more kinds of components selected from the components including the substances described in the above-mentioned additional component may be used.

The kneading temperature and kneading time can be arbitrarily selected according to the desired conditions such as the resin composition and the kind of kneader, but the kneading temperature is 150 to 350 ° C. and the kneading time is 20 minutes.
Minutes or less is preferred. If the temperature exceeds 350 ° C or 20 minutes,
Thermal degradation of the aromatic polycarbonate or styrene-based resin becomes a problem, and the physical properties and appearance of the molded product may deteriorate.

<Method of Forming Composition> The method of forming and processing the thermoplastic resin composition of the present invention is not particularly limited, and molding methods generally used for thermoplastic resins, that is, injection molding and hollow molding are used. Molding methods such as extrusion molding and press molding can be applied, and hollow and extrusion molding methods are preferred.

[0065]

EXAMPLES The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples.

The abbreviations and contents of the components used in the examples and comparative examples are as follows. -Polycarbonate: PC: 2,2-bis (4-oxyphenyl) propane-based polycarbonate (manufactured by Mitsubishi Engineering-Plastics Corporation, trade name Iupilon S2000, viscosity average molecular weight 25,000). -Styrene resin: HIPS: Styrene graft copolymer, rubber component polybutadiene (Dialex HT478, manufactured by Mitsubishi Chemical Corporation). -Polyphenylene ether: PPE: poly (2,6-dimethyl-1,4-phenylene ether) (trade name H-, manufactured by Nippon Polyether Co., Ltd.)
53, intrinsic viscosity 0.53 dl / g measured in chloroform at 30 ° C).・ Saturated polyester: PBT: polybutylene terephthalate (Kanebo Co., Ltd.)
PBT124, trade name, injection molding grade, phenol / 1,1,2,2-tetrachloroethane = 60/40
2.4 dl intrinsic viscosity measured at 20 ° C. in a weight% mixture
/ G) Phosphorus-based flame retardant: TPP: Triphenyl phosphate (Daichi Chemical Co., Ltd.)
Made). -Phosphite compound: PEP: bis (2,6-di-tert-butyl-4-)
Methylphenyl) pentaerythritol diphosphite (trade name MARK PEP-36, manufactured by Asahi Denka Co., Ltd.). -Polytetrafluoroethylene: PTFE: (manufactured by Daikin Chemical Industries, Ltd., trade name: Polyflon F201L)-Polyethylene: PE: (manufactured by Mitsubishi Chemical Corporation, trade name: Novatec S
F230).

Examples 1 to 3 and Comparative Example 2 The components (a) to (d) constituting the component (C) were thoroughly mixed and stirred with a supermixer at the mixing ratio shown in Table 1 beforehand. This is a TE ventilated TE manufactured by Nippon Steel Corporation.
The mixture was supplied to an X44 twin-screw extruder, and the pressure was reduced to 10 Torr from a vent port provided downstream of the first hopper, and the mixture was melt-kneaded under a kneading condition of a set temperature of 210 ° C. and a screw rotation speed of 250 rpm to obtain a composition. Then, it was pelletized. This was dried at 105 ° C. for 8 hours with a hot air drier to obtain Component (C). The average kneading time was 100 seconds.

Next, the components (A) to (E) and the additional components were mixed and stirred sufficiently in a mixing ratio shown in Table 1 with a super mixer, and then the mixture was added to a ventilated Nippon Steel Corporation. To a TEX44 twin-screw extruder, and the pressure is reduced to 10 Torr from a vent port installed downstream of the first hopper, at a set temperature of 210 ° C. and a screw rotation speed of 250 rpm.
Under the kneading conditions described above, the mixture was melt-kneaded to obtain a composition and then pelletized. This was dried with a hot air drier at 105 ° C. for 8 hours to obtain a thermoplastic resin composition. The average kneading time is 10
It was 0 seconds.

Comparative Examples 1 to 3 and 5 In Example 1, the components (A) to (B) were mixed at the mixing ratios shown in Table 1 without performing the melt kneading at the stage prior to preparing the component (C).
(B) The components (D) to (E), the components (a) to (b), and the additional components were the same as in Example 1 except that only the subsequent melt-kneading was performed. I got

(Evaluation Test) From the thermoplastic resin compositions obtained in the respective Examples and Comparative Examples, predetermined test pieces were molded by the following method, and each physical property value and various characteristics were measured. Are shown in Table 1. In addition, at the time of kneading and molding, polybutylene terephthalate and the composition are previously 120
C. and dried under reduced pressure for 5 hours.

(1) Melt flow rate (MFR): J
Conforms to IS K 7210. However, the temperature is 260 ° C,
The load was measured at 5 kg. (2) Flexural modulus: ISO R178-1974 Pr
The measurement was carried out using an Instron testing machine according to the method of the present invention (Osdure 12 (JIS K 7203)). (3) Izod impact strength (Izod): ISO R1
It was measured using an Izod impact tester manufactured by Toyo Seiki Seisakusho in accordance with 80-1969 (JIS K 7110) notched Izod impact strength. (4) Flame retardancy and total burning time: flame retardance is 1.6 mm
A vertical combustion test was performed using a UL-specified test piece for evaluation. In addition, the total combustion time is represented by a total of five combustion times defined in the UL standard. (5) Thermal deformation temperature: Using a HDT tester manufactured by Toyo Seiki Seisaku-sho, the evaluation was performed at a load of 4.6 kg according to JIS K 7207.

[0072]

[Table 1]

[0073]

According to the present invention, a composition comprising polyphenylene ether, a saturated polyester and a phosphorus-based flame retardant is blended in order to improve the compatibility and flame retardancy between the aromatic polycarbonate and the styrene resin. It was possible to obtain a thermoplastic resin composition having a significantly improved impact resistance, an excellent balance of mechanical strength, and a molded article having excellent flame retardancy.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 71/12 C08L 71/12

Claims (3)

[Claims] 1. A thermoplastic resin composition comprising a predetermined amount of the following components (C) to (E) based on 100 parts by weight of the total of the following components (A) and (B). (A) 95 to 5 parts by weight of an aromatic polycarbonate (B) 5 to 95 parts by weight of a styrene-based resin (C) 5 to 50 parts by weight of a melt-kneaded resin composition containing polyphenylene ether, a saturated polyester and a phosphorus-based flame retardant (D) Phosphorus flame retardant 0 to 100 parts by weight (E) Polytetrafluoroethylene 0 to 5 parts by weight 2. A melt-kneaded composition of the component (C) is a composition containing a predetermined amount of the following components (c) and (d) based on 100 parts by weight of the total of the following components (a) and (b). The thermoplastic resin composition according to claim 1. (A) 95 to 20 parts by weight of polyphenylene ether (b) 5-80 parts by weight of saturated polyester (c) 5-200 parts by weight of phosphorus-based flame retardant (d) Phosphite compound represented by the following formula 0.1 to 10 Parts by weight [In the formula, Ar represents an aromatic group having 6 to 30 carbon atoms or a substituted aromatic group, and n represents a number of 1 or 2. R is
When n is 1, it represents an alkylene group having 2 to 18 carbon atoms or an arylene group, and when n is 2, it represents an alkyltetrayl group having 4 to 18 carbon atoms. Ar may be the same or different, and the substituent of Ar and R may be a substituent containing an oxygen atom, a nitrogen atom, a sulfur atom or a halogen atom. ] 3. The heat according to claim 1, wherein the melt kneading of the polyphenylene ether, the saturated polyester and the phosphorus-based flame retardant constituting the component (C) is carried out at a temperature of 150 to 350 ° C. A method for producing a plastic resin composition.