JP2002179896A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an inexpensive material capable of achieving a reduction in both molding shrinkage percentage and weight without deteriorating excellent characteristics of a thermoplastic polyester resin. SOLUTION: This thermoplastic resin composition is obtained by compounding (A) 95-10 wt.% of the thermoplastic resin with (B) 4-50 wt.% of a rubber- modified styrene thermoplastic resin, (C) 1-40 wt.% of a polyphenylene ether resin, (D) 0.01-4 wt.% of a phosphorous ester compound and (E) 0.1-20 wt.% of a phosphoric ester compound.

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 which is excellent in mechanical properties such as moldability, strength and impact resistance, and provides a lightweight and inexpensive molded article.

[0002]

2. Description of the Related Art Thermoplastic polyester resins represented by polybutylene terephthalate and polyethylene terephthalate have excellent workability, mechanical properties, heat resistance, and other physical and chemical properties. It is widely used in the fields of electrical and electronic equipment parts and other precision equipment parts. In particular, polybutylene terephthalate has a high crystallization rate and is therefore suitable for injection molding.

However, on the other hand, polybutylene terephthalate is a crystalline resin, and therefore has a problem of a high molding shrinkage and a high specific gravity (1.31). On the other hand, reduction in molding shrinkage and weight reduction are desired,
There is also a high demand for cost reduction.

For the purpose of reducing the molding shrinkage and reducing the weight of polybutylene terephthalate, a method of blending another resin has been proposed. The resin to be compounded is polystyrene, A
S-resin, styrene resin represented by ABS resin, polypropylene, polycarbonate and the like. However, in each case, even though the molding shrinkage ratio can be reduced and the weight can be reduced, the mechanical properties are reduced and the moldability (fluidity) is deteriorated.

[0005]

SUMMARY OF THE INVENTION It has been desired to achieve a reduction in molding shrinkage and a reduction in weight without impairing the essential characteristics of polybutylene terephthalate, such as mechanical properties and fluidity.

[0006]

The present inventors have conducted intensive studies to solve these problems, and as a result, have found that thermoplastic polyester resins, rubber-modified polystyrene resins, polyphenylene ether resins, phosphite compounds and phosphorus compounds have been developed. By compounding the acid ester compound at a specific ratio,
Preferably, before blending the polyphenylene ether resin and the phosphite compound with other components, the melt-kneaded composition blended with the thermoplastic polyester resin in a specific ratio impairs the excellent properties of the polyester. Without reducing the molding shrinkage and reducing the weight, it was possible to provide an inexpensive material. That is, the present invention provides (A) 95 to 10% by weight of a thermoplastic polyester resin, (B) 4 to 50% by weight of a rubber-modified styrene-based thermoplastic resin, (C) 1 to 40% by weight of a polyphenylene ether resin, and (D) Phosphite compound 0.01 to 4% by weight
And (E) a thermoplastic resin composition containing 0.1 to 20% by weight of a phosphate compound.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. (A) Thermoplastic polyester resin As the (A) thermoplastic polyester resin in the present invention, any thermoplastic polyester resin can be used. Here, the thermoplastic polyester resin is a polymer or copolymer having an ester group composed of a dicarboxylic acid unit and a diol unit in a chain unit, and is usually a dicarboxylic acid or an ester derivative thereof and a diol or an ester derivative thereof. Is obtained by a polycondensation reaction using as a main component.

The dicarboxylic acid unit includes terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid,
2,6-naphthalenedicarboxylic acid, biphenyl-2,
2'-dicarboxylic acid, biphenyl-3,3'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, bis (4,4'-carboxyphenyl) methane, anthracenedicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid Aromatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, alicyclic dicarboxylic acids such as 4,4'-dicyclohexyldicarboxylic acid, adipic acid, sebacic acid, azelaic acid, and aliphatic dicarboxylic acids such as dimer acid; No. Of these, terephthalic acid is preferred.

The diol unit includes aliphatic or alicyclic diols having 2 to 20 carbon atoms, bisphenol derivatives and the like. Specific examples include ethylene glycol, tetramethylene glycol, propylene glycol, 1,5-pentanediol, Examples include 1,6-hexanediol, neopentyl glycol, decamethylene glycol, cyclohexanedimethanol, 4,4'-dicyclohexylhydroxymethane, 4,4'-dicyclohexylhydroxypropane, and a diol added with ethylene oxide of bisphenol A. Among them, tetramethylene glycol is preferred. Further, it may contain a triol unit such as glycerin and trimethylolpropane.

Therefore, in the present invention, polybutylene terephthalate (PBT) in which the main dicarboxylic acid unit is terephthalic acid and the main diol unit is tetramethylene glycol is preferred. That is, dicarboxylic acid units other than terephthalic acid and tetramethylene glycol,
The diol unit may be copolymerized. However, the proportion of terephthalic acid in the dicarboxylic acid unit is preferably at least 70 mol%, more preferably at least 90 mol%, from the viewpoint of mechanical properties and heat resistance. Similarly, in the diol unit, tetramethylene glycol is preferably at least 70 mol%, more preferably 90 mol%.
That is all.

The intrinsic viscosity of the PBT resin in the present invention is:
It is preferably 0.5 to 1.8 dl / g, more preferably 0.6 to 1.6 dl / g, as measured at 30 ° C. in a 1: 1 (weight) mixed solvent of tetrachloroethane and phenol.

(B) Rubber-modified styrene-based thermoplastic resin The (B) rubber-modified styrene-based thermoplastic resin in the present invention is composed of a rubbery polymer and a styrene-based polymer. As a preparation method, a simple mechanical blending method may be used, but in order to obtain good compatibility, a styrene-based monomer and other monomers as necessary in the presence of a rubbery polymer are used. Those obtained by a so-called graft copolymerization method for graft copolymerization are more preferred. The rubber-modified styrenic polymer (graft polymer) obtained by the method is obtained by polymerizing a styrenic monomer and optionally another monomer in the absence of a rubbery polymer. It is also desirable to use those obtained by a so-called graft-blend method in which a styrene-based polymer is blended.

Examples of the rubbery polymer include conjugated diene rubbers such as polybutadiene, styrene butadiene copolymer, hydrogenated styrene-butadiene block copolymer, and non-conjugated diene rubbers such as ethylene-propylene copolymer. Among them, conjugated diene rubbers, particularly polybutadiene, are preferred.

Examples of the styrene monomer include styrene, α-methylstyrene, bromostyrene and the like, among which styrene and / or α-methylstyrene are preferred.

The polymerization methods include emulsion polymerization, solution polymerization,
Suspension polymerization or the like can be applied. Such rubber-modified polystyrene resins are generally high impact polystyrene (HI)
PS).

The rubber content in the rubber-modified styrenic thermoplastic resin is preferably from 1 to 40% by weight, more preferably from 3 to 30% by weight.

The MFR reflecting the molecular weight of the rubber-modified styrene-based thermoplastic resin is preferably 0.5 to 15 g / 10 minutes under a load of 5 kg at 200 ° C., and more preferably 1.0 to 10 g / 10 minutes.

Polyphenylene ether resin, phosphite compound and phosphoric acid ester compound In the present invention, the total amount of (C) the polyphenylene ether resin and (D) the phosphite compound is added before mixing with other components. It is preferable to form a melt-kneading composition in which (A) a part of the thermoplastic polyester resin and, if necessary, (E) at least a part of the phosphate compound are blended. (C) Polyphenylene ether resin As the (C) polyphenylene ether resin in the present invention, a homopolymer or a copolymer having a structure represented by the following general formula (4) can be mentioned.

[0019]

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(Wherein Q¹ Is a halogen atom, primary
Or secondary alkyl group, phenyl group, aminoalkyl
Group, hydrocarbonoxy group or halohydrocarbonoxy group
Then Q ^Two Is a hydrogen atom, a halogen atom,
Is a secondary alkyl group, phenyl group, haloalkyl group, charcoal
Represents a hydrogen oxy group or a halohydrocarbon oxy group, m is
Represents a number of 10 or more. )

The primary alkyl group for Q ¹ and Q ² includes methyl, ethyl, n-propyl, n-butyl, n-
Amyl, isoamyl, 2-methylbutyl, n-hexyl, 2,3-dimethylbutyl, 2-, 3- or 4-
Methylpentyl, heptyl and the like can be mentioned. As the secondary alkyl group, isopropyl, sec-butyl, 1-
Ethylpropyl and the like can be mentioned. Q ¹ is preferably an alkyl group or a phenyl group, particularly preferably an alkyl group having 1 to 4 carbon atoms, and Q ² is preferably a hydrogen atom.

The homopolymer includes, for example, a polymer comprising 2,6-dimethyl-1,4-phenylene ether unit. As the copolymer, the above unit and 2,
A random copolymer comprising a combination with 3,6-trimethyl-1,4-phenylene ether unit is exemplified.

The intrinsic viscosity of the polyphenylene ether resin is preferably from 0.2 to 0.8 dl / g, more preferably from 0.1 to 0.8 dl / g, measured at 30 ° C. in chloroform.
25-0.7 dl / g, most preferably 0.3
0.6 dl / g. When the intrinsic viscosity is less than 0.2 dl / g, the impact resistance is insufficient, and when the intrinsic viscosity is 0.8 dl / g or more, the gel content is large and the appearance of the molded article is difficult.

(D) Phosphite Compound The (D) phosphite compound in the present invention is a phosphorus compound containing trivalent phosphorus in the molecule, and is preferably a compound represented by the general formula (1) or (6). ), And more preferably a compound represented by the general formula (1). When the compound represented by the general formula (1) is used, a material that does not easily cause poor appearance even when molded at a relatively high temperature can be obtained. As the phosphite compound, two or more compounds can be used in combination.

[0025]

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In the general formula (1), R ¹ represents an alkyl group having 1 to 20 carbon atoms or an aromatic group or a substituted aromatic group having 6 to 30 carbon atoms, preferably an aromatic group having 6 to 30 carbon atoms. Or a substituted aromatic group. n represents a number of 1 or 2; R ² represents an alkylene group or an arylene group having 2 to 18 carbon atoms when n is 1;
To 18 alkyltetrayl groups, and R ^{1 s} may be the same or different. Further, the substituent of R ¹ and R ² may be a substituent containing an oxygen atom, a nitrogen atom, a sulfur atom or a halogen atom.

Specific examples of R ¹ include methyl, ethyl, propyl, octyl, isooctyl, isodecyl, decyl, stearyl, lauryl, phenyl, 2-, 3- or 4-methyl. Phenyl group, 2,4
-, 2,6-dimethylphenyl group, 2,3,6-trimethylphenyl group, 2-, 3- or 4-ethylphenyl group, 2,4-, 2,6-diethylphenyl group, 2,3
6-triethylphenyl group, 2-, 3- or 4-ter
t-butylphenyl group, 2,4-, 2,6-di-ter
t-butylphenyl group, 2,6-di-tert-butyl-6-methylphenyl group, 2,6-di-tert-butyl-6-ethylphenyl group, octylphenyl group, isooctylphenyl group, 2-, Examples thereof include a 3- or 4-nonylphenyl group, a 2,4-dinorisphenyl group, a biphenyl group, and a naphthyl group.

When n is 1 as R ² , for example,
Examples thereof include a 1,2-phenylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, and a hexamethylene group. When n is 2, for example, tetrayl having a pentaerythrityl structure represented by the general formula (5) And the like.

[0029]

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In the general formula (5), R ^{10 to} R ¹⁷ each represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Examples of the phosphite compound represented by the general formula (1) include a phosphite compound wherein R ¹ is an aliphatic group, and a phosphite ester wherein R ¹ is an aromatic group or a substituted aromatic group. And the like, and preferably, a phosphite compound in which R ¹ is an aromatic group or a substituted aromatic group. Specific examples of the phosphite compound in which R ¹ is an aliphatic group include diisodecyl pentaerythritol diphosphite, dilauryl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, and the like.

R ¹ is an aromatic group or a substituted aromatic group,
Specific examples of the phosphite compound when n is 1 include (phenyl) (1,3-propanediol) phosphite, (4-methylphenyl) (1,3-propanediol) phosphite, and (2) , 6-dimethylphenyl)
(1,3-propanediol) phosphite, (4-t
tert-butylphenyl) (1,3-propanediol) phosphite, (2,4-di-tert-butylphenyl) (1,3-propanediol) phosphite,
(2,6-di-tert-butylphenyl) (1,3-
Propanediol) phosphite, (2,6-di-te)
rt-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-tert-butylphenyl) (1,2-
(Ethanediol) phosphite, (2,4-di-ter)
t-butylphenyl) (1,2-ethanediol) phosphite, (2,6-di-tert-butylphenyl)
(1,2-ethanediol) phosphite, (2,6-
Di-tert-butyl-4-methylphenyl) (1,2
-Ethanediol) phosphite, (2,6-di-te)
rt-butyl-4-methylphenyl) (1,4-butanediol) phosphite and the like.

Specific examples of the phosphite compound when n is 2 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-ter
t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butylphenyl)
Pentaerythritol diphosphite, bis (2,6-
Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-te
rt-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (biphenyl) pentaerythritol diphosphite, dinaphthylpentaerythritol diphosphite and the like.

[0034]

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In the general formula (6), R ¹⁸ , R ¹⁹ and R
²⁰ represents an alkyl group having 1 to 20 carbon atoms, an aromatic group having 6 to 30 carbon atoms or a substituted aromatic group, and preferably represents an aromatic group having 6 to 30 carbon atoms or a substituted aromatic group. . The substituent of R ¹⁸ , R ¹⁹ and R ²⁰ may be a substituent containing an oxygen atom, a nitrogen atom, a sulfur atom or a halogen atom, respectively. Specific examples of R ¹⁸ , R ¹⁹ and R ²⁰ include the groups shown as specific examples of R ¹ .

Specific examples of the phosphite compound represented by the general formula (6) include trioctyl phosphite,
Tridecyl phosphite, trilauryl phosphite,
Tristearyl phosphite, triisooctyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-dinolylphenyl) 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 the phosphite compound, 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.

Thermoplastic Polyester Resin The thermoplastic polyester resin directly blended with (C) the polyphenylene ether resin and (D) the phosphite compound is a part of the above-mentioned (A) thermoplastic polyester resin. Specific examples of such a thermoplastic polyester resin are preferably polybutylene terephthalate (PBT) and polyethylene terephthalate (PE).
T), polyethylene naphthalate (PEN), poly (1,4-cyclohexane dimethylene terephthalate)
(PCT). Among them, polybutylene terephthalate (PBT), particularly preferably component (C)
It is preferable to use PBT having a higher molecular weight than PBT which is not directly blended with component (D).

(E) Phosphate Compound The (E) phosphate compound in the present invention includes:
A phosphorus compound containing a pentavalent phosphorus in the molecule, preferably a compound represented by the general formula (2) or (3), more preferably a compound represented by the general formula (2) . When the compound represented by the general formula (2) is used, a molded article having less surface adhesion and less mold adhesion during molding can be obtained. As the phosphoric ester compound, two or more compounds can be used in combination.

[0040]

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In the formula, R ^{3 to} R ⁶ each have 1 to 6 carbon atoms.
Represents an alkyl group or an aryl group having 6 to 20 carbon atoms which may be alkyl-substituted, p, q, r, and s each represent a number of 0 or 1, X represents an arylene group, and y represents
Represents an integer of 1 to 5.

Examples of the phosphate compound represented by the general formula (2) include a condensed phosphate compound.
Examples of the arylene group interposed between pentavalent phosphorus atoms include groups derived from dihydroxy compounds such as resorcinol, hydroquinone, and bisphenol A.

As a specific example of the condensed phosphate compound, 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, etc. Is mentioned.

[0044]

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In the formula, R ^{7 to} R ⁹ each have 1 to 6 carbon atoms.
Represents an aryl group having 6 to 20 carbon atoms which may be alkyl-substituted, and u, v and w each represent 0
Or represents the number of 1.

Examples of the phosphate compound represented by the above formula (3) include triphenyl phosphate, tricresyl phosphate, diphenyl 2-ethylcridyl phosphate, tri (isopropylphenyl) phosphate, diphenyl methylphosphonate, and diethyl phenylphosphonate. , Diphenylcresyl phosphate, tributyl phosphate and the like. These compounds can be produced from phosphorus oxychloride or the like by a known method.

Compounding ratio (A) Thermoplastic polyester resin (referred to as component (A)).
same as below. ) Is 95 to 10% by weight based on the weight of the resin composition containing the components (A) to (E) (the same as the total weight of the thermoplastic resin composition excluding the component (F) described later). , Preferably 90 to 20% by weight, more preferably 85 to 30% by weight. When the component (A) is less than 10%, the tensile (bending) strength, heat resistance, crystallinity, moldability, fluidity, and the like, which are characteristics of the thermoplastic polyester, are not exhibited. On the other hand, if the component (A) exceeds 95%, the effects of improving impact strength and reducing molding warpage by the rubber-modified styrene-based thermoplastic resin and other components are not obtained. (B) The compounding ratio of the rubber-modified styrenic thermoplastic resin is 4 to the weight of the resin composition containing the components (A) to (E).
-50% by weight, preferably 8-45% by weight, more preferably 10-40% by weight. When the component (B) is less than 4% by weight, the impact strength is small, and the effect of reducing the molding warpage is insufficient. When the component (B) exceeds 50% by weight, the tensile strength, heat resistance, and crystallization speed are reduced. Difficulties such as a decrease may occur. (C) The compounding ratio of the polyphenylene ether resin is 1 to 1 with respect to the weight of the resin composition containing the components (A) to (E).
40% by weight, preferably 3 to 35% by weight,
More preferably, it is 5 to 30% by weight. Component (C) is 1
If it is less than 10% by weight, impact resistance, heat resistance and flame retardancy are insufficient, and if it exceeds 40% by weight, fluidity is insufficient. (D) The compounding ratio of the phosphite compound is determined by the component (A)
To 0.01 to the weight of the resin composition containing the component (E)
4% by weight, preferably 0.1 to 3.5% by weight, more preferably 0.3 to 3% by weight. When the component (D) is less than 0.01% by weight, the effect of adding the compatibilizer is small, and the effect of improving the physical properties of the composition is insufficient. May occur. (E) The compounding ratio of the phosphoric acid ester compound is as follows:
0.1 to 20 based on the weight of the resin composition containing the component (E)
% By weight, preferably 0.3 to 18% by weight,
More preferably, it is 0.5 to 15% by weight. Component (E)
Is less than 0.1% by weight, the improvement of the physical properties by compatibilization is insufficient, and if it exceeds 20% by weight, the heat resistance becomes unsatisfactory.

Mixing ratio of melt-kneading composition The above components (C) and (D) may be added to component (E) if necessary.
When a melt-kneading composition is blended with a part of the component (A) together with at least a part of the component (A), the blending ratio of the composition is as follows.
To 1 to 40% by weight, preferably 2 to 35% by weight, more preferably 3 to 30% by weight, based on the weight of the resin composition containing the component (E). If the amount is less than 1% by weight, the effect of adding the compatibilizer is small, and the effect of improving the physical properties of the composition is insufficient.
Difficulty may occur in the appearance of the molded product.

Component (A) constituting the melt-kneading composition,
The mixing ratio of (C), (D) and (E) is as follows, with the total amount of component (C) and component (A) being 100 parts by weight. Component (C) is 95 to 20 parts by weight, preferably 85 to 55 parts by weight. Component (A) is from 5 to 80 parts by weight, preferably from 15 to 45 parts by weight. If the proportion of the component (C) in the resin composition is less than 20 parts by weight, impact resistance, heat resistance and flame retardancy are insufficient, and if it exceeds 95 parts by weight, fluidity is insufficient. When the proportion of the component (A) is less than 5 parts by weight, the fluidity is insufficient, and
If it exceeds 0 parts by weight, impact resistance, heat resistance and flame retardancy are insufficient.

Component (D) is 0.1 to 10 parts by weight, preferably 0.2 to 8 parts by weight. When the amount is less than 0.1 part by weight, the effect of adding the compatibilizing agent is small, and the effect of improving the physical properties of the composition is insufficient.

When component (E) is blended,
0 parts by weight, preferably 5 to 50 parts by weight. If the proportion of the component (E) exceeds 100 parts by weight, the heat resistance will be unsatisfactory.

<Other Components> A flame retardant may be added to the thermoplastic resin composition of the present invention in order to impart flame retardancy. Flame retardants include organic halogen compounds, antimony compounds, phosphorus compounds, and other organic and inorganic compounds.

Examples of the organic halogen compound include brominated polycarbonate, brominated epoxy resin, brominated phenoxy resin, brominated polyphenylene ether resin, brominated polystyrene resin, brominated bisphenol A, pentabromobenzyl polyacrylate and the like.

Examples of the antimony compound include antimony trioxide, antimony pentoxide, sodium antimonate and the like.

The flame retardant of the phosphorus compound is a phosphorus compound other than (E) the phosphoric ester compound, and examples thereof include polyphosphoric acid, ammonium polyphosphate, and red phosphorus.

Other organic and inorganic flame retardants include nitrogen compounds such as melamine and cyanuric acid, and inorganic compounds such as aluminum hydroxide, magnesium hydroxide, silicon compounds and boron compounds.

Additives The thermoplastic resin composition of the present invention may optionally contain conventional additives other than the above-mentioned flame retardants. Examples of the additives include stabilizers such as antioxidants, ultraviolet absorbers, heat stabilizers, and weather stabilizers, lubricants, release agents, coloring agents such as dyes and pigments, catalyst deactivators, antistatic agents, and foaming agents. , A plasticizer, an impact modifier, a crystal nucleating agent, a crystallization accelerator and the like.

Other Thermoplastic Resins and Thermosetting Resins The thermoplastic resin composition of the present invention may contain, if necessary, other thermoplastic resins (for example, polyolefin resin, acrylic resin, polyamide resin, polyphenylene sulfide resin, At least one of a liquid crystal polyester resin, a polyacetal resin) and a thermosetting resin (for example, a phenol resin, a melamine resin, a silicone resin, an epoxy resin).
It can contain more than one species.

<Preparation and Application of Thermoplastic Resin Composition> The preparation of the thermoplastic resin composition of the present invention is not limited to a specific method, but is preferably performed by melt-kneading, and is usually used for thermoplastic resins. The known kneading method can be applied. However, it is important that the total amount of (C) the polyphenylene ether resin and (D) the phosphite compound be melt-kneaded with a part of the thermoplastic polyester resin (A) before blending with other components. By blending as such a melt-kneading composition, the component (A)
And component (B) cause macroscopic phase separation, thereby preventing the molded product from separating into a skin layer and a core layer.

As the kneading method, for example, a melt-kneading composition containing a part of the component (A), the total amount of the components (C) and (D) and, if necessary, at least a part of the component (E) is used. After previously formed by a melt-kneading method or the like, and pelletized or powdered, the components (B), the remainder of the components (A) and (E) and the component (F) are added, if necessary, to a substance which is an additional component. In addition, after uniformly mixing with a Henschel mixer, a ribbon blender, a V-type blender, or the like, the mixture can be kneaded with a single-screw or multi-screw kneading extruder, a roll, a Banbury mixer, a Labo Plast mill (Bradbender), or the like. The kneading temperature and the kneading time can be arbitrarily selected depending on conditions such as the type of the kneader, but the kneading temperature is preferably from 200 to 300 ° C. If it exceeds 300 ° C,
Thermal degradation of (A) the thermoplastic polyester resin or (B) the rubber-modified polystyrene-based resin becomes a problem, and the physical properties of the molded article and the appearance may deteriorate.

The molding method of the thermoplastic resin composition of the present invention is not particularly limited, and molding methods generally used for thermoplastic resins, namely, injection molding,
Molding methods such as hollow molding, extrusion molding, and press molding can be applied.

[0062]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. The abbreviations and contents of each component used in Examples and Comparative Examples are as follows. (1) Polybutylene terephthalate (PBT): (manufactured by Mitsubishi Engineering-Plastics Corporation, trade name Novadur (registered trademark) 5020S and 5040Z)
S) Characteristics of 5020S: phenol / tetrachloroethane =
Intrinsic viscosity measured at 30 ° C. in a 50/50 (weight ratio) mixed solvent is 1.24 dl / g. Characteristics of 5040ZS: phenol / tetrachloroethane = 50/50 (weight ratio) Intrinsic measured at 30 ° C. in a mixed solvent Viscosity 1.4 dl / g (2) High impact polystyrene (HIPS):
(A & M Co., Ltd., trade name: Dialex (registered trademark) HT744) Features of HT744: rubber (polybutadiene) content 8.8
% By weight, average rubber particle size 1.8 μm, number average molecular weight 92,
000, weight average molecular weight 230,000. (3) Polyphenylene ether resin (PPE): poly (2,6-dimethyl-1,4-phenylene ether),
(Product name: H-46, 30 ° C, manufactured by Nippon Polyether Co., Ltd.)
Intrinsic viscosity measured in chloroform at 0.46 d
1 / g). (4) phosphite compound: bis (2,6-di-
tert-butyl-4-methylphenyl) pentaerythritol diphosphite (Adeka Stab PEP-36, manufactured by Asahi Denka Co., Ltd.). (Hereinafter, also referred to as “phosphite PEP-36”.) (5) Phosphate ester compound: triphenyl phosphate (trade name: TPP, manufactured by Daihachi Chemical Co., Ltd.). (Less than,
Also called "phosphate ester TPP". )

[0063] <Evaluation of Physical Properties> specimens various test pieces for physical property evaluation, a thermoplastic resin composition obtained in example or comparative example, 6 hours at 120 ° C., after hot-air drying, was prepared by injection molding . The injection molding was performed under the conditions of a cylinder temperature of 250 to 260C and a mold temperature of 80C.

[0064]Evaluation method The physical property evaluation test of the resin composition was performed by the following method.
Was. (A) Tensile strength, tensile elongation at break: ASTM standard D-
ASTM using tensile specimens made according to 638
 A tensile test of D-638 was performed. Tensile strength is MP
a, Tensile elongation at break is expressed in units of%. (B) Flexural strength and flexural modulus: ASTM standard D-7
ASTM using bending test pieces prepared according to
A bending test of D-790 was performed. The bending strength is MPa,
The flexural modulus is expressed in units of GPa. (C) Izod impact value: ASTM standard D-256
Therefore, the prepared Izod impact test piece (notched, width
3.2 mm) using ASTM D-256 Izo.
d Impact test was performed. Izod impact value is in J / m
To display. (D) Specific gravity: The specific gravity of the Izod impact test piece was measured.
Using Archimedes' principle, weight in air and weight in water
Specific gravity was calculated from the amount. (E) Molding shrinkage: As a test piece, thickness 2 mm, length 6
Inject square plate of 0mm x 60mm width with film gate mold
It was prepared by molding. The flow direction (MD) and flow of the square plate
The molding shrinkage in the perpendicular direction (TD) was measured. Mold shrinkage
Is displayed in units of%. (F) Melt viscosity: Toyo Seiki Capillograph (Model 1
It measured in C). Capillary size 1mmφ × 10
mmL, temperature 270 ° C, shear rate 6080 sec ^-1Measured with
Specified. The melt viscosity is expressed in Pa · s.

[Examples 1 to 5] Melt-kneading composition The following components were mixed and stirred sufficiently in a supermixer at the following mixing ratio, (C) 80 parts by weight of polyphenylene ether resin, (A) 20 parts by weight of PBT5040ZS, D) 2 parts by weight of phosphite PEP36 and 60 parts by weight of (E) phosphate TPP Next, this mixture was supplied to a twin-screw extruder equipped with a vent port, and the mixture was supplied from a vent port provided downstream of the first hopper. 10
The mixture was melt-kneaded under a kneading condition of a set temperature of 250 ° C. and a screw rotation speed of 200 rpm, and then pelletized. This was dried with a hot air drier at 60 ° C. for 8 hours to obtain a melt-kneaded composition. Production speed is 15kg / hr
Met.

The components and the mixing ratios shown in Table 1 were sufficiently mixed and stirred in a V-type blender, and then supplied to a twin-screw extruder equipped with a vent port. Reduce torr and set temperature to 255
Under a kneading condition of 200 ° C. and a screw rotation speed of 200 rpm, the mixture was melt-kneaded into a composition, and then pelletized to obtain a thermoplastic resin composition. The production rate was 20 kg / hr. Table 1 shows the evaluation results of the thermoplastic resin compositions.

[Comparative Examples 1 to 5] Table 2 shows components and compounding ratios.
A thermoplastic resin composition was obtained in the same manner as in the above example, except that the composition was changed as shown in (1). Table 2 shows the evaluation results.

[0068]

[Table 1]

[0069]

[Table 2]

From the results of the examples in Table 1 and the comparative examples in Table 2, the molded articles made of the thermoplastic resin composition of the present invention have higher tensile elongation at break, tensile / bending strength and Izod impact than the comparative examples. High value, low specific gravity and low shrinkage. Also, the melt viscosity is low and the moldability is excellent.

[0071]

The thermoplastic resin composition of the present invention has excellent mechanical properties and moldability and is light in weight, so that it is useful for electric and electronic parts and precision molded parts having strict dimensional accuracy.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C08L 71/12 C08L 71/12 (72) Inventor Ryo Saito 5-6-1 Higashi-Yawata, Hiratsuka-shi, Kanagawa Prefecture Mitsubishi Engineering Plastics (72) Inventor Yoshitaka Kanazawa 5-6-1 Higashi-Hachiman, Hiratsuka-shi, Kanagawa Prefecture F-term (reference) 4J002 BN06X BN14X CF03W CF04W CF05W CF06W CF07W CF08W CF09W CH07Y EW047 EW066 FD130

Claims (9)

[Claims] (A) a thermoplastic polyester resin 95-1
0% by weight, (B) rubber-modified styrene-based thermoplastic resin 4 to
50% by weight, (C) polyphenylene ether resin 1-4
0% by weight, (D) phosphite compound 0.01 to 4
(E) a thermoplastic resin composition containing (E) 0.1 to 20% by weight of a phosphate compound. 2. The thermoplastic resin composition according to claim 1, wherein (A) the thermoplastic polyester resin is polybutylene terephthalate. 3. The thermoplastic resin composition according to claim 1, wherein the rubber content of the rubber-modified styrene-based thermoplastic resin (B) is 1 to 40% by weight. 4. The thermoplastic resin according to claim 1, wherein the rubbery polymer constituting the rubber-modified styrene-based thermoplastic resin (B) is a conjugated diene-based rubber. Resin composition. 5. A melt-kneading composition wherein the total amount of (C) the polyphenylene ether resin and (D) the phosphite compound is blended with a part of (A) a thermoplastic polyester resin before blending with other components. The thermoplastic resin composition according to any one of claims 1 to 4, wherein: 6. The blending ratio of the thermoplastic polyester resin (A) is 5 to 80% by weight in the total 100 parts by weight of (C) the polyphenylene ether resin and (A) the thermoplastic polyester resin constituting the melt-kneading composition. The thermoplastic resin composition according to claim 5, which is a part. 7. The thermoplastic resin composition according to claim 5, wherein the melt-kneading composition contains at least a part of (E) a phosphate compound. 8. The thermoplastic resin composition according to claim 1, wherein (D) the phosphite compound is a compound represented by the following general formula (1). . Embedded image (In the formula (1), R ¹ represents an alkyl group having 1 to 20 carbon atoms, an aromatic group or a substituted aromatic group having 6 to 30 carbon atoms, n represents a number of 1 or 2, and R ² represents , N is 1,
Represents an alkylene group or an arylene group having 2 to 18 carbon atoms, and when n is 2, represents an alkyltetrayl group having 4 to 18 carbon atoms, and R ¹ may be the same or different;
The substituent of R ¹ and R ² may be a substituent containing an oxygen atom, a nitrogen atom, a sulfur atom or a halogen atom. ) 9. The method according to claim 1, wherein the (E) phosphate compound is a phosphate compound represented by the following general formula (2) or (3). Thermoplastic resin composition. Embedded image (In the formula (2), R ^{3 to} R ⁶ each have 1 to 1 carbon atoms.
6 represents an alkyl group or an aryl group having 6 to 20 carbon atoms which may be alkyl-substituted, p, q, r, and s each represent a number of 0 or 1, and y represents an integer of 1 to 5 Represents X
Represents an arylene group. ) (In the formula (3), R ^{7 to} R ⁹ each have 1 to 1 carbon atoms.
Represents an alkyl group having 6 or an aryl group having 6 to 20 carbon atoms which may be alkyl-substituted, and u, v, and w each represent
Represents a number of 0 or 1. )