JPH08302119A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE: To obtain a thermoplastic resin composition excellent in heat resistance, impact resistance, moldability, etc., by adding a specified polymer to a composition comprising a thermoplastic polyester resin and a styrene resin. CONSTITUTION: This thermoplastic resin composition comprises 5-95wt.% thermoplastic polyester resin (A), 95-5wt.% styrene resin (B) and 1-100 pts.wt., per 100 pts., in total, A, B and C, graft copolymer (C) comprising 5-95wt.% polycarbonate resin segment and 95-5wt.% vinyl resin segment and having a multiphase structure in which a dispersed phase formed from one kind of segments are finely dispersed in a continuous phase formed from the other kind of segments. It is desirable that component C is one prepared by suspending a polycarbonate resin in water, adding a solution prepared by dissolving an organic peroxide and a radical polymerization initiator having a 10-hr half-life decomposition temperature of 40-90 deg.C to a vinyl monomer is added to the dispersion to infiltrate the solution into the resin and subjecting the entire mixture to polymerization by heating.

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 having excellent heat resistance, impact resistance, molding processability, etc., and its molded products are automobile parts, electric and electronic machine parts, industrial parts. It is effectively used in a wide range of fields such as parts.

[0002]

2. Description of the Related Art Thermoplastic polyester resins and styrene resins are used in many fields because of their excellent mechanical properties and heat resistance. However, although the thermoplastic polyester resin is excellent in moldability and mechanical strength,
Improvement of impact resistance is required. On the other hand, although the styrene-based resin has excellent impact resistance, improvement in heat resistance is required.

Therefore, by blending a thermoplastic polyester resin and a styrene resin, an excellent resin having both the advantages of the thermoplastic polyester resin and the advantages of the styrene resin is obtained. It is believed that a composition will be obtained, and compatibilizers for it are being developed. For example, as a compatibilizing agent in a blend of a thermoplastic polyester-based resin and a styrene-based resin, Japanese Patent Laid-Open No.
No. 0-63250 and JP-A-1-185348 disclose a thermoplastic resin having a multi-phase structure including an epoxy group-containing olefin copolymer and an epoxy group-containing olefin copolymer and a vinyl copolymer. However, heat resistance and molding processability (fluidity) were insufficient with a reactive olefin compatibilizer such as an epoxy group.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin composition comprising a thermoplastic polyester resin and a styrene resin, which is excellent in mechanical properties, impact resistance, heat resistance and molding processability. It is to provide a resin composition.

[0005]

[Means for Solving the Problems] As a result of intensive studies to solve the above problems, the present inventors have found that a thermoplastic polyester resin (I) and a styrene resin (II) are used.
When blending with a specific graft copolymer (II
By blending I) as a compatibilizer, the mechanical properties and impact resistance of the thermoplastic polyester resin (I) are combined with the advantages of the styrene resin (II). A thermoplastic resin composition having excellent properties, heat resistance, and moldability has been obtained. That is, according to the present invention, the thermoplastic polyester resin (I) is 5 to 95% by weight, and the styrene resin (II) is 9
5 to 5% by weight, and 5 to 95% by weight of a polycarbonate resin segment and 95 to 5% by weight of a vinyl resin segment, which is formed by the other segment in the continuous phase formed by one segment. Graft copolymer with a multiphase structure in which the dispersed phase is finely dispersed (II
I) is 1 to 100 with respect to 100 parts by weight of the total amount of the thermoplastic polyester resin (I) and the styrene resin (II).
It is a thermoplastic resin composition characterized by being mixed in parts by weight.

The aromatic polyester used in the present invention is
A polyester having an aromatic ring as a chain unit of a polymer, which is obtained by a condensation reaction of an aromatic dicarboxylic acid (or its ester-forming derivative) and diol (or its ester-forming derivative) as main components. It is a polymer or a copolymer. Examples of the aromatic dicarboxylic acid used herein include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid,
Bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4'-diphenylcarboxylic acid, 4,
Examples thereof include 4'-diphenyl ether dicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid and their ester-forming derivatives. The diol component is an aliphatic diol having 2 to 10 carbon atoms, that is, ethylene glycol or propylene glycol.
1,4-butanediol, neopentyl glyco-
1,5-pentanediol, 1,6-hexanediol, decamethylene diglycol, cyclohexanediol, etc., or a long-chain glycol having a molecular weight of 400 to 6000, that is, polyethylene glycol, poly -1,
Examples include 3-propylene glycol, polytetramethylene glycol and the like, and mixtures thereof.

Preferred thermoplastic aromatic polyesters used in the present invention are specifically polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate.
And polyethylene-2,6-naphthalate, polyethylene-1,2-bis (phenoxy) ethane-4,4'-dicarboxylate and the like. More preferred are polyethylene terephthalate and polybutylene terephthalate.

The styrene resin (II) used in the present invention refers to a homopolymer of styrene or a copolymer of styrene and another copolymerizable monomer. Examples of the copolymerizable monomer include nuclear substituted styrenes such as methylstyrene, dimethylstyrene and ethylstyrene, α-substituted styrenes such as α-methylstyrene and α-ethylstyrene, vinyl cyanide such as acrylonitrile and methacrylonitrile. ,
Acrylic acid or methacrylic acid [hereinafter acrylic and methacrylic are collectively referred to as (meth) acrylic], (meth) acrylic acid methyl-, ethyl-, isopropyl-, butyl-
At least one selected from alkyl esters of (meth) acrylic acid having 1 to 7 carbon atoms such as (meth) acrylic acid ester such as (meth) acrylic acid ester, maleic acid, fumaric acid, maleic anhydride, and maleimide Examples thereof include copolymers with the above monomers.

In addition, diene rubbers such as butadiene, styrene-butadiene copolymer and acrylonitrile-butadiene copolymer, ethylene-propylene rubbers such as ethylene-propylene copolymer and ethylene-propylene-non-conjugated diene copolymer. At least one rubber-like polymer selected from acrylic rubber, chlorinated polyethylene, ethylene-vinyl acetate copolymer and the like, styrene alone or with styrene, and the above-mentioned nucleus-substituted styrene as a copolymerizable monomer, Grafting with α-substituted styrene, vinyl cyanide, alkyl ester of (meth) acrylic acid having 1 to 7 carbon atoms, at least one monomer selected from maleic acid, fumaric acid, maleic anhydride, and maleimide. Alternatively, block copolymers can be exemplified.

Among these, polystyrene, styrene-butadiene copolymer, styrene-acrylonitrile copolymer and styrene-butadiene-acrylonitrile copolymer (ABS resin) are preferable, and ABS resin is particularly preferable.

In the present invention, the thermoplastic polyester resin (I) is blended with the styrene resin (II) in a proportion of 95 to 5 for the thermoplastic polyester resin (I).
%, Preferably 90 to 30% by weight, most preferably 90 to 50% by weight. Therefore, the styrene resin (II) is 5 to 95% by weight, preferably 10 to 70% by weight, and most preferably 10 to 50% by weight. If the content of the thermoplastic polyester resin (I) is less than 5% by weight, the mechanical strength will be poor, and if it exceeds 95%, the impact resistance will be low, such being undesirable.

The graft copolymer (III) used in the present invention is composed of a polycarbonate resin segment and a vinyl resin segment. The polycarbonate resin segment is a conventional polycarbonate. A viscosity average molecular weight is the same as that of the binder resin, that is, the interfacial polymerization method, the pyridine method, the solution polymerization method such as the chloroformate method, and the transesterification melting method. Is 2000 to 100,000, preferably 5000 to 5
0000, particularly preferably 6000 to 30,000. When the solution method is used, the polymer after the reaction
As a method of solidifying and recovering the polycarbonate resin from the binder resin solution, a method of adding a poor solvent to the polycarbonate resin solution to cause precipitation, and a polycarbonate resin
The solvent is distilled off from the resin solution to concentrate it, a method for forming a powder, a poor solvent is added to the polycarbonate resin solution,
The mixture is added to warm water under heating, suspended in warm water, the solvent and poor solvent are distilled off and solidified to produce a water slurry liquid, and the liquid in the solidification process is circulated through a wet mill. Although there are various methods such as a pulverization method, in the present invention, it is rational to use the water slurry solution of the polycarbonate resin as it is as the water suspension of the polycarbonate resin. Is preferred.

Preferable examples of the divalent phenol compound used for the production of the polycarbonate resin include bis (4-hydroxyphenyl) methane and bis (4-hydroxyphenyl) ether. Tell, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl)
Sulfide, bis (4-hydroxyphenyl) ketone,
1,1-bis (4-hydroxyphenyl) ethane, 2,
2-bis (4-hydroxyphenyl) propane, 2,2
-Bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2
-Bis (4-hydroxy-3,5-dibromophenyl)
Propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) )propane,
Examples are 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, and bis (4-hydroxyphenyl) diphenylmethane.

In the present invention, there is no problem even if a polycarbonate resin having a reactive unsaturated terminal group is used. The method for producing a polycarbonate resin having an unsaturated terminal group described above, as a molecular weight modifier or a terminal terminator,
A monofunctional compound having a double bond, or a production method similar to that of a conventional polycarbonate resin except that a monofunctional compound having a double bond is used in combination therewith, that is, an interfacial polymerization method, a pyridine method, a chloroformate method, etc. It is manufactured by the solution method. As the monofunctional compound having a double bond for introducing an unsaturated terminal group, acrylic acid, methacrylic acid, vinyl acetic acid, 2-pentenoic acid, 3-pentenoic acid, 5-hexenoic acid, 9-decenoic acid, Unsaturated carboxylic acids such as 9-undecenoic acid; acid chlorides or chloroformes such as acrylic acid chloride, methacrylic acid chloride, sorbic acid chloride, allyl alcohol chloroformate, isopropenylphenol chloroformate or hydroxystyrene chloroformate. Examples include phenols having an unsaturated acid such as isopropenylphenol, hydroxystyrene, hydroxyphenylmaleimide, allyl ester of hydroxybenzoic acid or methylallyl hydroxybenzoate. These compounds may be used in combination with a conventional end-stopping agent, and usually 1 to 1 mol of the above-mentioned divalent phenol compound.
It is used in the range of 25 mol%, preferably 1.5 to 10 mol%.

Polycarbonate-based resins are produced with the above-mentioned components as essential components, but are contained in an amount of 0.01 to 3 mol%, particularly 0.1 to 0.1% based on the divalent phenol-based compound as the branching agent.
A branched polycarbonate resin may be used in combination within the range of 1 to 1 mol%. Examples of such a branching agent include phloroglysin, 2,6-dimethyl-2,4,6-
Tri (hydroxyphenyl) heptene-3,4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl)
Heptene-2,1,3,5-tri (2-hydroxyphenyl) benzene, 1,1,1-4-hydroxy) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylpheno , A polyhydroxy compound exemplified by α, α ′, α ″ -tri (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, and 3,3-bis (4-hydroxyaryl) ) Oxyindole (= isatin bisphenol), 5-chloroisatin, 5,7-bromoisatin, 5-bromoisatin, etc. are exemplified.

The particle size of the polycarbonate resin at this time is preferably in the form of powder or pellets of about 0.1 to 5 mm. If the particle size is excessively large, it is difficult to disperse the graft copolymer (III) in the suspension when it is synthesized, and there is a drawback that the impregnation time of the vinyl monomer and the like becomes long. Further, it is more preferable that it is porous for impregnation.

The vinyl resin segment constituting the graft copolymer (III) used in the present invention is specifically an aromatic vinyl monomer such as styrene, nucleus-substituted styrene or α-substituted styrene, Vinyl cyanide monomer such as (meth) acrylonitrile, (meth) acrylate ester such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate It is a vinyl-based resin obtained by polymerizing one or more kinds of monomers selected from the group consisting of maleimide monomers such as body, phenylmaleimide, and cyclohexylmaleimide. In particular, a vinyl resin containing 50% by weight or more of an aromatic vinyl monomer is preferable because it has a good compatibilizing effect.

The graft copolymer (III) referred to in the present invention means that the vinyl resin segment is spherically and uniformly dispersed in the continuous phase formed by the polycarbonate resin segment, or The polycarbonate-based resin segment is spherically dispersed in the continuous phase formed by the vinyl-based resin segment, and the dispersed polymer has a particle diameter of 0.01 to 10 μm. When the dispersed resin particle size is less than 0.01 μm or exceeds 10 μm, the compatibility between the thermoplastic polyester resin (I) and the styrene resin (II) becomes insufficient, and for example, deterioration of appearance or impact resistance It is not preferable because the improvement effect such as is insufficient. The graft copolymer of the present invention (II
The number average degree of polymerization of the vinyl resin in I) is 10 to 500.
It is 0, preferably 100 to 2000. When the number average degree of polymerization is less than 10, the impact resistance of the thermoplastic resin composition of the present invention can be improved, but the heat resistance is lowered, which is not preferable. The number average degree of polymerization is 5000
If it exceeds, the melt viscosity is high, the moldability is lowered, and the surface gloss is lowered, which is not preferable. The graft copolymer (III) of the present invention has a polycarbonate resin segment of 5 to 95% by weight, preferably 30 to 90% by weight,
Most preferably, it comprises 50 to 80% by weight.
Therefore, the vinyl resin segment is 95 to 5% by weight, preferably 70 to 10% by weight, and most preferably 50% by weight.
-20% by weight. When the content of the polycarbonate resin segment is less than 5% by weight or exceeds 95% by weight, the effect of improving compatibility is insufficient, which is not preferable.

The graft copolymer (III) is used in an amount of 1 to 100 parts by weight, preferably 2 to 50 parts by weight, based on 100 parts by weight of the total amount of the thermoplastic polyester resin (I) and the styrene resin (II). More preferably, it is 3 to 30 parts by weight. When the amount of the graft copolymer (III) is less than 1 part by weight, the compatibility between the thermoplastic polyester resin (I) and the styrene resin (II) is not improved, resulting in delamination,
Sufficient impact strength cannot be obtained. Further, if it exceeds 100 parts by weight, mechanical properties and heat resistance are deteriorated, which is not preferable.

The grafting method for producing the graft copolymer (III) of the present invention may be any of well-known methods such as chain transfer method and ionizing radiation irradiation method, but the most preferable method is Is based on the method described below. This is because the grafting efficiency is high and secondary aggregation due to heat does not occur, so that the performance is more effectively expressed and the manufacturing method is simple.

The method for producing the thermoplastic resin composition of the present invention will be described in detail below. That is, 100 parts by weight of polycarbonate resin particles are suspended in water, and 5 to 99 parts by weight of a mixture of one or more vinyl monomers is added to 1 to 100 parts by weight of a radically polymerizable organic peroxide. One kind or a mixture of two or more kinds with respect to 100 parts by weight of the vinyl monomer.
10 parts by weight and a radical polymerization initiator having a decomposition temperature of 40 to 90 ° C. for obtaining a half-life of 10 hours, based on a total of 100 parts by weight of a vinyl monomer and a radically polymerizable organic peroxide. A solution in which 0.01 to 5 parts by weight of the radical polymerization initiator is dissolved is added, and the mixture is heated under conditions where decomposition of the radical polymerization initiator does not substantially occur. Vinyl monomer, radical polymerizable organic peroxide and radical polymerization initiator Is impregnated in the polycarbonate resin particles, then the temperature of the aqueous suspension is raised, and the vinyl monomer and the radically polymerizable organic peroxide are added in the polycarbonate resin particles. Copolymerization gives a grafted precursor. This grafted precursor may be directly melt mixed with the thermoplastic polyester resin (I) and the styrene resin (II). Further, the graft copolymer (III) in the present invention can be obtained by kneading the grafted precursor under melting at 150 to 350 ° C. At this time, the graft copolymer (III) can be obtained by separately mixing a polycarbonate-based resin or a vinyl-based resin with the grafting precursor and kneading the resulting mixture under melting. Most preferred is a graft copolymer (III) obtained by kneading a grafting precursor.

The radical-polymerizable organic peroxide is represented by the general formula (1)

Embedded image (In the formula, R ₁ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R ₂ is a hydrogen atom or a methyl group, R ₃ and R ₄ are each an alkyl group having 1 to 4 carbon atoms, and R ₅ is a carbon atom having 1 carbon atom. ~ 1
2 is an alkyl group, a phenyl group, an alkyl-substituted phenyl group or a cycloalkyl group having 3 to 12 carbon atoms. m is 1 or 2. ) Or a compound represented by the general formula (2)

[0024]

Embedded image (In the formula, R ₆ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₇ is a hydrogen atom or a methyl group, R ₈ and R ₉ are each an alkyl group having 1 to 4 carbon atoms, and R ₁₀ is a carbon atom having 1 carbon atom. ~ 1
2 is an alkyl group, a phenyl group, an alkyl-substituted phenyl group or a cycloalkyl group having 3 to 12 carbon atoms. n is 0, 1 or 2. The compound represented by these is preferable.

Specific examples of the radical-polymerizable organic peroxide represented by the general formula (1) include t-butylperoxyacryloyloxyethyl carbonate and t-amylperoxyacryloyloxyethyl carbonate. Bonnet, t-hexyl peroxyacryloyloxyethyl carbonate,
1,1,3,3-Tetramethylbutylperoxyacryloyloxyethyl carbonate, cumylperoxyacryloyloxyethyl carbonate, p-isopropylcumylperoxyacryloyloxyethyl carbonate ,
t-Butylperoxymethacryloyloxyethyl carbonate, t-amylperoxymethacryloyloxyethyl carbonate, t-hexylperoxymethacryloyloxyethyl carbonate, 1,1,3,3- Tetramethylbutylperoxymethacryloyloxyethyl carbonate, cumylperoxymethacryloyloxyethyl carbonate, p-isopropylcumylperoxymethacryloyloxyethyl carbonate, t-butylperoxymethacryloyloxy Ethyl carbonate, t-
Amyl peroxyacryloyloxy ethoxyethyl carr
Carbonate, t-hexylperoxyacryloyloxyethoxyethyl carbonate, 1,1,3,3-tetramethylbutylperoxyacryloyloxyethoxyethyl carbonate, cumylperoxyacryloyloxyethoxyethyl Carbonate, p-isopropyl cumyl peroxyacryloyloxyethoxyethyl carbonate,
t-butylperoxymethacryloyloxyethoxyethyl carbonate, t-amylperoxymethacryloyloxyethoxyethyl carbonate; t-hexylperoxymethacryloyloxyethoxyethyl carbonate,
1,1,3,3-Tetramethylbutylperoxymethacryloyloxyethoxyethyl carbonate, cumylperoxymethacryloyloxyethoxyethyl carbonate
, P-isopropylcumylperoxymethacryloyloxyethoxyethyl carbonate, t-butylperoxyacryloyloxyisopropyl carbonate, t-amylperoxyacryloyloxyisopropyl carbonate, t-hexyl Peroxyacryloyloxy isopropyl carbonate, 1,1,3,3-tetramethylbutyl peroxyacryloyloxy isopropyl carbonate, cumyl peroxyacryloyloxy isopropyl carbonate, p-isopropyl chloride Milperoxyacryloyloxy isopropyl carbonate, t-butyl peroxymethacryloyloxy isopropyl carbonate
, T-amyl peroxymethacryloyloxy isopropyl carbonate, t-hexyl peroxymethacryloyloxy isopropyl carbonate, 1,1,3,3-
Examples thereof include tetramethylbutyl peroxymethacryloyloxyisopropyl carbonate, cumylperoxymethacryloyloxyisopropyl carbonate, p-isopropylcumylperoxymethacryloyloxyisopropyl carbonate, and the like.

Further, as the compound represented by the general formula (2), t-butylperoxyallyl carbonate, t
-Amyl peroxyallyl carbonate, t-hexyl peroxyallyl carbonate, 1,1,3,3-tetramethylbutyl peroxyallyl carbonate, p-menthane peroxyallyl carbonate , Cumyl peroxyallyl carbonate, t-butyl peroxy methallyl carbonate, t-amyl peroxy methallyl carbonate, t-hexyl peroxy methallyl carbonate,
1,1,3,3-Tetramethylbutylperoxymethallyl carbonate, p-menthane peroxymethallyl carbonate
Bonnet, cumyl peroxymethalyl carbonate, t
-Butylperoxyallyloxyethyl carbonate, t
-Amyl peroxyallyloxyethyl carbonate, t
-Hexyl peroxyallyloxyethyl carbonate,
t-Butylperoxymetallyloxyethyl carbonate
T-amyl perxyl metalyloxyethyl carbonate
, T-hexylperoxymetallyloxyethyl carbonate, t-butylperoxyallyloxyisopropyl carbonate, t-amylperoxyallyloxyisopropyl carbonate, t-hexylperoxyallyloxyisopropyl carbonate Bonnet, t-butylperoxymetalloyloxyisopropyl carbonate, t-amylperoxymetalloyloxyisopropyl carbonate, t-hexylperoxymetalloyloxyisopropyl carbonate
And the like. Especially preferably,
t-Butylperoxyacryloyloxyethyl carbonate, t-butylperoxymethacryloyloxyethyl carbonate, t-butylperoxyallylcarbonyl carbonate
And t-butyl peroxymethallyl carbonate.

In the present invention, 150 parts by weight or less of inorganic filler is added to 100 parts by weight of the total amount of the resin components including the thermoplastic polyester resin (I), the styrene resin (II) and the graft copolymer (III). Agents can be added. Examples of the inorganic filler include powdery granules, flat plates, scales, needles, spheres, hollow fibers, and the like. Specifically, calcium sulfate, calcium silicate, clay, diatomaceous earth, talc, alumina, silica sand. , Glass powder, iron oxide, metal powder, graphite, silicon carbide, silicon nitride, silica, boron nitride, aluminum nitride, carbon black, and other granular fillers, mica, glass plate, sericite, pyrophyllite, aluminum flakes -Metal foil such as graphite, flat or scale-like filler such as graphite, hollow filler such as silas balun, metal balun, glass balun, pumice, glass fiber, carbon fiber, graphite fiber, whisker Examples thereof include mineral fibers such as-, metal fibers, silicon carbide-bite fibers, asbestos, and wstonite. If the blending amount of the filler exceeds 150 parts by weight, the impact strength of the molded product will be reduced, which is not preferable. The surface of the inorganic filler is stearic acid, oleic acid, palmitic acid or a metal salt thereof, paraffin wax, polyethylene wax or a modified product thereof, organic silane, organic borane, organic titanate or the like. It is preferable to process and apply.

In the present invention, within the scope not departing from the gist of the present invention, inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide, organic flame retardants such as halogen type and phosphorus type, organic fillers such as wood powder, Antioxidants, UV inhibitors,
Additives such as a lubricant, a dispersant, a coupling agent, a foaming agent, a cross-linking agent, a colorant, and an elastomer may be added.

The thermoplastic resin composition of the present invention has a temperature of 15
It is produced by melting and mixing at 0 to 350 ° C, preferably 200 to 330 ° C. If the temperature is lower than 150 ° C., the melting is incomplete, the melt viscosity is high, the mixing becomes insufficient, and phase separation or layered peeling appears in the molded product, which is not preferable. On the other hand, if it exceeds 350 ° C., the resin to be mixed is decomposed or gelated, which is not preferable. The melting and mixing method can be carried out by a commonly used kneader such as Banbury mixer, pressure kneader, kneading extruder, twin-screw extruder, and roll.

[0030]

The present invention will be described in more detail with reference to the following examples. In the following examples,% means% by weight unless otherwise specified. Reference Example 1 (Production of Graft Copolymer (III-A)) Sodium hydroxide (3.4 kg) was dissolved in water (4200 ml) and maintained at 20 ° C., and 2,2-bis (4-hydroxyphenyl) propane (6.6 kg) was added. , 8 g of hydrosulfite were dissolved. To this, 28000 ml of methylene chloride was added and stirred to obtain 260 g of p-tert-butylphenol.
Was added and then 3.3 kg of phosgene was bubbled in over 60 minutes. After the completion of blowing phosgene, vigorously stir to emulsify the reaction liquid, and after emulsification, add 8 g of triethylamine to about 1
Stirring was continued for polymerization. The polymerization solution was separated into an aqueous phase and an organic phase, and the organic phase was neutralized with phosphoric acid, and then repeatedly washed with water until the pH of the washing solution became neutral. Then, 35,000 ml of isopropanol was added to the polymerization product. Was allowed to settle. The precipitate was filtered and then vacuum dried to obtain a white powdery polycarbonate resin. This Polycarbonate
The viscosity average molecular weight (M
v) was 16,000. 700 g of this polycarbonate resin powder was placed in a stainless steel autoclave having an internal volume of 5000 ml, and 2500 ml of pure water and 2.5 g of polyvinyl alcohol as a suspending agent were added. Separately, 1.5 g of benzoylperoxide "Nypa-B" (trade name, manufactured by NOF CORPORATION) as a radical polymerization initiator, and t-butylperoxymethacryloyloxyethylcarbone as a radically polymerizable organic peroxide. (6 g) was dissolved in 300 g of styrene as a vinyl monomer, and this solution was put into the autoclave and stirred. Then oh
The polycarbonate resin powder was impregnated with the vinyl monomer containing the radical polymerization initiator and the radical polymerizable organic peroxide by keeping the toclave at 60 to 65 ° C. and stirring for 2 hours. . Then, the temperature was raised to 80 to 85 ° C., and the temperature was maintained for 7 hours to complete the polymerization, followed by washing with water and drying to obtain a grafted precursor (III-a). The styrene polymer in this grafted precursor (III-a) was extracted with ethyl acetate and the number average degree of polymerization was measured by GPC, and it was 900. Then, this grafted precursor (III-a) is extruded at 250 ° C. by a Labo Plastomill uniaxial extruder (manufactured by Toyo Seiki Seisakusho Co., Ltd.) to carry out a grafting reaction, thereby graft graft copolymer (III-A) Got This graft copolymer (III-A) was used as a scanning electron microscope "JEOL JSMT300" (JEOL Ltd.).
Particle size of 0.3 to 0.4 μm
It had a multi-phase structure in which the spherical resin of No. 1 was uniformly dispersed. At this time, the graft efficiency of the styrene polymer was 72.2% by weight.

Reference Example 2 (Production of Graft Copolymer (III-B)) In Reference Example 1, 300 g of styrene monomer as a vinyl monomer, 210 g of styrene monomer and 90 g of acrylonitrile monomer were used.
benzoyl peroxide 1.
5 g of di-3,5,5-trimethylhexanoyl peroxide "paroyl 355" (trade name, NOF Corporation)
(Manufactured by Nippon Oil & Fats Co., Ltd.) 0.3 g except that α-methylstyrene dimer- “NOFMA-MSD” (trade name, manufactured by NOF CORPORATION) was used as a molecular weight modifier. A precursor (III-b) and a graft copolymer (III-B) were obtained. At this time, the number average degree of polymerization of the styrene-acrylonitrile polymer was 1200, and the average particle size of the resin dispersed in the graft copolymer (III-B) was 0.3 to 0.4 μm. The graft efficiency of the styrene-acrylonitrile polymer was 69.
It was 8% by weight.

Reference Example 3 (Production of Graft Copolymer (III-C)) In Reference Example 1, instead of the powder of the polycarbonate resin, an epoxy group-containing olefin polymer "LEXPAR RA-" was used. Three
150 "(trade name, manufactured by Nippon Petrochemical Co., Ltd.) was used to obtain a graft copolymer (III-C) in the same manner as in Reference Example 1. At this time, the number average degree of polymerization of the styrene polymer is 90.
0, and the average particle size of the resin dispersed in the graft copolymer (III-C) was 0.3 to 0.4 μm. The graft efficiency of the styrene polymer is 77.1%.
Met.

Examples 1 to 10 Thermoplastic polyester resin (I) "Toray PBT resin"
140X06 "(displayed as PBT in the table), styrene resin (II)" Dialex HF-77 "(trade name, manufactured by Mitsubishi Kasei Co., Ltd.) (displayed as PS in the table) or" Styrac ABS 283 ". (Trade name, manufactured by Asahi Kasei Co., Ltd.) (displayed as ABS in the table), and the graft copolymer (III-A) or (III-B) obtained in Reference Example 1 or 2 were dry blended, The mixture was fed to a coaxial twin-screw extruder having a screw diameter of 30 mm set to a cylinder temperature of 250 ° C., and granulated after extrusion. The granulated resin was dried at 150 ° C. for 3 hours, then a test piece was prepared by injection molding, and the following test was performed. The results are shown in Table 1. (1) Izod impact value test (with notch): JIS K 7
110 (test piece 13mm × 65mm × 6mm, unit is [kg ・ cm /
cm ² ]) (2) Deflection temperature test under load: JIS K 7207 (test piece 13 mm
× 130mm × 6mm, measurement is performed at 18.6kg / cm ² ) (3) Bending strength test: JIS K 6758 (test piece 10mm × 130m
m × 4 mm, unit is expressed in [kg / cm ² ]) (4) Fluidity test (described in the table as spiral flow) Injection molding machine “TS-35-
"FV25 type" (trade name, manufactured by Tabata Machine Industry Co., Ltd.) was fitted with a mold having a semicircular diameter of 4.8 mm spiral flow groove, injection speed 95%, injection pressure 1000 kg / cm.
2. Molding was carried out at a temperature of 60 ° C. by injection molding, and the molded spiral length was measured and used as an index of fluidity. (5) Appearance test Regarding the appearance of the molded product, the presence or absence of a flow mark was visually determined and ranked as follows. Flow mark ⊚: No flow mark ∘: Slight flow mark ×: Flow mark on the entire surface

[0034]

[Table 1]

Examples 11 to 16 The grafting precursor (III-a) or graft copolymer (III-A) obtained in Reference Example 1 or the grafting precursor (III-a obtained in Reference Example 2 b) or an example using a graft copolymer (III-B), SEBS "Clayton G1650" (trade name, manufactured by Shell Chemical Co., Ltd.) (SEB
S), glass fiber (average fiber length 0.3 mm × diameter 10 μm) added or not added as an inorganic filler in Table 2 (abbreviated symbol PBT,
The meanings of PS and ABS are the same as in Table 1.

[0036]

[Table 2]

Comparative Examples 1 to 13 Graft copolymers (III-A) used in Examples 1 to 16
Or a graft copolymer (III-B) is not used, or an epoxy group-containing olefin polymer "LEXPAR RA-3150" (trade name, manufactured by Nippon Petrochemical Co., Ltd.) (shown as EGMA is used instead. (Displayed inside), styrene-
Examples using the maleic anhydride copolymer (95/5) (shown as SMA in the table) or the graft copolymer (III-C) obtained in Reference Example 3 are shown in Tables 3 and 4 (abbreviated symbols). (The meanings of PBT, PS and ABS are the same as in Table 1.)
Shown in

[0038]

[Table 3]

[0039]

[Table 4]

From these results, when the thermoplastic polyester resin (I) and the styrene resin (II) were blended, the specific graft copolymer (III-A) or (I
The thermoplastic resin composition of the present invention to which II-B) is added is superior in molding processability (fluidity), heat resistance, impact resistance, bending strength and appearance of the molded product to the thermoplastic resin composition of the comparative example. It turns out that it is a composition. On the other hand, in Comparative Examples, when the ethylene-glycidyl methacrylate copolymer or the styrene-maleic anhydride copolymer was used as the compatibilizing agent (Comparative Examples 8, 9, 11, 12), the thermoplastic polyester resin ( Since the compatibility between I) and the styrene resin (II) is insufficiently improved, impact resistance and heat resistance are low. Further, in the case of using a graft copolymer (III-C) of an epoxy group-containing olefin-based copolymer and a vinyl-based copolymer (Comparative Example 1
0, 13) have improved impact resistance to some extent, but it is understood that heat resistance and molding processability (fluidity) are insufficient.

[0041]

The thermoplastic resin composition of the present invention comprises a thermoplastic polyester resin (I) and a styrene resin (I).
It is a thermoplastic resin composition which is excellent in impact resistance, heat resistance, molding processability and surface appearance by making use of each of the advantages of I).
Therefore, the molded products are automobile parts, electric / electronic parts,
Can be widely used for industrial parts.

Claims (1)

[Claims] 1. A thermoplastic polyester resin (I) 5 to
95% by weight, styrene resin (II) 95 to 5% by weight, and polycarbonate resin segment 5 to 95% by weight
And vinyl resin segment 95 to 5% by weight,
Graft copolymer (III) showing a multiphase structure in which a dispersed phase formed by the other segment is finely dispersed in a continuous phase formed by one segment is a thermoplastic polyester resin (I) and A thermoplastic resin composition comprising 1 to 100 parts by weight based on 100 parts by weight of a total amount of styrene resin (II).