JPH03126756A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition, improved in compatibility, excellent in impact, chemical resistance, etc., and suitable as automotive parts, etc., by blending a composition composed of an aromatic polyester resin, aromatic polycarbonate- based resin, etc., with a specific thermoplastic resin of a multiphase structure as a compatibilizing agent. CONSTITUTION:A thermoplastic resin composition obtained by blending 100 pts.wt. total amount of (A) 3-95wt.% aromatic polyester-based resin, (B) 3-95wt.% aromatic polycarbonate-based resin and (C) 1-20wt.% butadiene-based copolymer prepared by carrying out graft polymerization of a vinylic monomer selected from methacrylic acid esters, etc., with a butadiene-based polymer with (D) 1-20 pts.wt. thermoplastic resin of a multiphase structure, obtained by copolymerizing a vinylic monomer with a radically (co)polymerizable organic peroxide expressed by formula I or II (R1 is H or 1-2C alkyl; R2 and R7 are H, methyl, etc.), in particles of an epoxy group-containing olefinic copolymer and having a specific disperse phase.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a thermoplastic resin composition having excellent heat resistance, impact resistance, surface properties, oil resistance, water resistance, etc. It is also used in a wide range of applications such as electronic mechanical parts and industrial parts.

[Prior Art] Aromatic polyester resins have excellent properties such as moldability, chemical resistance, dimensional stability, and weather resistance, and are widely used in various molded products.

However, the impact resistance is low, the deflection temperature under load is low, and there are problems with heat resistance, which may limit its use.

On the other hand, aromatic polycarbonate resins have excellent heat resistance, mechanical properties, and impact resistance, but have poor chemical resistance, and are made of acrylonitrile-butadiene ◆ styrene copolymer (ABS),
Methyl methacrylate-butadiene-styrene copolymer (MBS)-based resins have excellent impact resistance but have the disadvantage of poor chemical resistance.

A composition comprising an aromatic polyester resin and an aromatic polycarbonate resin is disclosed in, for example, JP-A-1-113456.
Although the compatibility of both resins is improved and the impact resistance is improved, the composition is not satisfactory because the surface properties and low-temperature impact strength are insufficient.

Furthermore, as disclosed in JP-A-1-165858, although the compatibility of both resins is improved and the impact resistance is improved, the surface properties and low-temperature impact strength are insufficient. There are no satisfying compositions.

Furthermore, in JP-A-1-185658, aromatic polyester resin, aromatic polycarbonate resin, and A
Although low-temperature impact strength and surface properties can be improved by combining BSL or MBS-based resins, heat resistance is still not sufficient.

[Problems to be Solved by the Invention] Therefore, an object of the present invention is to improve the compatibility of aromatic polyester resin, aromatic polycarbonate resin, and ABS or MBS resin, and to improve impact resistance, especially resistance at low temperatures. Excellent impact resistance, chemical resistance, surface properties, and heat resistance.
The objective is to provide a well-balanced resin composition.

[Means for Solving the Problems] As a result of intensive research to solve the above objects, the present invention is based on aromatic polyester resins, aromatic polycarbonate resins,
By blending a specific multiphase thermoplastic resin with a butadiene-based graft copolymer as a compatibilizer,
By improving the compatibility of aromatic polyester 5-based resin, aromatic polycarbonate-based resin, and butadiene-based graft copolymer, impact resistance,
In particular, we have completed a well-balanced thermoplastic resin composition with excellent impact resistance, chemical resistance, surface properties, and heat resistance at low temperatures.

That is, the present invention comprises (I) 3 to 95% by weight of aromatic polyester resin, (II) 3 to 95% by weight of aromatic polycarbonate resin, (III) butadiene polymer (a) and methacrylic acid ester (b) aromatic 1 to 20% by weight of a butadiene copolymer graft-copolymerized with one or more vinyl monomers selected from the group consisting of a monovinyl compound and a vinyl cyanide compound (iv), and (iv) an olefin containing an epoxy group. A thermoplastic resin composition comprising 5 to 95% by weight of a copolymer and 95 to 5% by weight of a vinyl (co)polymer obtained from at least one vinyl monomer, the composition comprising: mer and the following general formula (a) or (b) 3 CH2=C-C 1 10 (C1+2-CH-0), -C-0-0-C1 5 B R70R9 (b) [in the formula , R is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R2 and R7 are a hydrogen atom or a methyl group, Re is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R3, R4
and R8 and R9 are each an alkyl group having 1 to 4 carbon atoms, and R5N RIO is an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, or an alkyl group having 3 to 12 carbon atoms.
represents a cycloalkyl group, m is 1 or 2, and n
is 011 or 2] or a grafted precursor obtained by copolymerizing at least one radical (co)polymerizable organic peroxide represented by the following in epoxy group-containing olefin copolymer particles: Multiphase thermoplastic resins 1 to 1, which are melt-kneaded multiphase structures in which either an epoxy group-containing copolymer or a vinyl (co)polymer forms a dispersed phase with a particle size of 0.001 to 10 μm. This is a thermoplastic resin composition containing 20 parts by weight.

The aromatic polyester used in the present invention is a polyester having an aromatic ring in the chain unit of the polymer, and the main components are an aromatic dicarboxylic acid (or its ester-forming derivative) and a diol (or its ester-forming derivative). It is a polymer or copolymer obtained by a condensation reaction.

The aromatic dicarboxylic acids mentioned here include terephthalic acid; isophthalic acid; phthalic acid; 2,6-naphthalenedicarboxylic acid; 1,5-naphthalenedicarboxylic acid; bis(p-
carboxyphenyl)methane; anthracene dicarboxylic acid; 4,4'-diphenyl dicarboxylic acid; 4,4'-diphenyl ether dicarboxylic acid; 1,2-bis(phenoxy)ethane-4,4'-dicarboxylic acid or ester-forming derivatives thereof Examples include.

In addition, the diol component includes aliphatic diols having 2 to 10 carbon atoms, that is, ethylene glycol; propylene glycol; 114-butanediol; neopentyl glycol; II 5-bentanediol; 1,6-hexanesiol: decamethylene diglycol; Cyclohexanediol, etc., or long chain glycols with a molecular weight of 400 to eooo, i.e. polyethylene glycol: Boly-1
, 3-propylene glycol; polytetramethylene glycol, and mixtures thereof.

Preferred thermoplastic aromatic polyesters used in the present invention include polyethylene terephthalate;
Polypropylene terephthalate; polybutylene reterephthalate; polyhexamethylene terephthalate; polyethylene-2,6-su-phthalate; polyethylene-1,2-bis(phenoxyethane-4,4'-dicarboxylate) and the like. More preferred. is polyethylene terephthalate;
It is polybutylene terephthalate.

The intrinsic viscosity of these thermoplastic aromatic polyesters is trifluoroacetic acid (25)/methylene chloride (75) 100
mI! Medium, the concentration is 0.32g and measured under 25±0.10. Preferably, the intrinsic viscosity is 0.4 to 4.0 dl/
It is g.

If it is less than 0.4 dJ, the thermoplastic aromatic polyester resin will not be able to exhibit sufficient mechanical strength, which is not preferable.

Moreover, if it exceeds 4. Odf/g, the fluidity during melting will decrease and the surface gloss of the molded product will decrease, which is not preferable.

The aromatic polycarbonate resin used in the present invention includes 4,
4,4-dioxysialkane polycarbonate 10-, including 4-dihydroquine diphenyl-2,2-propane (commonly known as bisphenol), but especially 4,4-dihydroxydiphenyl-2,2-propane. Polycarbonate having a number average molecular weight of 15,000 to 80,000 is preferred.

These polycarbonates are manufactured by any method.

For example, in the production of polycarbonate of 4,4-dihydroxydiphenyl-2,2-propane, 4,4-dihydroxydiphenyl-2,2-propane is used as the dioxy compound, and phosgene is added in the presence of an aqueous caustic alkali solution and a solvent. Examples include a method of manufacturing by blowing, and a method of manufacturing by transesterifying 4,4-dihydroxydiphenyl-2,2-propane and carbonic acid diester in the presence of a catalyst.

The butadiene-based graft copolymer used in the present invention is obtained by polymerizing two or more compounds selected from vinyl cyanide compounds, aromatic vinyl compounds, and unsaturated carboxylic acid alkyl ester compounds in the presence of a butadiene-based rubber. This is the resulting graft copolymer (a).

Further, if necessary, it may contain a copolymer (b) obtained by polymerizing two or more compounds selected from vinyl cyanide compounds, aromatic vinyl compounds, and unsaturated carboxylic acid alkyl ester compounds.

The composition ratio of the conjugated diene rubber and the above-mentioned compound in the graft copolymer (a) is not particularly limited, but a composition ratio of 5 to 80% by weight of the conjugated diene rubber and 95 to 20% by weight of the above-mentioned compound is preferable. The composition ratio of the above-mentioned compounds is preferably 0 to 30% by weight of the vinyl cyanide compound, 30 to 80% by weight of the aromatic vinyl compound, and 0 to 70% by weight of the unsaturated carboxylic acid alkyl ester compound.

The particle diameter of the conjugated diene rubber is not particularly limited, but is preferably 0.05 to 1 μm.

The composition ratio of the above compounds in the copolymer (b) is vinyl cyanide compound ○~30M%, aromatic vinyl compound 50~30M amount%.
It is preferable that the amount of the unsaturated carboxylic acid alkyl ester compound is 90% by weight and 40% by weight of the unsaturated carboxylic acid alkyl ester compound O. Copolymer (b)
Intrinsic viscosity of [30°C1 dimethyl formaldehyde (D
MF)] is also not particularly limited, but is preferably 0.25 to 1.0. Conjugated diene rubbers include polybutadiene,
Examples include butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, and the like. Examples of vinyl cyanide compounds include acrylonitrile and methacrylate, and examples of aromatic vinyl compounds include styrene and α.
- Methylstyrene, vinyltoluene, dimethylstyrene, chlorostyrene, etc., and unsaturated carboxylic acid alkyl ester compounds such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate,
Examples include hydroxylethyl acrylate.

Methods for producing butadiene-based graft copolymers include emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, and emulsion polymerization.
Examples include suspension polymerization method.

The epoxy group-containing olefin polymer used in the multiphase structure thermoplastic phase 3 used in the present invention is, in part, an olefin produced by high-pressure radical polymerization, an unsaturated glycidyl group-containing monomer, and other unsaturated monomers. It is a ternary or multicomponent copolymer with ethylene, and the olefin of the above copolymer is particularly preferably ethylene.
Weight %, glycidyl group-containing monomer 0. E5-40% by weight
, other unsaturated monomers in an amount of O to 39.5% by weight is preferred.

Examples of the unsaturated glycidyl group-containing monomer include glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconate, monoglycidyl butene tricarboxylate, diglycidyl butene tricarboxylate, triglycidyl butene tricarboxylate, and α- chloroallyl, maleic acid, crotonic acid,
Examples include glycidyl esters such as fumaric acid, glycidyl 4-ethers such as vinyl glycidyl ether, allyl glycidyl ether, glycidyloxyethyl vinyl ether, styrene-p-glycidyl ether, and p-glycidyl styrene, but particularly preferred ones include glycidyl methacrylate,
Mention may be made of acrylic glycidyl ethers.

Other unsaturated monomers include at least one monomer selected from olefins, vinyl esters, α,β-ethylenically unsaturated carboxylic acids or derivatives thereof,
Specifically, olefins such as propylene, butene-1, hexene-1, decene-1, octene-1, styrene,
Vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, acrylic acid, methacrylic acid,
Methyl, ethyl, propyl, butyl, 2-ethylhexyl, cyclohexyl of acrylic acid or methacrylic acid,
Esters such as dodecyl and octadecyl, maleic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid monoesters and diesters, vinyl ethers such as vinyl chloride, vinyl methyl ether, vinyl ethyl ether, and acrylic acid amide compounds, etc. (meth)acrylic acid esters are particularly preferred.

Specific examples of the epoxy group-containing olefin copolymer include ethylene/glycidyl methacrylate copolymer, ethylene/vinyl acetate/glycidyl methacrylate copolymer,
Examples include ethylene/ethyl acrylate/glycidyl methacrylate copolymer, ethylene/carbon oxide/glycidyl methacrylate copolymer, ethylene/glycidyl acrylate copolymer, ethylene/vinyl acetate/glycidyl acrylate copolymer, etc. . Among them, ethylene/
These are glycidyl methacrylate copolymer, ethylene/ethyl acrylate/glycidyl methacrylate copolymer, or ethylene/vinyl acetate/glycidyl methacrylate copolymer.

These epoxy group-containing olefin copolymers can be used as a mixture.

The method for producing an epoxy group-containing olefin copolymer by high-pressure radical polymerization includes the above-mentioned 60 to 99.5% by weight of ethylene,
One or more unsaturated glycidyl group-containing monomers 0.5-40
% by weight of at least one other unsaturated monomer 0-39.
5% by weight of the monomer mixture in the presence of a radical polymerization initiator of o,oooi to 1% by weight based on the total weight of all their monomers at a polymerization pressure of 500 to 4000 kg/cJ, preferably 1000 to 3500 kg/c+ff, reaction temperature 50 to 400'C, preferably 100 to 350'C, in the presence of a chain transfer agent and optionally an auxiliary agent, in a tank or tube reactor. This is a method of contacting and polymerizing simultaneously or in stages.

Examples of the radical polymerization initiators include peroxides, hydroperoxides, azo compounds, amine oxide compounds,
Common initiators such as oxygen may be mentioned.

In addition, as a chain transfer agent, hydrogen, propylene, butene-
1,01 to C20 or higher saturated aliphatic hydrocarbons and halogen-substituted hydrocarbons, such as methane, ethane,
Propane, butane, isobutane, n-hexane, n-hebutane, cycloparaffins, chloroform, and saturated aliphatic alcohols with carbon tetrachloride NCI 17- to C20 or higher, such as methanol, ethanol, propatool and impropatur , CI to C20 or higher, such as saturated aliphatic carbonyl compounds such as carbon dioxide, acetone and methyl ethyl ketone, and aromatic compounds such as toluene, diethylbenzene and xylene.

Another example of the epoxy group-containing olefin copolymer of the present invention is a modified product obtained by adding the above-mentioned unsaturated glycidyl group-containing monomer to a conventional olefin homopolymer or copolymer.

The olefin polymers include homopolymers such as low density, medium density, and high density polyethylene; polypropylene; polybutene-1; poly-4-methylpentene-1; ethylene-propylene copolymers; ethylene-butene-1 Copolymer; ethylene-hexene-1 copolymer; ethylene-4-methylpentene-1 copolymer; other α-ole 18 mainly composed of ethylene such as ethylene-octene-1 copolymer
- Copolymers with fins, copolymers with other α-olefins mainly composed of propylene, such as propylene-ethylene block copolymers; ethylene-vinyl acetate copolymers; ethylene-acrylic acid copolymers; Ethylene-methacrylic acid copolymer; Copolymer of ethylene and ester of acrylic acid or methacrylic acid such as methyl, ethyl, propyl, isopropyl, butyl; Ethylene-maleic acid copolymer; Ethylene-propylene copolymer rubber: Ethylene-propylene-diene copolymer rubber; liquid polybutadiene;
The present invention also includes ethylene-vinyl acetate-vinyl chloride copolymers and mixtures thereof, or blends thereof with different types of synthetic resins or rubbers.

The vinyl (co)polymer in the multiphase thermoplastic resin used in the present invention specifically includes styrene, nuclear substituted styrene such as methylstyrene, dimethylstyrene, ethylstyrene, isopropylstyrene, chlorstyrene, α -Substituted styrene Vinyl aromatic monomers such as α-methylstyrene, α-ethylstyrene; C1-7 alkyl esters of acrylic acid or methacrylic acid, such as methyl, ethyl, propyl (meth)acrylate; (Meth)acrylic acid ester monomers such as isopropyl and butyl; (meth)acrylonitrile monomers such as acrylonitrile or methacrylonitrile; vinyl ester monomers such as vinyl acetate and vinyl propionate; acrylamide, methacrylamide, etc. (meth)acrylamide monomer; maleic anhydride, maleic acid mono- and di-
It is a (co)polymer obtained by polymerizing one or more types of vinyl monomers such as esters. Among these, vinyl aromatic monomers, (meth)acrylic acid ester monomers, (meth)acrylonitrile monomers and vinyl ester monomers are preferably used.

In particular, a vinyl (co)polymer containing 50% by weight or more of a vinyl aromatic monomer or a (meth)acrylic acid monomer is the most preferred embodiment since it has good dispersibility in polyoxymethylene.

The multiphase thermoplastic resin referred to in the present invention refers to an epoxy group-containing olefin copolymer or vinyl (co)polymer matrix containing a vinyl (co)polymer or epoxy group-containing olefin as a different component. A copolymer that is uniformly dispersed in a spherical shape.

The particle size of the dispersed polymer is o, ooi ~ 10 μm1
Preferably it is 0.01 to 5 μm.

If the dispersed resin particle size is less than o, ooi μm or more than 5 μm, the aromatic polyester resin, aromatic polycarbonate resin, and butadiene graft copolymer will not be sufficiently compatible, resulting in deterioration in appearance or impact resistance, for example. This is not preferable because the improvement effect may be insufficient.

The number average degree of polymerization of the vinyl (co)polymer in the multiphase thermoplastic resin of the present invention is 5 to io, o.

O1 is preferably 10 to 5,000.

If the number average degree of polymerization is less than 5, it is possible to improve the impact resistance of the thermoplastic resin composition of the present invention, but the heat resistance decreases, which is not preferable. Moreover, if the number average degree of polymerization exceeds 10,000, the melt viscosity will increase, moldability will decrease, and surface gloss will decrease, which is not preferable.

The multiphase thermoplastic resin of the present invention contains 5 to 95% by weight, preferably 20 to 9% by weight of the epoxy group-containing olefin copolymer.
It consists of 0% by weight. Therefore, vinyl (
The amount of co)polymer is 95-5% by weight, preferably 80-10% by weight.

If the content of the epoxy group-containing olefin copolymer is less than 5% by weight, the effect of improving impact resistance will be insufficient, which is not preferable.

In addition, 95% by weight of epoxy group-containing olefin copolymer
If it exceeds 100%, a sufficient effect of improving impact resistance can be obtained, but it is not preferable because heat resistance decreases.

The grafting method for producing the multiphase thermoplastic resin of the present invention may be any of the generally well-known methods such as chain transfer method and ionizing radiation method, but the most preferred method is the following method. This is due to The reason is that the grafting efficiency is high and secondary aggregation due to heat does not occur.
This is because the expression of performance is more effective than that of 22-, and the manufacturing method is simpler.

Hereinafter, the method for producing the multiphase thermoplastic resin composition of the present invention will be specifically explained.

That is, 100 parts by weight of an epoxy group-containing olefin copolymer is suspended in water, and 5 to 400 parts by weight of a vinyl monomer of the following type is mixed with the following general formula (a) or (b).
In order to obtain a half-life of 10 hours, one or a mixture of two or more radical (co)polymerizable organic peroxides represented by 0.1 to 10 parts by weight per 100 parts by weight of the vinyl monomer. A radical copolymerization initiator having a decomposition temperature of 40 to 90°C is dissolved in an amount of 0.01 to 5 parts by weight per 100 parts by weight of the vinyl monomer and the radical (co)polymerizable organic peroxide. The resulting solution is heated under conditions that do not substantially cause decomposition of the radical polymerization initiator, and the vinyl monomer,
A radical (co)polymerizable organic peroxide and a radical polymerization initiator are impregnated into an epoxy group-containing olefin copolymer, and when the impregnation rate reaches 50% or more of the initial value, the temperature of this aqueous suspension is increased. and vinyl monomer and radical (
A grafting precursor (A) is obtained by copolymerizing a co)polymerizable organic peroxide in an epoxy group-containing olefin copolymer.

This grafted precursor is also a multiphase thermoplastic.

Therefore, this grafting precursor (A) can be directly applied to aromatic polyester resin, aromatic polycarbonate resin,
and a butadiene-based graft copolymer.

The multiphase thermoplastic resin of the present invention can also be obtained by wet-bulbing the grafted precursor (A) while melting it at 100 to 300°C. At this time, a multiphase thermoplastic resin can also be obtained by separately mixing an epoxy group-containing olefin copolymer (B) or a vinyl-based (co)polymer (C) with the grafting precursor and kneading it while melting. Can be done. Most preferred is a thermoplastic resin with a multiphase structure obtained by kneading a grafted precursor.

The radical (co)polymerizable organic peroxides represented by the general formulas (a) and (b) are represented by the general formula % () [wherein R' is a hydrogen atom or a carbon number of I to 2]. Alkyl group, R2 is hydrogen atom or methyl group N R3 and R4
are each an alkyl group having 1 to 4 carbon atoms, and R5 is an alkyl group having 1 to 4 carbon atoms.
~12 alkyl group, phenyl group, alkyl-substituted phenyl group or cycloalkyl group having 3 to 12 carbon atoms,
m is 1 or 2].

In addition, the radical (co)polymerizable organic peroxide represented by the general formula (b) is the formula () [wherein N Re is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms NR7 is a hydrogen atom or a methyl group, and Ra,
Re is an alkyl group having 1 to 4 carbon atoms, R□. represents an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, or a cycloalkyl group having 3 to 12 carbon atoms, and n is 011 or 2. This is a compound represented by

Examples of the radical (co)polymerizable organic peroxide represented by the general formula (a) include t-butylperoxyacryloyloxyethyl carbonate, t-amylperoxyacryloyloxyethyl carbonate, and t-hexylperoxyacrylate. Royloxyethyl carbonate, 1,1
, 3.3-tetramethylbutylperoxyacryloyloxyethyl carbonate, cumylperoxyacryloyloxyethyl carbonate, p-isoprobylperoxyacryloyloxyethyl carbonate, t-butylperoxyphthacryloyloxyethyl carbonate , t-amylperoxymethacryloyloxyethyl carbonate, t-hexylperoxymethacryloyloxyethyl carbonate), 1,1,3.3-tetramethylbutylperoxymethacryloyloxyethyl carbonate, cumylperoxymethacryloyloxyethyl carbonate , p-isoprobylcumylperoxymethacryloyloxyethyl carbonate, t-butylperoxymethacryloyloxyethyl carbonate, t-amylperoxyacryloyloxyethoxyethyl carbonate, t-hexylperoxyacryloyloxyethoxyethyl carbonate), 1 , 1,3.3-tetramethylbutylperoxyacryloyloxyethoxyethyl carbonate, cumylperoxyacryloyloxyethoxyethyl carbonate, p-isopropylperoxyacryloyloxyethoxyethyl carbonate, t-butylperoxyphthacryloyloxyethoxyethyl carbonate , t-amylperoxyacryloyloxyethoxyethoxyethyl carbonate, t-hexylperoxymethacryloyloxyethoxyethyl carbonate, 1,1.3
, 3-tetramethylbutylperoxymethacryloyloxyethoxyethoxyethyl carbonate, cumylperoxyacryloyloxyethoxyethyl carbonate, p-isoprobylcumylperoxymethacryloyloxyethoxyethyl carbonate, t-butylperoxyacryloyloxyisopropyl carbonate, t-amylperoxy Acryloyloxyisopropyl carbonate, t-hexylperoxyacryloyloxyisopropyl carbonate), 1,1,3.3-tetramethylbutylperoxyacryloyloxyisopropyl carbonate, cumylperoxyacryloyloxyisopropyl carbonate, p
-isopropylperoxyacryloyloxyisopropyl carbonate, t-butylperoxyphthacryloyloxyisopropyl carbonate, t-amylperoxyacryloyloxyisopropyl carbonate, t-hexylperoxymethacryloyloxyisopropyl carbonate, 1,1.3.3-tetra Examples include methylbutylperoxyacryloyloxyisopropyl carbonate, relperoxyphthacryloyloxyisopropyl carbonate, and p-isopropylperoxyacryloyloxyisopropyl carbonate.

Furthermore, as a compound represented by general formula (b), t
-Butylperoxyallyl carbonate, t-amylperoxyallyl carbonate, t-hexylperoxyallyl carbonate, 1,L 3,3-tetramethylbutylperoxyallyl carbonate, p-menthane peroxyallyl carbonate, cumylperoxyallyl carbonate, t- Butyl peroxy methallyl carbonate, t-amyl peroxy methallyl carbonate, t
-hexylperoxyallyl carbonate, p-menthane peroxymethallyl carbonate, cumylperoxy29 siphthalyl carbonate, t-butylperoxyallyloxyethyl carbonate, t-amylperoxyallyloxyethyl carbonate, t-hexylperoxyallyl carbonate Roxyethyl carbonate, t-butylperoxyphthalyloxyethyl carbonate, t-amylperoxyallyloxyethyl carbonate, t-hexylperoxyallyloxyethyl carbonate, t-butylperoxyallyloxyisopropyl carbonate, t-amylperoxyallyloxyisopropyl carbonate, t-hequinleberoxyallyloxyisopropyl carbonate,
Examples include t-butylperoxyphthalyloxyisopropyl carbonate, t-amylperoxyallyloxyisopropyl carbonate, and t-hequinleberoxyallyloxyisopropyl carbonate.

Among these, preferred are t-butylperoxyacryloyloxyethyl carbonate, t-butylberoxyphthacryloyloxyethyl carbonate, t-butylperoxyallyl carbonate, and t-butylperoxymethallyl carbonate.

In the present invention, the above (I) + (II) + (II
0 to 100 parts by weight of the resin component containing I)+(■)
Up to 150 parts by weight of inorganic fillers can be included.

Examples of the above-mentioned inorganic filling shrines include powder-like, flat-like, scaly, needle-like, spherical or hollow shapes, and fibrous shapes, and specific examples include calcium sulfate, calcium silicate, clay, diatomaceous earth, talc, alumina, and silica sand. Powder-like fillers such as glass powder, iron oxide, metal powder, graphite, silicon carbide, silicon nitride, silica, boron nitride, aluminum nitride, carbon black; mica, glass plate, sericite, pyrolite, aluminum flakes, etc. Flat or scaly filling materials such as metal foil and graphite; hollow filling shrines such as glass balloons, metal balloons, glass balloons, and pumice; glass fibers,
carbon fiber, graphite fiber, whiskers, metal fiber,
Examples include mineral fibers such as silicon carbide fibers, asbestos, and wolstonite.

If the blending amount of the filler exceeds 150 parts by weight, the mechanical strength such as impact strength of the molded article will decrease, which is not preferable.

In addition, the surface of the inorganic filler contains stearic acid, oleic acid,
It is preferable to perform surface treatment using 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.

The thermoplastic resin composition of the present invention has a temperature of 150 to 350°C.
, preferably by melting and mixing at 180 to 3308C. If the temperature is less than 150'C, the melting may be incomplete or the melt viscosity may be high, resulting in insufficient melting and phase separation or delamination may occur in the molded product, which is not preferable. Moreover, if the temperature exceeds 350°C, the resins to be mixed may decompose or gel, which is not preferable.

The melt mixing can be carried out using a commonly used mixer such as a mixing roll, a Banbury mixer, a kneader mixer, a kneading extruder, a twin-screw extruder, or a roll.

The present invention further includes inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide, organic flame retardants such as halogen-based and phosphorus-based flame retardants, antioxidants, ultraviolet inhibitors, lubricants, dispersants, etc., without departing from the gist of the present invention. Additives such as foaming agents, crosslinking agents, coloring agents, and engineering plastics such as other polyolefin resins, polyamides, polyphenylene ethers, and polyphenylene sulfides may be added.

[Example] Hereinafter, the present invention will be explained in more detail with reference to Examples.

Production of mc multiphase structure thermoplastic resin A] Volume 5j! Pure water in a stainless steel autoclave
00g of polyvinyl alcohol was added thereto, and 2.5g of polyvinyl alcohol was further dissolved therein as a suspending agent. As an epoxy group-containing olefin copolymer, ethylene/glycidyl methacrylate copolymer (glycidyl methacrylate content: 15% by weight) "Lexpar J-
3700J [Product name, manufactured by Nippon Petrochemical Co., Ltd.] 700
g was added and stirred and dispersed under a nitrogen atmosphere. Separately, benzoyl peroxide “Niper B” as a radical polymerization initiator [trade name, manufactured by NOF Corporation] 1.5 g
1 6 g of t-butylperoxyphtacryloyloxyethyl carbonate as a radical (co)polymerizable organic peroxide
is dissolved in 300 g of styrene as a vinyl monomer,
This solution was put into the autoclave and stirred.

Next, the autoclave was heated to 60 to 65°C and stirred for 2 hours to transform the vinyl monomer containing the radical polymerization initiator and the radical (co)polymerizable organic peroxide into an epoxy group-containing olefin copolymer. impregnated inside. Next, after confirming that the impregnated vinyl monomer, radical (co)polymerizable organic peroxide, and radical polymerization initiator are at least 50% by weight, the temperature is increased to 80 to 80% by weight.
The temperature was raised to 5°C, maintained at this temperature for 7 hours to complete polymerization, washed with water and dried to obtain grafted precursor 4. The styrene polymer in this grafted precursor was extracted with ethyl acetate, and the number average degree of polymerization was measured by GPC and found to be 900.

Next, this grafted precursor was extruded at 200° C. using a "Laboplast Mill-Screw Extruder" (Toyo Seiki Co., Ltd.) to cause a grafting reaction, thereby obtaining a multiphase thermoplastic resin A.

This multiphase thermoplastic resin was examined using a scanning electron microscope (rJEO).
When observed using OL JSM T300J [manufactured by JEOL Ltd.], it was found to be a multiphase thermoplastic resin in which perfectly spherical resin with a particle size of 0.3 to 0.4 μm was uniformly dispersed.

The grafting efficiency of the styrene polymer at this time was 77.
It was 1% by weight.

Production of iC multiphase structure thermoplastic resin B) In Reference Example 1, the styrene monomer as the vinyl monomer was changed to 300 g of methyl methacrylate monomer, and n-dodecyl mercaptan was added as the molecular weight regulator. A multiphase structure thermoplastic resin B was obtained by repeating Reference Example 1 except that .6 g was used.

At this time, the number average degree of polymerization of the methyl methacrylate polymer was 7001, and the average particle diameter of the resin dispersed in this resin composition was 0.1 to 0.2 μm.

! f! JjLL (Production of multiphase structure thermoplastic resin C) In Reference Example 1, styrene monomer 3 as the vinyl monomer
00 g of styrene 210 g1 was mixed with 90 g of acrylonitrile monomer, and 1.5 g of benzoyl peroxide was mixed with di-3,5°5-trimethylhexanoyl peroxide "Perloyl 355J [trade name, manufactured by NOF Corporation]" 3g and added α-methylstyrene dimer “Nofmar MSD” as a molecular weight regulator [trade name,
A multiphase structure thermoplastic resin C was obtained by repeating Reference Example 1, except that 0.3 g of Nippon Oil & Fats Co., Ltd.] was used.

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 this resin composition was 0.3 to 0.4 μm.

Real jlLL-Unini L Polyethylene terephthalate with intrinsic viscosity 3.5df/g)
(expressed as PBT), a polycarbonate resin with a number average molecular weight of 82.000, a butadiene-based graft copolymer shown in Table 1, and a multiphase thermoplastic resin obtained in the reference example were melted and mixed in the proportions shown in Table 2. did.

The melting and mixing method is to tri-blend each resin pellet, then supply it to a coaxial twin-screw extruder with a screw diameter of 30 mm set at a cylinder temperature of 250'C [manufactured by Plastic Engineering Research Institute Co., Ltd.] Melts inside
Mixed. After the mixed resin is granulated, it is heated to 150'C.
After drying for 3 hours, test pieces were prepared by injection molding.

The size of the test piece and the test method are as follows.

(1) Izotsu impact value (with notch): 1.3mmXB
5mmX[imm (JIS K7110) (2)
Load deflection temperature: 10+nmXl30mm XBmm (JIS
K7207) (3) Appearance of molded product: 87- The presence or absence of flow marks and the quality of gloss were observed with the naked eye and ranked as follows.

(a) Flow mark ◎: No flow mark at all ○: Slight flow mark ×: Flow mark present (b) Good or bad gloss ◎: Very good gloss ○: Good gloss ×: Poor gloss (hereinafter referred to as margin) 38- 9- Pour pure water eoog into a stainless steel autoclave (manufacture of multi-phase structure thermoplastic resin) container 11.
Furthermore, 0.6 g of polyvinyl alcohol was dissolved as a suspending agent. In this, 1.0 g of polymeric peroxide shown by the following formula (II = 2 to 40) and 0.2 g of t-butylperoxyphtacryloquine ethyl carbonate were added to 20 g of n-butyl acrylate.
The solution dissolved in the above was put into the autoclave and stirred. Next, the temperature of the autoclave was raised to 60°C, and polymerization was carried out for 2 hours. After polymerization, the autoclave was cooled to room temperature, 180 g of methyl methacrylate was added, and after impregnating for a working time,
Polymerization was carried out at 80°C for 2 hours, washed with water and dried to obtain a block copolymer having peroxide bonds in the butyl acrylate segments. After premixing 150 g of this block copolymer and 350 g of ethylene/glycidyl methacrylate copolymer (glycidyl methacrylate content 15%),
A multiphase thermoplastic resin was obtained by grafting reaction at 200'C in a Laboplast Mill-axial extruder.

An example in which the butadiene-based graft copolymer and/or multiphase thermoplastic resin used in Example 1 was omitted, and a sample produced in Reference Example 4 instead of multiphase thermoplastic resin B was used. Table 3 shows an example using a thermoplastic resin having a multiphase structure.

(Left below) ~ Example in which the multiphase structured thermoplastic resin of Examples 1 to 9 was replaced with the grafted precursor obtained in the reference example and average fiber length of 5.0 m
Table 4 shows an example in which glass fibers with an m1 diameter of 10 μm were blended.

(Left below) From the above, the thermoplastic resin composition of the present invention, which is a blend of thermoplastic polyester resin, polycarbonate resin, and butadiene graft copolymer, has high impact resistance, especially low-temperature impact strength, It can be seen that while the composite material has excellent heat resistance and surface appearance, the comparative example has no improvement in impact resistance or heat resistance and has insufficient compatibility.

[Effects of the Invention] The thermoplastic resin composition of the present invention takes advantage of the advantages of aromatic polyester resin, polycarbonate resin, and butadiene graft copolymer, and has excellent impact resistance, heat resistance, and surface appearance. It is a resinous organism. Therefore, it can be widely used in automobile parts, electrical/electronic parts, industrial parts, etc.

46-

Claims (1)

[Claims] (1) (I) 3-95% by weight of aromatic polyester resin, (II) 3-95% by weight of aromatic polycarbonate-based resin, (III) Butadiene-based polymer (a) with methacrylic acid ester (b) aromatic 1 to 20% by weight of a butadiene copolymer graft-copolymerized with one or more vinyl monomers selected from the group consisting of monovinyl compounds (c) and vinyl cyanide compounds (d), and (IV) epoxy A thermoplastic resin composition comprising 50 to 95% by weight of a group-containing olefin copolymer and 95 to 5% by weight of a vinyl (co)polymer obtained from at least one vinyl monomer, the vinyl monomer comprising: field and the following general formula (a
) or (b) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(a) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(b) [In the formula, R_1 is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R_2 and R_7 is a hydrogen atom or a methyl group,
R_6 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R
_3, R_4 and R_8, R_9 each have 1 carbon number
~4 alkyl group, R_5, R_1_0 have 1 to 1 carbon atoms
2 alkyl group, phenyl group, alkyl-substituted phenyl group or cycloalkyl group having 3 to 12 carbon atoms, m is 1 or 2, and n is 0, 1 or 2] ) A grafted precursor in which at least one polymerizable organic peroxide is copolymerized in olefin copolymer particles containing an epoxy group, or a multiphase structure obtained by melt-kneading the grafted precursor. A thermoplastic resin composition containing 1 to 20 parts by weight of a multiphase thermoplastic resin in which either a polymer or a vinyl (co)polymer forms a dispersed phase with a particle size of 0.001 to 10 μm.