JPS62209165A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition outstanding in processability and both impact and heat resistances, by blending polyphenylene ether, polyamide and/or polyester and respective specific functional group-carrying impact- resistant reinforcer and styrene resin. CONSTITUTION:The following four components: (A) 5-60wt% of a polyphenylene ether resin, (B) 93.5-5wt% of a polyamide and/or polyester, (C) 0.5-80wt% of a styrene resin prepared by modification with a functional group selected from carboxyl, acid anhydride, epoxy, hydroxyl and amino groups, with the amount of the functional group added being 5X10<2>-1X10<6>g/ equiv. and (D) 1-50wt% of a rubbery polymer and/or thermoplastic elastomer (pref. prepared by modification, with a specific functional group in a similar manner as in the case of the component C, of an ethylene-alpha-olefin copolymer with the weight ratio of ethylene to alpha-olefin being 95/5-5/95 and Mooney viscosity 5-200 are kneaded in a multi-step system to obtain the objective composition in which the component A is dispersed as particles of an average size <=5mum.

Description

DETAILED DESCRIPTION OF THE INVENTION a. Field of Industrial Application The present invention relates to a thermoplastic resin composition having excellent processability, impact resistance and heat resistance.

b. Conventional technology Polyphenylene ether resin has excellent mechanical properties, electrical properties, and heat resistance, as well as good dimensional stability, so it is attracting attention as a resin suitable for a wide range of applications. However, its major disadvantage is that it has poor moldability and impact resistance.

In order to improve the molding processability of polyphenylene ether resin, it was proposed in Japanese Patent Publication No. 45-99 to incorporate polyamide.
No. 7 was also blended with polyester in 1973.
-21664, polyphenylene ether resin and polyester or polyamide have very poor compatibility, and the resulting resin composition has poor mechanical properties (especially when the polyester content exceeds 20%). The molded articles obtained by injection molding of the resin composition had very low impact resistance. Further, even when attempts were made to add various rubber components to improve the impact resistance of the resin composition, the impact resistance was hardly improved.

Problems to be Solved by the C0 Invention The present inventors aimed to obtain a resin composition that has excellent processability, impact resistance, and heat resistance and can be used in a wide range of applications. By blending polyamide and/or polyester with an impact reinforcing agent having a specific functional group and a styrene resin in a specific ratio, and dispersing polyphenylene ether in a specific particle size in the resin composition, It has been discovered that a thermoplastic resin composition having unprecedented performance can be obtained, and the present invention has been achieved based on this knowledge.

The means for solving the d0 problem, that is, the present invention, is as follows: (a) Polyphenylene ether resin 5 to 60% by weight (c) Styrene resin 0.5 to 8
0% by weight and (dl impact resistant reinforcing agent 1 to 50% by weight), wherein the (c1 and (d) components are carboxyl groups, acid anhydride groups, epoxy groups, hydroxyl groups and amine groups). A thermoplastic resin composition modified with at least one selected functional group, in which component (a) is dispersed, and the average particle diameter of the dispersed particles is 5 μm or less. This is what we provide.

The polyphenylene ether resin as the Ta component used in the present invention is a polymer consisting of repeating structural units represented by the following general formula (1), and specific examples include poly(2,6-dimethylphenylene- 1,4-ether), poly(2,6-ethylphenylene-1,4-ether), poly(2゜6-dipromephenylene-1,4-ether), poly(2-methyl-6 -ethylphenylene-1,4-ether), poly(2-chloro-6-methylphenylene-1,4-ether), poly(2-methyl-6=isopropylphenylene-1,4-ether), poly(2-methylphenylene-1,4-ether), poly(2-chloro-6-methylphenylene-1,4-ether), ,6-Ji n
-propylphenylene-1,4-ether), poly(
2-chloro-6-promphenylene-1,4-ether), poly(2-chloro-6-ethylphenylene-1,
4-ether), poly(2-methylphenylene-1,4
-ether), poly(2-chlorophenylene-1,4
-ether), poly(2-phenylphenylene-1,
4-ether), poly-(2-methyl-6-phenylphenylene-1゜4-ether), poly(2-bromo-
6-phenylphenylene-1,4-ether), poly(
2,4'-methylphenylphenylene-1,4-ether), poly(2,3,6-drimethylphenylene-1,
4-ether), their copolymers, and their styrenic compound graft copolymers.

The blending amount of the polyphenylene ether resin in the thermoplastic resin composition of the present invention is 5 to 60% by weight, preferably 10 to 60% by weight, and more preferably 10 to 50% by weight.

If the amount of the polyphenylene ether resin is less than 5% by weight, no significant effect on improving heat resistance will be observed, and if it exceeds 60% by weight, processability will be poor and the polyphenylene ether will not form dispersed particles.

The polyamide (bl component) used in the present invention is usually composed of a linear diamine represented by the following formula % formula % (wherein, X is an integer between 4 and 12) and a linear diamine represented by the following formula 1 formula % ( In the formula, y is an integer between 2 and 12.) Those produced by condensation with a linear carboxylic acid represented by the following formula, those produced by ring-opening polymerization of lactam, etc. can be used. Preferred examples of polyamide include nylon 6.6, nylon 6.9, and nylon 6.10.
, nylon 6.12, nylon 6, nylon 12, nylon 1). Examples include nylon 4.6.

Also nylon 6/6.6, nylon 6/6.10, nylon 6/12, nylon 6/6.12, nylon 6/6
．． Copolyamides such as 6/6.10 and nylon 6/6.6/12 can also be used.

Furthermore, nylon 6/6. T (T: terephthalic acid component)
, semi-aromatic polyamides obtained from aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid and meta-xylene diamine, or alicyclic diamines, polyamides obtained from meta-xylene diamine and the above-mentioned linear carboxylic acids,
Mention may be made of polyesteramides, polyetheramides and polyesteretheramides. Note that the polyamide may be used alone, or two or more types of polyamides may be used in combination.

The polyester component (b) used in the present invention includes:
Aliphatic polyesters, aromatic polyesters, wholly aromatic polyesters, etc. are used.

Preferred polyesters are those produced by condensation polymerization of a dicarboxylic acid component represented by the following general formula (■) and a diol component.

The dicarboxylic acid and diol components may be used alone or in combination of two or more.

Particularly preferred polyesters are polyethylene phthalate, polybutylene terephthalate and modified products thereof.

Note that polyester may be used alone, or two or more types of polyester may be used in combination.

The above-mentioned polyamides and polyesters as component (b) may be used alone or in combination.

The amount of component (b) used is 93.5 to 5% by weight, preferably 80 to 25% by weight, more preferably 80 to 35% by weight.
Weight%.

If the amount of component (b) exceeds 93.5% by weight, no significant effect on improving heat resistance will be observed, and if it is less than 5% by weight, processability will be poor.

The styrenic resin which is the component (c) of the present invention is a polymer mainly composed of an aromatic vinyl compound, which has a carboxyl group,
Aromatic vinyl compounds used here include a small number of functional groups selected from acid anhydride groups, epoxy groups, hydroxyl groups, and amino groups.
Styrene, α-methylstyrene, methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene,
Examples include motsupromustyrene, dibromustyrene, p-tert-butylstyrene, ethylstyrene, and vinylnaphthalene, and these may be used alone or in combination of two or more. A preferred aromatic vinyl compound is styrene.

A method for modifying the c1 component with a functional group such as a carboxyl group, an acid anhydride group, an epoxy group, or a hydroxyl group is a method of copolymerizing an unsaturated compound having the above functional group, or a chain transfer agent having the above functional group. There are a method of polymerization using a polymerization initiator having the above functional group, a method of polymerization using a polymerization initiator having the above-mentioned functional group, and a method consisting of a combination of these.

The content of the above-mentioned functional group in component (c1) of the present invention, that is, the equivalent, is preferably 5 x 10'' to IX 10 bg equivalent, more preferably l x 103 to 5 x 10'g equivalent, particularly preferably 1 x 10'' to 3 x 10'g equivalent. The equivalent weight of these functional groups can be determined by titration, infrared spectroscopy, or the like.

Examples of carboxyl group-containing unsaturated compounds used here include acrylic acid, methacrylic acid, crotonic acid,
Examples include cinnamic acid, itaconic acid, and maleic acid, with acrylic acid and methacrylic acid being preferred.

These may be used alone or in combination of two or more.

Examples of unsaturated compounds containing an acid anhydride group include maleic anhydride, itaconic anhydride, chloromaleic anhydride, citraconic anhydride, butenyl succinic anhydride, and tetrahydrophthalic anhydride. Particularly preferred unsaturated acid anhydrides include Maleic anhydride. These may be used alone or in combination of two or more.

The epoxy group-containing unsaturated compound is a compound having an epoxy group and an unsaturated group copolymerizable with an olefin and an ethylenically unsaturated compound in the molecule.

For example, the following general formulas (III), (IV) and (V)
These are unsaturated epoxy compounds such as unsaturated glycidyl esters, unsaturated glycidyl ethers, epoxy alkenes, and p-glycidyl styrenes as shown in the following.

There are 7 groups.
” Specifically, glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl esters, butene carboxylic acid esters, allyl glycidyl ether, 2
-Methyl allyl glycidyl ether, styrene-p-glycidyl ether, 3,4-epoxybutene, 3,4-
Epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3-methylpentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide, p-glycidylstyrene Examples include. These can be used alone or in combination of two or more.

The hydroxyl group-containing unsaturated compound is a compound that has at least one unsaturated bond (double bond, triple bond) and also contains a hydroxyl group.

Typical examples include alcohols with double bonds, alcohols with triple bonds, esters of -valent or divalent unsaturated carboxylic acids and unsubstituted dihydric alcohols,
Examples include esters of the unsaturated carboxylic acid with unsubstituted trihydric alcohols, esters with unsubstituted tetrahydric alcohols, and esters with unsubstituted five or more alcohols.

Among the hydroxyl compounds used in the present invention,
Representative examples of suitable ones include 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene.
butene, 3-hydroxy-2-methyl-1-propene,
cis-5-hydroxy-2-pentene, trans-5-
Hydroxy-2-pentene, cis-1,4-dihydroxy-2-butene, trans-1,4-dihydroxy-2
-butene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxyethyl crotonate, 2,3,4°5.6-pentahydroxyhexyl acrylate, 2.
Examples include 3,4.5.6-pentahydroxyhexyl methacrylate, 2,3,4.5-tetrahydroxypentyl acrylate, and 2,3,4.5-tetrahydroxypentyl methacrylate.

These may be used alone or in combination of two or more.

The amino group-containing unsaturated compound is a vinyl monomer having at least one type of amino group or substituted amino group represented by the following general formula, and specific examples include aminoethyl acrylate, propylaminoethyl acrylate, Alkyl ester derivatives of acrylic acid or methacrylic acid, such as dimethylaminoethyl methacrylate, aminopropyl methacrylate, phenylaminoethyl methacrylate and cyclohexylaminoethyl methacrylate;
Vinylamine derivatives such as N-vinyldiethylamine and N-acetylvinylamine, allylamine derivatives such as allylamine, methacrylamine and N-methylallylamine, acrylamide derivatives such as acrylamide and Nt-methylacrylamide, and p-aminostyrene. Aminostyrenes such as are used. Among them, allylamine, aminoethyl methacrylate, aminopropyl methacrylate, aminostyrene, and the like are particularly preferred because they can be obtained economically on an industrial scale.

These amino group- or substituted amino group-containing unsaturated compounds may be used alone or in combination of two or more.

The amount of each of the above-mentioned unsaturated compounds used is 0.1 to 0.1 in component (c).
A range of 30% by weight is preferred.

Preferred examples of carboxyl group-containing chain transfer agents include thioglycolic acid, thiomalic acid, and mercaptopropionic acid.

Examples of amino group-containing chain transfer agents include mercaptomethylamine, β-mercaptoethylamine, T-mercaptoprobylamine, N-(β-mercaptoethyl)-N-
Methylamine, N-(β-mercaptoethyl)-N-ethylamine, N-(β-mercaptoethyl)-N-phenylamine, N-(β-mercaptoethyl)-N-cyclohexylamine, Bis-(4-amino phenyl) disulfide, bis-(2-aminophenyl) disulfide, bis-(3-aminophenyl) disulfide,
p-mercaptoaniline, 0-mercaptoaniline, m
-Mercaptoanili and their hydrochlorides, etc. Preferably β-mercaptoethylamine, T-
These are mercaptopropylamine, β-mercaptoethylamine hydrochloride, γ-mercaptopropylamine hydrochloride, and bis-(4-aminophenyl) disulfide.

As the carboxyl group-containing polymerization initiator, all carboxyl group-containing azo compounds and carboxyl group-containing peroxide compounds can be used.

Preferred carboxyl group-containing azo compounds are represented by the following general formula %, and preferred examples include azobisvaleric acid and azobiscyanopropionic acid.

Suitable examples of carboxyl group-containing peroxides include succinic acid peroxide.

As a polymerization initiator containing an amino group, α,α′-azobis(γ-amino-α,γ-dimethylvaleronitrile)
, α, α′-azobis(γ-methylamino-α, T-dimethylvaleronitrile), α, α′azobis(γ-ethylamino-α, γ-dimethylvaleronitrile), α, α
'-Azobis(γ-propylamino-α, T-dimethylvaleronitrile), α.

α-Azobis (T-dimethylamino-α, γ-dimethylvaleronitrile), α, α′-Azobis (γ-diethylamino-α, T-dimethylvaleronitrile) α, α′-
Azobis (T-dipropylamino-α.

T-dimethylvaleronitrile) and p-aminobenzoyl peroxide.

Preferably α, α′-azobis (γ-amino-α).

T-dimethylvaleronitrile).

The carboxyl group-containing chain transfer agent and the amino group-containing chain transfer agent may be selected from a small number of these chain transfer agents (one kind may be used or they may be used in combination with other known chain transfer agents, From the viewpoint of processability and impact resistance of the thermoplastic resin composition of the present invention, the amount used is 0.01 to 5 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the monomer component.
．． The amount is in the range of 1 to 5 parts by weight, more preferably 0.1 to 3 parts by weight.

When using a carboxyl group-containing polymerization initiator or an amino group-containing polymerization initiator, at least one selected from these polymerization initiators is used, or in combination with other known polymerization initiators. However, from the viewpoint of processability and impact resistance of the thermoplastic resin composition of the present invention, the amount used is 1 monomer.
The range is from 0.01 parts by weight to 5 parts by weight, preferably from 0.1 to 5 parts by weight, and more preferably from 0.1 to 3 parts by weight.

Furthermore, other vinyl monomers copolymerizable with the aromatic vinyl compound can be copolymerized with the (c1 component) of the present invention.

Other copolymerizable vinyl monomers include vinyl cyanide compounds such as acrylonitrile and methacrylonitrile;
Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-
Acrylic acid alkyl esters such as ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate ,
Methacrylic acid alkyl esters such as cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, benzyl methacrylate, maleimide, N-methylmaleimide, N
-ethylmaleimide, N-butylmaleimide, N-laurylmaleimide, N-phenylmaleimide, N-(p-
Maleimide compounds such as (bromophenyl)maleimide can be used, and one type or two or more types of these copolymerizable vinyl monomers can be used.

These copolymerizable vinyl monomers are used as (c) of the present invention.
50% by weight or less, preferably 20% by weight or less in the ingredients,
More preferably, the copolymerization can be carried out so that the content is 10% by weight or less.

Component (c) of the present invention is emulsion polymerization, which is a known polymerization method,
It can be obtained by bulk polymerization, suspension polymerization, solution polymerization, bulk-suspension polymerization, bulk-solution polymerization, etc.

The amount of component fc) used in the thermoplastic resin composition of the present invention is 0.5 to 80% by weight, preferably 0.5 to 80% by weight.
It is 60% by weight, more preferably 0.5 to 40% by weight.

If it is less than 0.5% by weight, the impact resistance and heat resistance will be poor, and if it exceeds 80% by weight, the heat resistance will be poor.

As the impact resistant reinforcing agent which is component (d) of the present invention, rubbery polymers and thermoplastic elastomers are used.
It is modified with at least one functional group selected from L4, an acid anhydride group, an epoxy group, a hydroxyl group, and an amino group.

As a method for deforming with the above-mentioned functional group, at least one selected from the above-mentioned carboxyl group, acid anhydride group, epoxy group, hydroxyl group, unsaturated compound containing an amino group, chain transfer agent, and polymerization initiator is added to the rubbery polymer. It can be obtained by coalescence and/or addition to thermoplastic elastomers.

When adding the unsaturated compound, chain transfer agent, and polymerization initiator to the rubbery polymer and/or thermoplastic elastomer, the amount of these used is preferably 0 to the rubbery polymer and/or thermoplastic elastomer. .01~50
% by weight, more preferably 0.1 to 10% by weight,
Particularly preferably 0.2 to 5% by weight.

If the amount of modification is too large or too small, the impact resistance will be poor.

The rubbery polymers used here include polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, diene rubber such as polyisoprene, ethylene-α-olefin copolymer, ethylene-
There are non-diene rubbers such as α-olefin-polyene copolymers, polyacrylic esters, etc.
Used in one species or in combination of two or more.

Examples of thermoplastic elastomers include styrene-butadiene block copolymers, hydrogenated styrene-butadiene block copolymers, ethylene-propylene elastomers, styrene-grafted ethylene-propylene elastomers, and ethylene ionomer resins. Styrene-butadiene block copolymers include AB type, ABA type, ABA type
Includes tapered type, radial teleblock type, etc.

These may be used alone or in combination of two or more.

Further, the above rubbery polymer and the above thermoplastic elastomer can also be used in combination.

Preferred rubbery polymers and thermoplastic elastomers from the standpoint of impact resistance include styrene-butadiene copolymers, ethylene-α-olefin copolymers, polyacrylic esters,
These include styrene-butadiene block copolymers, hydrogenated styrene-butadiene block copolymers, and more preferably styrene-butadiene copolymers, ethylene-α
These include olefin copolymers and styrene-butadiene block copolymers.

In view of the thermal stability of the resulting composition, ethylene-α-olefin copolymers are particularly preferred.

The weight ratio of ethylene and α-olefin in the ethylene-α-olefin copolymer used here is 95:5 to 5:9.
5, preferably 95:5 to 20:80, more preferably 92:8 to 60:40, particularly preferably 85
: 15-70:30.

Ethylene and α-olefin! 1ffi ratio to 20:
Workability is particularly good when the range is 80 to 30 near 0.

In addition, the iit ratio of ethylene and α-olefin was set to 80:
A range of 20 to 70:25 provides particularly good impact resistance.

Mooney viscosity (M
LI-4, +oo”C) is 5~2o from the viewpoint of impact resistance.
o, preferably 5 to 100, more preferably 5 to 50
It is. Impact resistance is particularly good when the Mooney viscosity is in the range of 10 to 30.

Furthermore, the amount of cyclohexane-insoluble content of the ethylene-α-olefin copolymer affects the processability and impact resistance of the thermoplastic resin composition of the present invention, and is preferably 50% by weight or less, preferably 50% by weight or less.
% by weight or less.

The α-olefin used here is an unsaturated hydrocarbon compound having 3 to 20 carbon atoms, and specific examples include propylene, butene-1, pentene-1, hexene-1
, heptene-1,4-methylbutene-1,4-methylpentene-1, and the like. A particularly preferred book is Propylene.

The dl component of the present invention is a combination of the rubbery polymer and/or the thermoplastic elastomer, an unsaturated compound having the specific functional group, a chain transfer agent, and a polymerization initiator. Mix oxides, e.g. 100-3
0.25-3 at 00°C, preferably 150-250°C
It can be obtained by heat treatment (kneading) for 0 minutes (preferably 1 to 10 minutes). Moreover, a copolymer obtained in advance and the rubbery polymer and/or the thermoplastic elastomer can also be polymerized.

These reactions can be carried out using an extruder, kneader, Banbury mixer, or the like. Alternatively, it can be obtained by dissolving each of the above components in an organic solvent and heating the solution.

As the solvent used at this time, a hydrocarbon having 6 to 12 carbon atoms, a halogenated hydrocarbon having 1 to 12 carbon atoms, tetrahydrofuran, or the like is used.

The heating temperature varies depending on the type of organic peroxide used as a polymerization initiator, but is usually 40 to 300°C.
1 Preferably the temperature is 50 to 200°C, and the heating time is 1 minute to
The time is 10 hours, preferably 5 minutes to 5 hours.

After the reaction is completed, the product solution is poured into a polymer-insoluble solvent such as alcohol and solidified, or solidified by steam stripping and then dried.

Furthermore, one or more types selected from other vinyl monomers copolymerizable with the unsaturated compound having a specific functional group of the present invention can also be used in combination.

Examples of the other copolymerizable vinyl monomers include the aromatic vinyl compound, the vinyl cyanide compound, the acrylic acid alkyl ester, the methacrylic acid alkyl ester, and the maleimide compound.

The peroxide used in the production of the dl component is
All known organic peroxides can be used.

For example, 2,5-dimethyl-2,5-di(tert-
butylperoxy)hexyne-3,2,5-dimethyl-
2,5-di(tert-butylperoxy)hexane,
2.2-bis(tert-butylperoxy)-p-diisopropylbenzenedicumyl peroxide, di-t
er t-butyl peroxide, tert-butyl peroxybenzoate, l, 1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 2,4-dichlorobenzoyl peroxide, benzoyl peroxide, p-chlorobensyyl peroxide, p-chlorobenzoyl peroxide, azobisisobutyronitrile, etc., preferably 2.5-
Dimethyl-2,5-di(tert-butylperoxy)
Hexane, 2,5-dimethyl=2,5-di(tert
-butylperoxy)hexyne-3.

The amount of organic peroxide used here is 0.05-2 parts by weight, preferably 0.1-1 parts by weight, based on 100 parts by weight of the rubbery polymer and/or thermoplastic elastomer.

Furthermore, in obtaining component (d) of the present invention, a known antioxidant may be used in combination, if necessary.

(The amount of functional groups added that modifies the dl component is 5X10t
~1 x 106 g/equivalent is preferred, more preferably 1 x 103 to 5 x 10 Sg equivalent.

The amount of the component (d) used in the thermoplastic resin composition of the present invention is 1 to 50% by weight, preferably 2 to 30% by weight, and more preferably 5 to 25% by weight. 1% by weight
If it is less than 50% by weight, no improvement in impact resistance will be observed, and if it exceeds 50% by weight, processability will be poor.

In the thermoplastic resin composition of the present invention, it is necessary that the polyphenylene ether resin as the component (a) is dispersed in the continuous phase of the component (b), and the dispersed (al component The weight average particle diameter of is 5 μm or less, preferably 3 μm or less, and more preferably 1 μm or less.

The dispersed particle size can be measured by observing a section of the composition with an electron microscope. The weight average particle diameter referred to here was calculated using the following formula.

Although dispersed particles observed under an electron microscope do not necessarily maintain a perfect circular shape, the average value of the longest diameter and the shortest diameter of the particles is taken as the particle diameter. The weight average particle diameter of the dispersed particles is 5
If it exceeds μm, impact resistance and heat resistance will be poor.

In order to achieve the purpose of dispersing component (a) as small particles, component (c) of the present invention plays a major role.

That is, it is considered that the dispersibility is significantly improved due to the interaction between the specific functional group modifying the styrene resin of the component (c) and the component (b).

Moreover, it also changes depending on the kneading method and the method of adding various polymer components when obtaining the thermoplastic resin composition of the present invention.

Preferred methods for adding various polymers and kneading methods are as follows.

(1) After kneading (al component, (c1 component, and (dl component)), (bl component is added.

■ After adding component (a) and component (c1), component (b) and component (dl) are added.

■ After adding the (a) component and the (dl component), the fb) component and (c) component are added.

A multistage kneading method of two or more stages is preferred.

Further, a method of kneading in which the mixing conditions are made stronger in the second and subsequent stages than in the first stage gives preferable results.

Furthermore, in the thermoplastic resin composition of the present invention, (
The dl component exists in various forms, including (a) incorporated into the component, (b) dispersed in the component, and a mixture of both forms. , all are preferable.

The thermoplastic resin composition of the present invention is heated to 200°C to 300°C using various extruders, Banbury mixers, kneaders, rolls, etc.
It can be obtained by kneading each component at a temperature within the range of °C.

A preferred kneading method is a method using an extruder, and a preferred extruder is a two-wheel co-rotating extruder.

When the composition of the present invention is obtained using a twin-screw co-rotating extruder, a screw having a kneading function and a feeding function is preferably used. The kneading function is preferably dispersed in two or more places, and it is better to make the kneading function of the second stage and subsequent stages sequentially stronger than that of the first stage. The kneading function can be strengthened by using a combination of screw parts that have the ability to transport, not transport, reverse transport, or compress the molten resin. Two-wheel co-rotating extruders that meet these conditions include TEM manufactured by Toshiba Machine, P CM manufactured by Ikegai Iron Works, and WERIJER&P.
Examples include an extruder manufactured by FLEIDERER.

When using the thermoplastic resin composition of the present invention, glass fibers, carbon fibers, metal fibers, glass beads, asbestos,
Fillers such as wallasnite, calcium carbonate, talc, and barium sulfate can be used alone or in combination. Among these fillers, glass fibers and carbon fibers preferably have a fiber diameter of 6 to 60 μm and a fiber length of 30 μm or more.

It is preferable that these fillers are contained in an amount of 5 to 15 parts by weight based on 100 parts by weight of the thermoplastic resin composition.

Additionally, known additives such as flame retardants, antioxidants, plasticizers, colorants, and lubricants may be added.

Preferred flame retardants and antioxidants are phosphorus compounds.

Furthermore, other polymers may be used depending on the required performance, such as polyethylene, polypropylene, BR, NBR, and SBR.

5-a-S block copolymer, hydrogenated 5-B-S, polystyrene, AS resin, IIIPs, ABS resin, AB
S resin, polysulfone, polyether sulfone, N-phenylmaleimide copolymerized styrene resin, MBS, methyl methacrylate-styrene copolymer, 5-I-S block copolymer polyimide, pps, polyetheretherketone, fluoride A vinylidene polymer or the like can be appropriately blended.

The thermoplastic resin composition of the present invention can be used as various molded products by injection molding, sheet extrusion, vacuum molding, irregular molding, foam molding, and the like.

The various molded products obtained by the above molding method take advantage of their excellent properties to be used in automobile exteriors, interior parts, electrical equipment, etc.
It can be used for various electronic-related parts, housings, etc.

e. Examples The present invention will be explained in more detail by the following Examples and Production Examples, but these are merely illustrative and do not limit the content of the present invention.

Note that in each side below, parts and % indicate parts by weight and % by weight, respectively.

Production Example-1 Polyphenylene ether used in Examples and Comparative Examples was obtained by the following method.

1) ffl theory - (4 Ribini U2 "Leave Su! Hill" Ji≦≧
=Taseritan Seiji 2.6-xylenol, cupric bromide as a catalyst, di-n
A polymerization reaction was carried out using -butylamine in a toluene solution at 30° C. while blowing oxygen. After the polymerization reaction is complete, add an aqueous solution of trisodium ethylenediaminetetrabutyrate,
The catalyst was removed.

The polymer solution phase was removed from the resulting product mixture by centrifugation. While stirring the polymer solution vigorously, methanol was gradually added to form a slurry. After separating the solid content, it was thoroughly washed with methanol and dried to obtain Polymer A-1.

Polymer A measured at 30°C using chloroform solvent
-1 [η] was 0.40.

2) ■ of polymerization A-2 (polyphenylene ether) In the production of polymer A-1, 2,6-xylenol was converted into 2,6-xylenol/2,3 as a phenol compound.
．． 6-1-limethylphenol = 90/10 (mole ratio)
Polymerization was carried out in place of the mixture of 1 and 2 to obtain polymer A-2.

[η] of Polymer A-2, which was measured in the same manner as Polymer A-1, was 0.40.

Component (c) of the present invention used in Hoshisan Charcoal 2 Main Examples and Comparative Examples was obtained by the following method.

After replacing the inside of a stainless steel reaction vessel with a stirrer with nitrogen, 48.5 parts of styrene, 1.5 parts of glycidyl methacrylate, 0.425 parts of tert-dodecyl mercaptan, and 1.0 parts of sodium dodecylbenzenesulfonate were added in a nitrogen stream. 140 parts of ion-exchanged water were added. While circulating 70°C hot water through the jacket, add 0.1 part of ethylenediaminetetraacetic acid sodium salt, 0.003 part of ferrous sulfate,
Formaldehyde sodium sulfoxylate dihydrate 0
．． After adding an aqueous solution consisting of 2 parts of ion-exchanged water and 15 parts of ion-exchanged water and 0.3 parts of cumene hydroperoxide, and carrying out a polymerization reaction for 2 hours, 48.5 parts of styrene, 1.5 parts of glycidyl methacrylate, and tert-dodecyl 0.425 parts of mercaptan, 1.0 parts of sodium dodecylbenzenesulfonate, 90 parts of ion-exchanged water, and 0.3 parts of cumene hydroperoxide were added, and the polymerization reaction was further carried out for 3 hours. A calcium chloride aqueous solution was added to the obtained polymer latex, and after washing, dehydration, and drying, polymer C-
I got 1.

2) -Heavy cooling (≧2-2-2) Under the production conditions of Polymer C-1, each polymerization was carried out by replacing the amount of glycidyl methacrylate and the glycidyl methacrylate with other compounds of the present invention.

Table 1 shows the obtained polymer.

Table 1 (Tairaku ■232 manufactured by Arcopolymer) 1) ■1 The dl component of the present invention used in Examples and Comparative Examples was obtained by the following method.

Ethylene-propylene rubber (JSRE manufactured by Japan Synthetic Rubber)
P-02P, Mooney viscosity ML, 1. . . 'C24
), 1 part of maleic anhydride and 0.3 parts of organic peroxide (Kayahexasa AD manufactured by Kayaku Nuri) were premixed in advance using a 55 Tsuru φ extruder (single full-flight type screw). A polymerization reaction was carried out by melt-kneading at 200° C. and a screw rotation speed of 3 Orpm (residence time of about 4 minutes).

Acetone extraction from the obtained reaction product (boiling point x 2 hours)
The purified polymer was molded into a film, and the graft m of maleic anhydride was determined by infrared spectroscopic analysis.

The graft ratio was 0.5 parts by weight based on 100 parts by weight of ethylene-propylene.

2) - Under the production conditions of Watasum Aoi ni" 2 Zuto" l sadistic polymer D-1, polymers D-2 to D-
4 is a result of varying the amount of maleic anhydride. D-5,
D-6 is obtained by changing the ethylene-propylene copolymer species. Polymers D-7 and D-8 are obtained by replacing the ethylene-propylene copolymer with another rubbery polymer or thermoplastic elastomer. Polymers D-9 to D-13 are those in which maleic anhydride was replaced with another compound. Polymer D-14 is obtained by replacing maleic anhydride with a styrene-maleic anhydride copolymer.

Table 2 shows the results of measuring the grafting rate of maleic anhydride for each of the obtained polymers D-2 to D-12.

Table-2 Dailark■332 (Arcobo Rimer Offshore Example, Comparative Example) The various polymers mentioned above were mixed in the composition ratios shown in Table 3.

In addition, the first stage component and second stage component shown in Table 3 refer to the polymer component (1) added in the first stage in the extrusion kneading process, and then the (2) component added in the second stage. Indicates that it was added midway through.

As an extruder, a PCM-45 (twin-screw extruder) manufactured by Ikegai Iron Works was used. A kneading area was provided, and an area with a higher kneading degree was further provided after the second-stage component addition supply port to pelletize the resin composition. The barrel temperature was set at 320℃ at the highest point, and the screw rotation speed was 20rpI1) to 300r.
p1).

After thoroughly drying the obtained pellet-shaped thermoplastic resin composition in a vacuum dryer, test pieces were prepared using an injection molding machine, and the impact resistance and heat resistance were checked, and the dried pellets were used to process them. The gender was evaluated.

■Negative Example 1) Comparative Example 3 uses component (d) that has not been modified with the specific functional group of the present invention, and Comparative Example 4 is outside the scope of the present invention. These use component (d) modified with the monomer, but these have significantly inferior impact resistance.

Comparative Examples 5 and 6 used component (c) that was not modified with the specific functional group of the present invention, and these were (al
The dispersed particle size of the component is outside the range of the present invention, and impact resistance,
Poor heat resistance.

Comparative Example-9 has a polymer composition within the scope of the present invention, but
Since the degree of kneading is low, the dispersed particle size of the Al component is outside the range of the present invention, and the heat resistance and impact resistance are poor.

10 Effects of the invention The composition of the invention contains fcl modified with a specific functional group,
As shown in the examples in which component (d) is used and the dispersed particle size of component (a) is within a specific range, the physical properties of impact resistance, heat resistance, and moldability are highly balanced. It is a resin.

Therefore, since the composition of the present invention has highly balanced physical properties, it can be used for molding automobile exteriors, interior parts, various electric/electronic parts, housings, etc. that require high quality. It provides products and has extremely high industrial value.

Claims (4)

[Claims] (1) (a) Polyphenylene ether resin 5-60% by weight (b) Polyamide and/or polyester 93.5%
-5% by weight (c) 0.5-80% by weight of a styrene resin and (d) 1-50% by weight of an impact reinforcing agent, wherein the (c) and (d) components are carboxyl modified with at least one functional group selected from a group, an acid anhydride group, an epoxy group, a hydroxyl group, and an amino group, and in which component (a) is dispersed in the composition, and the average particle diameter of the dispersed particles. 1. A thermoplastic resin composition characterized in that the particle diameter is 5 μm or less. (2) The impact reinforcing agent (d) is a rubbery polymer modified with at least one functional group selected from carboxyl group, acid anhydride group, epoxy group, hydroxyl group, and amino group and/or heat The thermoplastic resin composition according to claim (1), which is a plastic elastomer. (3) Claim (1) characterized in that the amount of the functional group that modifies components (c) and (d) added is 5 x 10^2 to 1 x 10^6 g/equivalent; or The thermoplastic resin composition according to any one of item (2). (4) The impact resistance reinforcing agent (d) is an ethylene-α-olefin copolymer having a weight ratio of ethylene and α-olefin of 95:5 to 5:95 and a Mooney viscosity of 5 to 200. Claim No. (1) characterized in that
The thermoplastic resin composition described in .