JPH0715055B2 - Resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention is a resin composition excellent in mechanical properties such as appearance, heat resistance and impact resistance of a molded product, and having good moldability, dimensional accuracy and chemical resistance. Regarding

<Prior Art> Aromatic polyesters typified by polybutylene terephthalate and polyethylene terephthalate have excellent mechanical properties, electrical properties, solvent resistance, etc., and are therefore used for automobile parts, electric / electronic parts and other mechanical parts. Is widely used for. However, since aromatic polyester has problems such as a low heat deformation temperature under load, a large molding shrinkage ratio, and a large linear expansion coefficient, it cannot be used as it is in applications where load is applied at high temperatures or applications where dimensional accuracy is required. Not applicable. For this reason, a method of filling a reinforcing agent such as glass fiber has been proposed, but it has drawbacks such as poor appearance of the molded product or warping. However, there is a problem that it cannot be applied to severe applications.

On the other hand, polyphenylene ether is a resin having excellent heat resistance and dimensional accuracy, but it has a drawback that it has difficulty in melt processing because it has a high curing point, or it decomposes during melt processing. It was For this reason, a styrene-based resin is usually blended and used, but in this case, there is a problem that the heat resistance decreases and the solvent resistance of the polyphenylene ether, which is originally not so good, further decreases.

Therefore, a method of further adding polyester to polyphenylene ether (JP-A-49-50050),
A method of blending polybutylene terephthalate with polyphenylene ether having a polymerization degree of 10 or more (JP-A-49-
No. 75662), a method of blending polyphenylene ether with polyethylene terephthalate (JP-A-5959).
No. 159847) has been proposed.

<Problems to be Solved by the Invention> Although the moldability and solvent resistance of the polyphenylene ether and the dimensional accuracy and the heat distortion temperature under load of the aromatic polyester are improved by the above method, There is a problem that the dispersion is large, or the resin is not well dispersed only by blending the polyphenylene ether and the aromatic polyester, and a resin having good moldability and mechanical properties such as impact resistance cannot be obtained.

<Means for Solving Problems> Therefore, as a result of intensive investigations by the present inventors in order to solve the above problems, as a result, a polyphenylene ether modified product obtained by reacting a specific compound and an aromatic polyester were identified. It has been found that a resin composition having excellent appearance, heat resistance and mechanical properties of a molded article, and further having good moldability, dimensional accuracy and chemical resistance can be obtained by containing an epoxy compound, and thus reached the present invention.

That is, the present invention provides (A) general formula (In the formula, R _{1 to} R ₄ are each hydrogen, halogen, a hydrocarbon group, a substituted hydrocarbon group, a cyano group, an alkoxy group, a phenoxy group or a nitro group.) A polyphenylene ether having a repeating unit. With respect to 100 parts by weight, (a) a carbon-carbon double bond or a carbon-carbon triple bond in the molecule and (b) a carboxylic acid group, an acid anhydride group,
Polyphenylene ether modified product 5 to 95 obtained by reacting 0.1 to 20 parts by weight of a compound having at least one group selected from acid amide group, imide group, carboxylic acid ester group, epoxy group, amino group and hydroxyl group at the same time. (C) General formula (II) with respect to 100 parts by weight of a resin composition consisting of 5% by weight and (B) 5 to 95% by weight of aromatic polyester. (However, R ₅ and R ₆ are substituted or unsubstituted alkylene groups and alkylidene groups, R _{7 to} R ₉ are hydrogen or methyl groups, and R _{10 to} R ₁₄ are hydrogen, halogen, substituted and unsubstituted hydrocarbons. Group, a cyano group, an alkoxy group, a phenoxy group or a nitro group respectively, and m is an integer of 0 to 20), and a resin composition containing 0.05 to 30 parts by weight of the epoxy compound. Is.

The polyphenylene ether used in the preparation of the modified polyphenylene ether (A) used in the present invention is represented by the general formula (I), and a homopolymer or a copolymer having two or more kinds of repeating units can be used. Is. Specific examples of R _{1 to} R _{4 in} the general formula (I) include hydrogen, chlorine, bromine, methyl, ethyl, propyl, isopropyl,
Allyl, butyl, phenyl, benzyl, methylbenzyl, chloromethyl, cyanoethyl, cyano, methoxy,
Groups such as ethoxy, phenoxy and nitro are preferred.

In addition, examples of specific polymers include poly-1,4-phenylene ether, poly-2,6-dimethyl-1,4-phenylene ether, poly-2,6-diethyl-1,4-phenylene ether, Poly-2,6-dipropyl-1,4-phenylene ether, poly-2-methyl-6-allyl-1,4-phenylene ether, poly-2,6-dimethoxy-1,4-phenylene ether, poly-2 , 6-Dichloromethyl-1,4-phenylene ether, poly-2,5-dimethyl-phenylene ether, poly-2,3,5,6-tetramethyl-1,4-phenylene ether, poly-2,6-dibromomethyl -1,4-phenylene ether, poly-2,6-dichloro-1,4-phenylene ether, poly-2,6-dibromo-1,4-phenylene ether, poly-2,3,5,6-tetrafluoro- 1,4-phenylene ether, poly-2,6-diphenyl-1,4-phenylene Etc. Le and poly-2,6-ditolyl-1,4-phenylene ether. Among these poly-2,6-dimethyl-1,4
-Phenylene ether is most preferred.

The phenylene ether used in the present invention preferably has an intrinsic viscosity measured in chloroform at 25 ° C. of 0.10 to 1.
It is desirable that it is in the range of 50 dl / g, more preferably 0.15 to 1.00 dl / g, and most preferably 0.20 to 0.75 dl / g. When the intrinsic viscosity of polyphenylene ether is less than 0.10 dl / g, the mechanical properties of the resin composition become poor, while when it exceeds 1.50 dl / g, the mechanical properties also deteriorate due to poor dispersion, The object of the present invention cannot be achieved.

The polyphenylene ether in the present invention can be produced by various methods. There is a method in which a phenol represented by is oxidized by introducing a gas containing oxygen in the presence of a catalyst containing a metal species such as Fe, Mn, Co, and Cu, and polymerized.

Further, (a) a carbon-carbon double bond or a carbon-carbon triple bond (b) a carboxylic acid group, an acid anhydride group, an acid amide group, an imide group, a carboxylic acid in the molecule used for the preparation of the component (A). Preferred specific examples of the compound having one or more groups selected from ester group, epoxy group, amino group and hydroxyl group at the same time include maleic anhydride, hymic acid anhydride, itaconic acid anhydride, glutaconic acid anhydride, citraconic acid anhydride,
Aconitic anhydride, 5-norbornene 2-methyl-2-
Carboxylic acid, phthalic acid, fumaric acid, maleimide, maleic hydrazide, reaction product of maleic anhydride and diamine, for example (Wherein R represents an aliphatic or aromatic group), etc., methylnadic acid anhydride, dichloromaleic anhydride, maleic acid amide, soybean oil, tung oil, castor oil, linseed oil, Natural oils and fats such as hemp oil, cottonseed oil, sesame oil, rapeseed oil, peanut oil, camellia oil, olive oil, coconut oil and sardine oil, epoxidized natural oils and fats such as epoxidized soybean oil, acrylic acid, butenoic acid, crotonic acid, vinyl Acetic acid, methacryl stage, pentenoic acid, angelic acid, tibric acid, 2-pentenoic acid, 3-pentenoic acid, α-ethylacrylic acid, β-methylcrotonic acid, 4-pentenoic acid, 2-hexenoic acid, 2-methyl- 2-pentenoic acid, 3
-Methyl-2-pentenoic acid, α-ethyl crotonic acid, 2,
2-dimethyl-3-butenoic acid, 2-heptenoic acid, 2-octenoic acid, 4-decenoic acid, 9-undecenoic acid, 10-undecenoic acid, 4-dodecenoic acid, 5-dodecenoic acid, 4-tetradecenoic acid, 9 -Tetradecenoic acid, 9-hexadecenoic acid, 2-octadecenoic acid, 9-octadecenoic acid, eicosenoic acid, docosenoic acid, erucic acid, tetracosenoic acid, mycolic acid, 2,4-pentadienoic acid, 2,4-hexadienoic acid, diallylacetic acid , Geranium acid, 2,4-decadienoic acid, 2,4-dodecadienoic acid, 9,12-hexadecadienoic acid, 9,12-octadecadienoic acid, hexadecatrienoic acid, linoleic acid, linolenic acid, octadecatriene acid,
Eicosadienoic acid, eicosatrienoic acid, eicosatetraenoic acid, ricinoleic acid, eleostearic acid, oleic acid, eicosapentaenoic acid, erucic acid, docosadienoic acid, docosatrienoic acid, docosatetraenoic acid, docosapentaenoic acid, tetracosenoic acid Unsaturated carboxylic acids such as hexacocenoic acid, hexacodienoic acid, octacocenoic acid, traacontenoic acid and tetrahydrophthalic acid, or esters of these unsaturated carboxylic acids, acid amides, anhydrides, glycidyl esters or allyl alcohol, crotyl alcohol, methyl vinyl Carbinol, allyl carbinol, methyl propenyl carbinol, 4-penten-1-ol, 10-undecen-1-ol, propargyl alcohol, 1,4-pentadien-3-ol, 1,4-hexadiene 3-ol, 3,5-hexadiene-2-ol, 2,4-hexadiene-1-ol, formula _{CnH 2 n -5 OH, CnH 2} n -7 OH, CnH 2 n -9 OH ( where, n Is a positive integer), 3-butene-1,2-
Unsaturated alcohols such as diols, 2,5-dimethyl-3-hexene-2,5-diol, 1,5-hexadiene-3,4-diol, 2,6-octadiene-4,5-diol, or such An unsaturated amine in which the OH group of the unsaturated alcohol is replaced with a -NH ₂ group, Unsaturated glycidyl ether substituted with or low polymerization of butadiene, isoprene, etc.
About 0 to 10,000) or a high molecular weight product (for example, an average molecular weight of 10,000 or more) to which maleic anhydride or phenol is added, or an amino group, a carboxylic acid group, a hydroxyl group, an epoxy group or the like introduced. Among them, maleic anhydride, methylnadic acid anhydride, tetrahydrophthalic anhydride, glycidyl methacrylate, diglycidyl tetrahydrophthalate, and maleimide can be preferably used.

In the definition of the compound having a specific structure in the present invention,
It goes without saying that a compound containing two or more functional groups of group (a) and two or more (same or different) of functional groups of group (b) is also included. It can also be used.

The amount of the specific compound used in the present invention is, based on 100 parts by weight of polyphenylene ether, 0.1 to 20 parts by weight, preferably
It is in the range of 0.3 to 15 parts by weight. If the amount is less than 0.1 part by weight, the effect of the present invention tends to be small, which is not preferable. Further, even if it exceeds 20 parts by weight, there is almost no difference in effect, which is not economical.

The following method can be adopted for the preparation of the component (A).

(A) A method of adding a compound having a specific structure to a solution containing polyphenylene ether and stirring the solution at a temperature of 60 ° C to 150 ° C for several tens of minutes to several hours.

(B) A method of melting each component in a range of 220 ° C. to 370 ° C. for 20 seconds to 30 minutes, preferably 40 seconds to 5 minutes in a system substantially containing no solvent.

The method (a) is preferably used when there is an existing reaction apparatus or purification apparatus, but the method (b) can be modified by light equipment such as a general-purpose single-screw or twin-screw extruder. It is possible, and there is an effective aspect such that it can be changed in a short time without a solvent removal step and a polymer purification step.

The component (A) may be prepared in the coexistence of a radical generator, and examples of the radical generator include known organic peroxides and diazo compounds, and preferable specific examples thereof include benzoyl peroxide and dicarboxylic acid. Examples thereof include mill peroxide, di-tert-butyl peroxide, tert-butyl cumyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide and azobisisobutyronitrile.

It is economical to use the radical generator in an amount of 30 parts by weight or less, preferably 20 parts by weight or less, based on 100 parts by weight of the specific compound.

In particular, when a compound having a carboxylic acid group or an acid anhydride group is used, the effect of the present invention is further exhibited by using a radical generator.

The modified polyphenylene ether used in the present invention may be blended and / or grafted with another polymer in an amount of 50% by weight or less, preferably 30% by weight or less. Such polymers include polycarbonate, polysulfone,
Examples thereof include polyamides, polyolefins, vinyl polymers, rubbery polymers, and the like, which may be used alone or in combination of two or more. Of these, vinyl polymers and rubber polymers are particularly preferable.

The (B) aromatic polyester used in the present invention is a polyester having an aromatic ring in the polymer chain unit and comprises 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 containing the main component.

The aromatic dicarboxylic acid referred to here is terephthalic acid,
Isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,
4'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 2,2'-bis (p-carboxyphenoxy) ethane or its ester-forming derivative, etc. may be mentioned.

If the acid component is 30 mol% or less, adipic acid, sebacic acid, azelaic acid, aliphatic dicarboxylic acids such as dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, fats such as 1,4-cyclohexanedicarboxylic acid It may be substituted with dicarboxylic acids other than aromatic dicarboxylic acids such as cyclic dicarboxylic acids and their ester forming derivatives.

The diol component is an aliphatic diol having 2 to 10 carbon atoms, that is, ethylene glycol, propylene glycol, 1,4-butanediol, 3-methyl-1,3-propanediol, neopentyl glycol, 1,5-pentanediol. , 1,6-hexanediol, decamethylenediglycol, cyclohexanediol, cyclohexanedimethanol, etc., and a small amount has a molecular weight of 400 to 6,0.
A long-chain glycol of 00, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol or the like may be copolymerized.

Examples of preferred aromatic polyesters used in the present invention include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexylene dimethylene terephthalate, polyethylene-2,6-naphthalate and the like. Most preferred are polybutylene terephthalate and polyethylene terephthalate, which have mechanical strength of.

The aromatic polyester used in the present invention has a reduced viscosity of 0.5 to 2.5 measured in orthochlorophenol at 25 ° C.
dl / g, preferably 0.8-2.0 dl / g, more preferably 1.0-
It is desirable to be in the range of 1.7 dl / g. When the reduced viscosity of the aromatic polyester is less than 0.5 dl / g, the mechanical properties are low because it does not mix uniformly with the polyphenylene ether, while when it exceeds 2.5 dl / g, the moldability becomes poor and neither is preferable. .

Mixing ratio of polyphenylene ether modified product (A) and aromatic polyester (B) in the composition of the present invention (A) /
(B) has a polymerization ratio of 95/5 to 5/95, preferably 85/15 to 15/8
5, more preferably 70/30 to 30/70. When the addition amount of the modified polyphenylene ether is less than 5% by weight, only a resin having a low heat distortion temperature can be obtained. On the other hand, when it exceeds 95% by weight, the solvent resistance and the moldability are poor, which is not preferable. .

Next, the epoxy compound which is the component (C) of the present invention is a compound represented by the above general formula (II). General formula (II)
R ₅ and R ₆ are preferably those having 1 to 36 carbon atoms, and specific examples thereof include methylene, ethylene, propylene, isopropylene, butylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, and Examples thereof include groups such as decamethylene, dodecamethylene, hexadecamethylene and octadecamethylene.
R _{7 to} R ₉ are each hydrogen or a methyl group. Specific examples of R _{10 to} R ₁₄ include hydrogen, chlorine, bromine, methyl, ethyl, propyl, isopropyl, allyl, butylphenyl, benzyl, methylbenzyl, chloromethyl, cyanoethyl,
Examples include groups such as cyano, methoxy, ethoxy, phenoxy and nitro.

Also, in the formula When two or more substituted and unsubstituted phenylethylene units represented by are present, the arrangement of the substituted and unsubstituted phenylethylene units is such that the carbon at the α-position (that is, the carbon to which the phenyl group is bonded) is adjacent, β Position carbons may be adjacent to each other, α-position and β-position carbons may be adjacent to each other, and these may be mixed. In addition to the divalent epoxy compound of the present invention, an epoxy compound of a monocarboxylic acid, which is a by-product during production, may be mixed in an amount of 50% or less.

Then, as a specific example of the epoxy compound represented by the general formula (II), And so on.

The addition amount of the epoxy compound as the component (C) in the present invention is 100 parts by weight of a polyphenylene ether composition comprising a modified polyphenylene ether and an aromatic polyester.
The amount is 0.05 to 30 parts by weight, preferably 0.2 to 20 parts by weight, more preferably 1 to 10 parts by weight. If the amount added is less than 0.05 parts by weight, the impact resistance will not be sufficiently improved, and if it exceeds 30 parts by weight, the heat distortion temperature will decrease and gelation will occur during melt processing.

In the present invention, it is also preferable to use various rubber components in combination from the viewpoint of improving impact resistance. Examples of such rubber components include the following (i) to (iii).

(I) Epoxy group-containing copolymer composed of α-olefin and epoxy group-containing unsaturated monomer (ii) 0.01 to ethylene-unmodified ethylene-based copolymer composed of ethylene and α-olefin having 3 or more carbon atoms To 10% by weight of unsaturated carboxylic acid or its derivative obtained by graft reaction (iii) Hydrogenated or unhydrogenated conjugated diene and aromatic vinyl block copolymer or its block copolymer 0.01 to polymer
Modified Block Copolymer Obtained by Grafting 10% by Weight of Unsaturated Carboxylic Acid or Its Derivative The epoxy group-containing copolymer of (i) above is prepared by using α-olefin and an epoxy group-containing unsaturated monomer. It can be produced by a known method such as a high pressure radical polymerization method, a solution polymerization method or an emulsion polymerization method.

Examples of the α-olefin include ethylene, propylene and butene-1, and ethylene can be preferably used.

Further, examples of the epoxy group-containing unsaturated monomer include glycidyl ethers such as allyl glycidyl ether and 2-methylallyl glycidyl ether, and glycidyl esters of the following general formula.

(In the formula, R ₁₅ is a hydrogen atom, a lower alcohol group or a lower alcohol group substituted with a glycidyl ester group.) Specific examples of the glycidyl ester include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylic acid, and glycidyl itaconate. And so on. Preferred epoxy group-containing unsaturated monomers include glycidyl methacrylate and glycidyl acrylate.

The copolymerization amount of the epoxy group-containing unsaturated monomer in the epoxy group-containing polymer is appropriately in the range of 0.1 to 30% by weight, preferably 1 to 20% by weight.

Further, if it is 40% by weight or less, unsaturated monomers copolymerizable with the above copolymers, that is, vinyl ethers, vinyl acetates such as vinyl acetate and vinyl propionate, acrylic acids such as methyl, ethyl, propyl and butyl. And methacrylic acid esters, acrylonitrile,
One or more types of styrene, carbon monoxide, etc. may be copolymerized.

Preferred examples of the epoxy group-containing copolymer in the present invention include ethylene / glycidyl methacrylate copolymer,
Ethylene / vinyl acetate / glycidyl methacrylate copolymer, ethylene / methyl methacrylate / glycidyl methacrylate copolymer, ethylene / glycidyl acrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer, ethylene / glycidyl ether Examples thereof include copolymers, and among them, ethylene / glycidyl methacrylate copolymer is most preferable.

In the present invention, together with the epoxy group-containing copolymer, an ethylene-based copolymer comprising ethylene and an α-olefin having 3 or more carbon atoms and / or a diene-based copolymer comprising ethylene, an α-olefin having 3 or more carbon atoms and a non-conjugated diene. If a copolymer is used in combination, impact resistance can be further improved. Specific examples of these copolymers include ethylene / propylene copolymer, ethylene / butene-1 copolymer, ethylene / pentene-1 copolymer, ethylene / propylene / butene-1 copolymer, ethylene / propylene / 5-ethylidene-2-norbornene copolymer, ethylene / propylene / 1,4-hexadiene copolymer, ethylene / propylene / dicyclopentadiene copolymer, etc., among which ethylene / propylene copolymer and ethylene / butene- One copolymer is preferred.

When a compound that accelerates the reaction between the epoxy compound and the carboxylic acid is further added to the composition of the present invention, the effect that the impact resistance can be further improved is obtained. These compounds include triphenylamine, 2,4,6-
Tertiary amines such as tris (dimethylaminomethyl) phenol, phosphites such as triphenylphosphite, triisodecylphosphite, phosphonium compounds such as triphenylallylphosphonium bromide,
Examples include tertiary phosphines such as triphenylphosphine, carboxylic acid metal salts such as lithium stearate, sulfonic acid metal salts such as sodium 3,5-dicarbomethoxybenzenesulfonate, and sulfate ester salts such as sodium lauryl sulfate. Preferably, 0.001 to 5% by weight is added to the resin composition.

The modified ethylene copolymer (ii) is 0.01 to 10% by weight of an unsaturated carboxylic acid or a derivative thereof with respect to an unmodified ethylene copolymer composed of ethylene and α-olefin having 3 or more carbon atoms. Can be obtained by a graft reaction.

Α- with 3 or more carbon atoms in the unmodified ethylene-based copolymer
Olefin is preferably propylene, butene-1,
Pentene-1,3-methylpentene-1, octacene-1
And the like, and propylene and butene-1 are more preferable, and these can be used in combination of two or more kinds. Further, in the unmodified ethylene-based copolymer, a non-conjugated diene may be further copolymerized.

As these non-conjugated dienes, 5-methylidene-2-norbornene, 5-ethylidene-2-norbornene, dicyclopentadiene, 4-hexadiene and the like can be preferably used.

When no non-conjugated diene is contained, the copolymerization ratio of ethylene and α-olefin having 3 or more carbon atoms is 40/60 to 99/1 (molar ratio), preferably 70/30/95/5 (molar ratio). .

The ethylene-based copolymer containing a non-conjugated diene has a copolymerization amount of α-olefin having 3 or more carbon atoms of 5 to 80 mol%, preferably 20 to 60 mol%, and a copolymerization amount of the non-conjugated diene of 0.1 to 0.1 mol%. -20 mol%, preferably 0.5-10 mol%.

It is important that the unmodified ethylene copolymer has a crystallinity of preferably 60% or less, more preferably 35% or less. If the crystallinity is higher than 60%, the effect of improving the impact resistance of the aromatic polyester tends to be small. Here, the crystallinity is a value measured by the X-ray method according to the description in Journal of Polymer Science, Vol. 18 (1955), pages 17 to 26.

Specific examples of the unmodified ethylene-based copolymer include ethylene / propylene copolymer, ethylene / butene-1 copolymer, ethylene / propylene / dicyclopentadiene copolymer, ethylene / propylene / 5-ethylidene-2- Norbornene copolymers and the like are preferred, and among them, ethylene / propylene copolymers and ethylene / butene-1 copolymers containing no non-conjugated diene have good heat resistance and can be more preferably used.

The unsaturated carboxylic acid that is graft-reacted with the unmodified ethylene-based copolymer to obtain a modified ethylene-based copolymer is preferably acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid, or itacone. acid,
Examples include citraconic acid and butenedicarboxylic acid. Also,
Examples of their derivatives include alkyl esters, glycidyl esters, acid anhydrides or imides, and of these, glycidyl esters, acid anhydrides and imides are preferable.

Preferred specific examples of unsaturated carboxylic acids or their derivatives include maleic acid, fumaric acid, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylic acid, diglycidyl itaconate, diglycidyl citracone, butenedicarboxylic acid diglycidyl, tetrahydrophthalic acid diglycyl, Maleic anhydride, itaconic anhydride,
Examples thereof include citraconic acid anhydride, maleic acid imide, itaconic acid imide, and citraconic acid imide. In particular, glycidyl methacrylate, maleic anhydride, itaconic anhydride, and maleic acid imide are preferably used. Two or more kinds of these unsaturated monomers may be used in combination.

The graft reaction amount of the unsaturated monomer must be 0.01 to 10% by weight, preferably 0.05 to 5% by weight. If the graft reaction amount of the unsaturated monomer is less than 0.01% by weight, the impact resistance is not sufficiently improved, and if it exceeds 10% by weight, the heat resistance of the aromatic polyester is impaired. Is also not preferable. The graft reaction here means that the unsaturated carboxylic acid or its derivative chemically bonds to the unmodified ethylene-based copolymer.

The modified ethylene-based copolymer is easily produced by a conventional method, for example, by adding an unsaturated carboxylic acid or a derivative thereof to an unmodified ethylene-based copolymer and melt-kneading at 150 to 300 ° C. be able to. As a device for melt mixing, a screw extruder, a Banbury mixer or the like can be used. Further, when the organic peroxide is used in an amount of 0.001 to 0.0% by weight with respect to the unmodified ethylene-based copolymer during the melt mixing, the graft reaction can be caused more efficiently. As such an organic peroxide, one having a molecular weight of 200 or more is preferable.

Specifically, tert-butyl cumyl peroxide, di-
tert-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) Hexin-3, α, α′-di (tert-butylperoxy) diisopropylbenzene and the like.

The block copolymer (III) is a block copolymer of a hydrogenated or unhydrogenated conjugated diene and an aromatic vinyl, and the modified block copolymer is 0.01 to 0.01% based on the unmodified block copolymer. It can be obtained by grafting 10% by weight of unsaturated carboxylic acid or its derivative.

Examples of the conjugated diene used as a raw material for the unhydrogenated block copolymer include 1,3-butadiene, isoprene (2,3-dimethyl-1,3-butadiene), and 1,3-pentadiene. -Butadiene and isoprene are preferably used, and as the aromatic vinyl hydrocarbon, styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, vinylnaphthalene and the like are preferably used. it can.

Further, the hydrogenated block copolymer of a conjugated diene and an aromatic vinyl hydrocarbon means that at least 80% of the unsaturated content of the unhydrogenated block copolymer is reduced by hydrogenation, It is preferable that the ratio of aromatic double bonds reduced by hydrogenation is 10% or less.

Preferred specific examples of the hydrogenated and unhydrogenated block copolymers are hydrogenated or unhydrogenated styrene / butadiene /
Styrene triblock copolymers, hydrogenated or unhydrogenated styrene / isoprene / styrene triblock copolymers, etc. Among them, styrene / butadiene /
A styrene triblock hydrogenated copolymer is more preferably used.

Examples of the unsaturated carboxylic acid and its derivative obtained by graft-reacting the above-mentioned hydrogenated or unhydrogenated conjugated diene and aromatic vinyl block copolymer to obtain a modified block copolymer include the modified ethylene-based copolymer of (ii) The compounds mentioned in the section of polymer can be used as well.

The modified block copolymer can be easily produced, for example, by adding an unsaturated carboxylic acid or a derivative thereof to an unmodified hydrogenated or unhydrogenated block copolymer and melt-kneading at 150 to 300 ° C. can do. As a device for melt mixing, a screw extruder, a Banbury mixer or the like can be used.

It is considered that this grafting reaction proceeds by a so-called "ene" reaction between the unsaturated bond in the hydrogenated or unhydrogenated block copolymer and the unsaturated carboxylic acid or its derivative. Therefore, when using a hydrogenated block copolymer obtained by hydrogenation at a high hydrogenation rate, an organic peroxide is 0.001 relative to the hydrogenated block copolymer during melt mixing.
Grafting reaction can be efficiently generated by using ~ 0.1%. Such organic peroxides include (i
The same compounds as those described in the item of modified ethylene copolymer of i) can be used.

The melt flow rate (hereinafter abbreviated as MFR) of the impact modifiers (i) to (III) in the present invention is preferably in the range of 0.05 to 200, more preferably 0.1 to 100, still more preferably 0.5 to 50. It is a range. If the MFR is out of the above range, the impact resistance improving effect tends to be small.
Here, MFR is a value obtained according to ASTM D1238 (measured at 190 ° C.), and the unit is g / 10 minutes.

The amount of the impact modifiers (i) to (III) added in the present invention is the total amount of each or when two or more types are used in combination, and the total amount of the modified polyphenylene ether and the aromatic polyester.
1 to 60 parts by weight, preferably 2 to 40 parts by weight, and more preferably 3 to 30 parts by weight are desirable with respect to 100 parts by weight. If the addition amount is less than 1 part by weight, the impact resistance improving effect is small, and if it exceeds 60 parts by weight, the heat resistance tends to be poor.

Incidentally, with respect to the composition of the present invention, within a range that does not impair the object of the present invention, fibrous and granular fillers and reinforcing agents (for example, glass fiber, carbon fiber, asbestos, gypsum fiber,
Wollastonite, mica, clay, talc, alumina,
Titanium oxide, calcium carbonate, barium sulfate, glass beads, glass flakes, etc.), antioxidants and heat stabilizers (including hindered phenols, hydroquinones, thioethers, phosphites and their substitutions and combinations thereof), UV absorption Agents (eg various resorcinols, salicylates, benzotriazoles,
Benzophenone, etc.), lubricants and mold release agents (eg stearic acid and its salts, montanic acid and its salts, half esters, esters, etc.), dyes and pigments (eg cadmium sulfide, phthalocyanines, carbon black, etc.) Flame retardants (eg decapromodiphenyl ether, halogen-based compounds such as brominated polycarbonate, melamine or cyanuric acid-based, phosphorus-based, etc.), flame retardant aids (eg antimony oxide), antistatic agents (eg sodium dodecylbenzene sulfonate, poly One or more usual additives such as alkylene glycol), a plasticizer (for example, phosphoric acid ester such as triphenyl phosphate, phthalic acid ester, benzoic acid ester, etc.) and a crystallization accelerator can be added. One or more other thermoplastic resins (for example, polyethylene, polypropylene, polystyrene, ABS resin, acrylic resin, fluororesin, polyamide, polyacetal, polycarbonate, polysulfone, polyester elastomer, etc.) may be added.

The method for producing the resin composition of the present invention is not particularly limited, but preferably a polyphenylene ether modified product, an aromatic polyester, an epoxy compound and, if necessary, other additives such as an impact modifier at 250 to 320 ° C., more preferably 260 ~ 310
A method of melt mixing at ℃ is mentioned. By performing the melt mixing in such a temperature range, the dispersion of each component becomes good, and a resin composition having excellent mechanical properties can be obtained.

Examples of the apparatus for melt mixing include a mixing roll, a Banbury mixer, a kneader, an extruder, and the like, and the extruder is preferably used. As the extruder, either a single-screw extruder or an extruder having two or more screws can be used, but it is particularly preferable to use a twin-screw extruder.

When obtaining a molded article from the resin composition of the present invention, injection molding,
Usual methods such as extrusion molding and blow molding can be applied, and the obtained molded product exhibits good performance.

<Examples> The present invention will be described in more detail with reference to the following examples.

In addition, the part in an Example shows a weight part.

Reference Example 1 (Production of Modified Polyphenylene Ether A-1) 3 parts of maleic anhydride and 100 parts of maleic anhydride per 100 parts of polyphenylene ether powder having an intrinsic viscosity of 0.51
10 parts of 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 was charged into a 40 mmφ extruder set at 300 ° C., and the reaction was carried out by extrusion to give a polyphenylene ether modified product (A -1) was produced. 10 g of the obtained pellets were collected, made into a fine powder with a pulverizer, heated and refluxed with a Soxhlet extruder for 48 hours using 100 ml of methanol, and then dried under reduced pressure at 90 ° C. for 8 hours to obtain a sample.
The infrared absorption spectrum of this sample was measured, and it was confirmed that maleic anhydride reacted with 2.4 parts per 100 parts of polyphenylene ether.

Reference Example 2 (polyphenylene ether modified products A-2 to A-
Production of 4) In place of maleic anhydride in Reference Example 1, purification by reactive Soxhlet extraction was performed in the same manner as in Reference Example 1 except that one selected from diglycidyl tetrahydrophthalate, acrylamide and maleimide was used, and a measurement sample was prepared. Obtained. By measuring the infrared absorption spectra of these samples, the following polyphenylene ether modified product A
It was confirmed that -2-A-4 were obtained.

(Polyphenylene ether modified product) <Modified compound><Reaction rate of modified compound> (parts / polyphenylene ether 100 parts) A-2: diglycidyl tetrahydrophthalate 2.1 A-3: acrylamide 2.2 A-4: maleimide 2.4 Examples 1 to 1 11, Comparative Examples 1 to 9 Modified polyphenylene ether prepared in Reference Example (A-
1-A-4) and polyethylene terephthalate (B-1) having a reduced viscosity of 1.10 or polybutylene terephthalate (B-2) having a reduced viscosity of 1.45 and the following epoxy compound (C-
1 or C-2) in the proportions shown in Table 1 and mixed at 280 ° C.
Melt-mixed and pelletized with the extruder set to. 280 using a Koka flow tester on the obtained pellets
The melt viscosity was measured at ℃ and molded using a screw in-line type injection molding machine set at 260 ℃ to obtain a test piece for measuring physical properties. Appearance observation of the obtained test piece
Izod impact value according to ASTM D256, ASTM D6
The heat distortion temperature was measured according to 48. Heat distortion temperature is 5
The measurement was repeated twice, and the average value and the difference between the highest value and the lowest value were determined. The results are shown in Table 1.

(Epoxy compound) As is clear from the results shown in Table 1, the composition of the present invention in which the specific epoxy compound is used in combination with the polyphenylene ether modified product and the polyester has a high heat distortion temperature, and its physical properties are stable with little variation. In addition, it has a good balance of impact resistance and moldability (molding fluidity, appearance of molded product).

Example 12 In addition to the composition of Example 2, the impact modifier (D
Extrusion, molding and evaluation were carried out in the same manner as in Example 2 except that 20 parts of No. a to D-4) were contained.
e). The results are shown in Table 3.

Further, instead of D-1 to D-5, an ethylene / vinyl acetate copolymer (MFR 4.0 g / 10 min) (D-6) and D-2, D
-3 unmodified ethylene / butene-1 (90/10 molar ratio) copolymer (D-7), ethylene / propylene (80
(/ 20 mole ratio) Example using one type of copolymer (D-8) (No.
Tables 3 and 4 are also shown for reference.

As is clear from the results of Table 3, when a specific impact modifier was further used in combination with the composition comprising the modified polyphenylene ether of the present invention, the aromatic polyester and the specific epoxy compound, a molded article was obtained. The appearance is good, the heat distortion temperature is high, the variation is small, and the impact resistance and molding fluidity are remarkably improved.

<Effects of the Invention> The molded product from the resin composition of the present invention has excellent mechanical properties such as appearance of the molded product, heat resistance and impact resistance, and is also excellent in moldability, dimensional accuracy and chemical resistance. ,
It is useful as an outer panel material for automobiles.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location C08L 67/00 LPF (56) References JP 62-15326 (JP, A) JP 62 -257958 (JP, A) JP 63-350 (JP, A) JP 63-39958 (JP, A) JP 63-89566 (JP, A)

Claims (1)

[Claims] 1. A general formula (A) (In the formula, R _{1 to} R ₄ are each hydrogen, halogen, a hydrocarbon group, a substituted hydrocarbon group, a cyano group, an alkoxy group, a phenoxy group or a nitro group.) A polyphenylene ether having a repeating unit. 100 parts by weight of (a) carbon-carbon double bond or carbon-carbon triple bond in the molecule and (b) carboxylic acid group, acid anhydride group, acid amide group, imide group, carboxylic acid ester group, epoxy 5 to 95% by weight of a polyphenylene ether modified product obtained by reacting 0.1 to 20 parts by weight of a compound having at least one group selected from a group, an amino group and a hydroxyl group, and (B) 5 to 95 parts by weight of an aromatic polyester % With respect to 100 parts by weight of the polyphenylene ether composition comprising (C) the general formula (II) (However, R ₅ and R ₆ are substituted or unsubstituted alkylene groups and alkylidene groups, R _{7 to} R ₉ are hydrogen or methyl groups, and R _{10 to} R ₁₄ are hydrogen, halogen, substituted and unsubstituted hydrocarbons. Group, a cyano group, an alkoxy group, a phenoxy group or a nitro group, each m is an integer of 0 to 20), and a resin composition containing 0.05 to 30 parts by weight of the epoxy compound.