JPS63122755A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition having excellent impact resistance, solvent resistance and high-temperature rigidity and suitable for automobile bumper, door panel, etc., by compounding a polyphenylene ether resin with specific amounts of a specific aromatic polymer, modified polyolefin, etc. CONSTITUTION:(A) A polyphenylene ether is compounded with (B) 5-900pts.wt. (based on 100pts.wt. of the component A) of an aromatic polymer having carboxyl (anhydride) group, (C) 5-900pts.wt. (based on 100pts.wt. of A+B) of a modified polyolefin having carboxyl (anhydride) group or a mixture of the modified polyolefin and a polyolefin, (D) 5-40pts.wt. (based on 100pts.wt. of A+B+C) of a hydrogenated block copolymer containing a vinyl aromatic compound polymer block A and a conjugated diene polymer block B and optionally graft-polymerized with an alpha,beta-unsaturated carboxylic acid (anhydride) and (E) 0.1-20pts.wt. (based on 100pts.wt. of the sum of A-D) of one or more metallic compounds capable of supplying a 1-3-valent metallic ion.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention provides a resin composition with excellent impact resistance, solvent resistance, and heat-resistant rigidity. Bad: Adding a specific compound when mixing polyphenylene ether resin and polyolefin, or
By chemically modifying polyolefin with a specific compound, the compatibility of the paper and composition is improved, thereby realizing a resin composition with excellent impact resistance, solvent resistance, and heat-resistant rigidity.

[Prior art]

Polyolefins have excellent moldability, toughness, water resistance, organic solvent resistance, chemical resistance, etc., and are low in specific gravity and inexpensive, so they have been widely used for various molded products and sheets, but they are required for heat resistance. However, there are improvements to be made, which are an obstacle to developing new uses.

On the other hand, although polyphenylene ether resin has excellent heat resistance, its range of use is limited because it has drawbacks in moldability and solvent resistance. For example, it is blended with styrene resin and used for the purpose of improving moldability and impact strength, but its range of use is limited due to the drawback of solvent resistance. Not suitable for fields where durability is required.

Various blend compositions have been proposed to combine the advantages and compensate for the disadvantages of polyolefins and polyphenylene ethers. ), but they cannot always satisfy the relatively high mechanical strength level required in the industrial field. In addition, for the purpose of further improving the compatibility of polyolefin and polyphenylene ether resin and improving mechanical strength, compositions containing a block copolymer of side-illuminated styrene and butadiene or hydrogenated products thereof have been developed. Things (Unexamined Japanese Patent Publication No. 1983)
-71158, JP-A-54-88960, JP-A-5
No. 9-100159, etc.), and a composition obtained by adding an inorganic filler to these components (%
No. 3556) etc. have been proposed, and the roll molding processability and mechanical strength can be improved. Because it consists of a combination of polyolefins, the organic solvent resistance of polyolefins cannot be fully exhibited. In addition, a large amount of polyolefin exceeding 20% by weight is blended with polyphenylene ether resin, and a diblock copolymer or radial teleblock copolymer consisting of an alkenyl aromatic compound and a conjugated diene and their hydrogen are added as compatibilizers. Composition formed by adding an additive polymer (Japanese Patent Application Laid-Open No. 58-1035
57 and Japanese Patent Application Laid-Open No. 60-76547), and as shown in the same publication, compatibility can be improved and tensile properties, brittleness, etc. can be improved, but compatibility Improvement alone is not sufficient to satisfy the relatively high levels of stiffness, heat resistance, and balance between these and impact strength required in the field of industrial parts.

As described above, it is currently not possible to obtain a resin composition containing polyphenylene ether resin and polyolefin that has a relatively high level of mechanical strength balance and good solvent resistance required in the field of industrial parts. be.

[Summary of the invention]

In view of the above problems, as a result of repeated research, the present inventor has found that the relatively high level of impact resistance required in the field of industrial parts,
A resin composition with heat-resistant rigidity and solvent resistance has been obtained.

That is, the gist of the present invention is the following (a)
, (b), (e), (d) and (e) (a) Aromatic polymer having a carboxyl group or its anhydride group=(
a) 5 to 900 parts by weight per 100 parts by weight of component (e) Modified polyolefin having a carboxyl group or its anhydride group alone, or a blend consisting of this and polyolefin = total of components (a) and (b) 100
5 to 900 parts by weight (d) having a vinyl aromatic compound polymerization block A and a conjugated diene compound polymerization block B, in which an α,β-unsaturated carboxylic acid or its anhydride is graft-polymerized. A certain hydrogen adduct of a block copolymer: Total of (a), (b) and (c) 1
5 to 40 parts by weight per 00 parts by weight (e) One or more metal compounds capable of supplying monovalent, divalent or trivalent metal ions: (a), (b), (c) and (d ) is 0.1 to 20 parts by weight based on a total of 100 parts by weight.

Hereinafter, the invention will be specifically explained, and examples will be described.

[Detailed description of the invention]

L Component (1) Polyphenylene ether (<L” component)
a-1 Borifuenylene ethyl used in the present invention,
The general formula each independently represents a hydrocarbon group containing no hydrogen, no-rogen, or tertiary α-carbon atom, a halohydrocarbon group having at least two carbon atoms between the no-rogen atom and the phenyl nucleus, Nine substituents are selected from the group consisting of hydrocarbon oxy groups and non-hydrocarbon oxy groups having at least two carbon atoms between the no-rogen atom and the phenyl nucleus. Q may be the same or different.

A classic example of polyphenylene ether is poly(
2,6-dimethyl-1,4-phenylene) (216-diether-1,4-phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, '? ' Li(2-1f-6-furopyru-1,4-)unishin) ether, poly(2,6-diprobyl-1,4-phenylene) ether, poly(2-
Ethyl-6-broby-1,4-phenylene) ether, poly(2,6-diphthyl-1゜4-phenylene) ether, poly(2,6-cygropenyl-1,4-phenylene) ether, poly(2゜6-dilauryl) -1,4-7
22lene) ether 1, I-'IJ (2,6-diphenyl-1,4-phenylene) ether, poly(2,6-simethoxy 1,4-)unisine) ether, poly(2,
6-jethoxy-1,4-phenylene) ether, poly(2-methoxy-6-nitoxy-1,4-phenylene)
Ether, poly(2-ethyl-6-styaryloxy-1,4-)unisine) ether, BoIJ (2,6-dichloro-1,4-phenylene) ether, poly(2-methyl-6-phenyl) -1,4-)unisine) ether, poly(2,6-shihenjiru-1,4-phenylene) ether, yNIJ(2-ethoxy-1,4-)unisine) ether, poly(2-chloro- 1,4-phenylene)ether, poly(2,5-dibromo-1,4-)unisine)
There are ethers and equivalents.

Also, a copolymer of 2,6-dimethylphenol and 2.3.6-)limethylphenol, 2,6-dimethylphenol,! : Copolymer of 2.3,5.6-titramethylphenol, 2,6-diethylphenol,! : 2,3
．． Mention may also be made of copolymers such as copolymers of 6-trimethylphenol.

Furthermore, the polyphenylene ether used in the present invention is
It also includes modified polyphenylene ethers such as polyphenylene ethers defined by the above general formula grafted with styrenic monomers (eg, EVA, styrene, p-methylstyrene, α-methylstyrene, etc.).

Methods for producing polyphenylene ether corresponding to the above are known, for example, U.S. Pat.
No. 306875, No. 3257357 and No. 3257
No. 358 specifications and Japanese Patent Publication No. 52-1788
No. 0 and JP-A-50-51197.

A group of polyphenylene ethers which are preferred for the purposes of the present invention are those with alkyl substituents in the two positions ortho to the ether oxygen atom and copolymers of 2,6-dialkyl phenylene phenols. Furthermore, it is a graft polymer obtained by grafting a styrene monomer onto these polyphenylene ether skeletons.

a-2 Furthermore, in the present invention, polyphenylene ether can be used together with the following polystyrene polymer.

The styrenic polymer used in the present invention is known per se, and has the general formula (wherein R is hydrogen or an alkyl group having 1 to 4 carbon atoms, and 2 is a halogen or an alkyl group having 1 to 4 carbon atoms. represents a substituent that is an alkyl group, and p is an integer of 1 to 5.)
The polymer must contain at least 10% by weight of repeating structural units derived from the vinyl aromatic compound represented by the formula. Examples of such styrenic polymers include homopolymers of styrene or its derivatives, and styrene-containing copolymers, such as styrene-conjugated diene block copolymers, styrene-acrylonitrile copolymers (5AN), and styrene-acrylonitrile-butadiene copolymers. Further examples include styrenic polymers mixed with or modified with natural or synthetic diastereomeric substances such as polybutadiene, polyisoprene, butyl rubber, EPDM, ethylene-propylene copolymers, and natural rubber.

Preferred styrenic polymers for the present invention are homopolystyrene and rubber-reinforced polystyrene made with a butadiene-styrene copolymer comb. The common ratio of the styrene polymer to the polyphenylene ether resin is preferably within a range that does not impair the excellent properties of the polyphenylene ether resin, and is preferably 20 to 100 parts by weight of the polyphenylene ether resin and 0 to 80 parts by weight of the styrene polymer. A resin mixture consisting of is preferred.

(2) Aromatic polymer having a carboxyl group or its anhydride group (Φ) component) The aromatic polymer having a carboxyl group or anhydride group used in the present invention includes both of these. In particular, (1) a copolymer of a vinyl aromatic compound and an α,β-unsaturated carboxylic acid or its anhydride (iD) a modified polyphenylene ether resin having a carboxyl residue; used.

Regarding (i).

In the above (1), the vinyl aromatic compound has a chemical structure represented by the following general formula.

R' In the formula, R1 and R2 are selected from hydrogen and a lower alkyl group or alkenyl group having 1 to 6 carbon atoms, and R3 and R
4 is selected from the group consisting of hydrogen, a lower alkyl group having 1 to 6 carbon atoms, chlorine, bromine, R'% R' and R7 are hydrogen,
It may be selected from the group consisting of lower alkyl groups and alkenyl groups having 1 to 6 carbon atoms, or R and R may be linked together with a hydrocarbyl group to form a naphthyl group.

Specific examples of vinyl aromatic compounds include styrene, halamethylstyrene, α-methylstyrene, vinylxylene, vinyltoluene, vinylnaphthalene, divinylbenzene,
There are bromostyrene and cyclo-O-styrene. Among these, styrene, α-methylstyrene, paramethylstyrene, vinyltoluene, and vinylxylene are preferred, and styrene is more preferred.

On the other hand, the α,β-unsaturated carboxylic acid or its acid anhydride used in the copolymerization of the vinyl aromatic compound and the α,β-unsaturated carboxylic acid or its anhydride include acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid,
Crotonic acid, fumaric acid, and maleic anhydride are used.

Moreover, when it is a polybasic acid such as maleic acid or fumaric acid, its half alkyl ester may be used. Among these, in copolymerization with vinyl aromatics, acrylic esters, methacrylic esters, acrylonitrile, acrylamide, vinyl chloride, etc. may be used in combination with vinyl monomers.

Preferred examples of such copolymers include styrene-maleic anhydride copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, and styrene-methyl methacrylate-maleic anhydride copolymer. Among them, styrene-roleic anhydride copolymer and styrene-acrylic acid copolymer are particularly preferred.

The proportion of α,β-unsaturated carboxylic acid or its anhydride in the copolymer is preferably 5% by weight or more. Further, the proportion of vinyl aromatics in the copolymer is preferably 70% by weight or more.

(About 10.

In (ii) above, the modified polyphenylene ether resin having a carboxyl group is prepared using a known method (for example, A
, J., CH.A.L.K. and A.S., H.A.Y.
＋ Journey of Polymer 5cien
ce: Part A-1, vow, 7.

691-705 (1969)),
It has a cyclic structural unit represented by the general formula. where the ether oxygen atoms of one unit are connected to the benzene nucleus of the next adjacent unit, and each Q independently represents hydrogen, halogen, or tertiary α-
A hydrocarbon group containing no carbon atoms, a halohydrocarbon group having at least two carbon atoms between the halogen atom and the phenyl nucleus, a hydrocarbon oxy group and at least two carbon atoms between the halogen atom and the phenyl nucleus represents a monovalent substituent selected from the group consisting of halohydrocarbonoxy groups having carbon atoms of represents a monovalent substituent selected from the group consisting of carboxylalkyl groups, and at least one Q' of ty must be a substituent having a carboxyl group. t and m are integers, preferably m/L+m=0.01 to 0.5.

The mixing ratio of component (b) to component (a) is preferably 5 to 900 parts by weight per 100 parts by weight of component (a),
A more preferable range is 10 to 500 parts by weight. If it is less than 5 parts by weight, delamination occurs, and if it exceeds 900 parts by weight,
Impairs the properties of polyphenylene ether.

(3) A modified polyolefin having a carboxyl group or its anhydride group alone, or a mixture thereof with a polyolefin (component (c)) The polyolefin used in the present invention is a compound having a carboxyl group or its anhydride group in advance. A chemically modified polyolefin can be used, and the polyolefin itself can also be used together with a polymer that has been chemically modified in advance without undergoing such chemical modification.

Specific examples of polyolefins used include polyethylene, polypropylene, polybutene-1, polypentene-1, polyhexene-1, and poly-4-methylpentene-1.
Examples include α-olefin polymers such as 1 and the like. Copolymers obtained from a plurality of olefin monomers selected from ethylene, pyrene, butene-1, pentene-1, hexene-1, octene-1,4-methylpentene-1, etc., specific examples include , ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-propylene-butene copolymer, and the like.

These polyolefins can be obtained by polymerization by known methods and can be used in combination.

The modified polyolefin referred to in the present invention includes copolymerization of an olefin monomer and α,β-unsaturated carboxylic acid or its anhydride, graft polymerization of α,β-unsaturated carboxylic acid or its anhydride to the above polyolefin, etc. , can be obtained using known methods.

Moreover, as a method for later graft polymerizing the polyolefin, when blending the polyolefin with other components (a), (b), (d), and (e), α.

It is also possible to carry out graft polymerization simultaneously with blending in the presence of a β-unsaturated carboxylic acid or its anhydride, with or without a radical initiator.

Chemically modified polyolefins include ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, maleic anhydride grafted polypropylene, maleic anhydride grafted ethylene-propylene copolymer, etc.
Of these, ethylene-acrylic acid copolymers, maleic anhydride kraft polypropylene, and the like are preferred. The proportion of α,β-unsaturated carboxylic acid or its anhydride in the modified polyolefin is preferably 0.51% to 20% by weight.

In component (e), the blending ratio when blending modified polyolefin and polyolefin depends on the degree of modification of modified polyolefin, but generally modified polyolefin 5
A preferred blend is ~95 parts by weight of the polyolefin and 5 to 95 parts by weight of the polyolefin. When the modified polyolefin is 5 parts by weight or less,
This is not preferable because the impact strength decreases.

The amount of component (c) added is 5 to 900 parts by weight based on the total of 100 parts by weight of components (a) + (b), and 20 to 2 parts by weight.
00 parts by weight is more preferred. If it is less than 5 parts by weight, there is no effect of improving oil resistance, and if it exceeds 900 parts by weight, the properties of the polyphenylene ether resin will be impaired.

(4) Hydrogenation of a block copolymer having a vinyl aromatic compound polymerization block A and a conjugated diene compound polymerization block B, in which an α,β-unsaturated carboxylic acid or its anhydride may be graft-polymerized. (Component (d)) (i) One of the hydrogenated components of the block copolymer used as component (d) in the resin composition of the present invention is a chain block "A" derived from a vinyl aromatic compound. This is a block copolymer in which the aliphatic unsaturated groups in block B of a vinyl aromatic compound-conjugated diene block copolymer having a structure each having at least one chain block rBJ derived from a conjugated diene are reduced by hydrogenation. The arrangement of blocks A and B includes a linear structure or a so-called radial teleblock structure having a branched structure. Further, a part of these structures may include random chains derived from a random copolymerization portion of a vinyl aromatic compound and a conjugated diene. Among these, those with a linear structure are preferred, and those with a diblock structure are more preferred. The vinyl aromatic compound forming block A has a chemical structure represented by the following general formula.

In the formula, R1 and R2 are selected from hydrogen and a lower alkyl group or alkenyl group having 1 to 6 carbon atoms, and R3 and R
4 is selected from the group consisting of hydrogen, a lower alkyl group having 1 to 6 carbon atoms, chlorine, and bromine, and R5, R6, and R7 are selected from the group consisting of hydrogen, a lower alkyl group having 1 to 6 carbon atoms, and an alkenyl group. Alternatively, R and R may be linked together with a hydrocarbyl group to form a naphthyl group.

Specific examples of vinyl aromatic compounds include styrene, paramethylstyrene, α-methylstyrene, vinylxylene, vinyltoluene, vinylnaphthalene, divinylbenzene,
There are bromostyrene and hydrochlorostyrene. Among these, styrene, α-methylstyrene, paramethylstyrene, vinyltoluene, and vinylxylene are preferred, and styrene is preferred.

Specific examples of conjugated dienes include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3
-7” tadiene, 1,3-pentadiene, etc.
Among these, 1,3-butadiene, 2-methyl-1
, 3-butadiene is preferred. In addition to these conjugated dienes, small amounts of ethylene, propylene,
Lower olefinic hydrocarbons such as 1-butene, cyclopentadiene, and nonconjugated dienes may be contained.

The proportion of repeating units derived from the vinyl aromatic compound in the partially hydrogenated vinyl aromatic compound-conjugated diene block copolymer is preferably in the range of 10 to 80% by weight, and 15 to 60% by weight. A range of t% is more preferable.

Among the aliphatic chain moieties in these block copolymers,
The proportion of unsaturated bonds derived from the conjugated diene and remaining without being hydrogenated is preferably 20% or less, more preferably 1.10% or less. Further, about 25% or less of the aromatic unsaturated bonds derived from the alkenyl aromatic compound may be hydrogenated.

As a guideline for their molecular weight, these hydrogenated block copolymers have a toluene solution viscosity of 3,000 to 30 cps (concentration 15% by weight) or 10,000 to 50 cps (concentration 20% by weight)
Preferably, it falls within this range. If the value is larger than these, the moldability of the composition becomes difficult, and if the value is smaller than these, the mechanical strength of the composition is undesirably low.

Many methods have been proposed for producing vinyl aromatic compound-conjugated diene block copolymers. Typical methods include, for example, the specification of Japanese Patent Publication No. 40-23798, U.S. Pat.
There is a method described in No. 0996, etc., in which block copolymerization is carried out in an inert solvent using a lithium catalyst or a Ziegler type melting medium.

Hydrogenation treatment of these block copolymers can be carried out by methods described in the specifications of Japanese Patent Publications No. 42-8704, No. 63-6636, or No. 46-20814, or by hydrogenation treatment in an inert solvent. Hydrogenation is carried out in the presence of a hydrogenation catalyst. In this hydrogenation, at least 5 of the olefinic double bonds in polymer block B are
0%, preferably 80% or more are hydrogenated, and 25% or less of the aromatic unsaturated bonds in polymer block A are hydrogenated.

These hydrogen additives are 5hel I Chemical
Company F) Kraton G-grade salts, such as GX-1701 and G-165.
It is sold under the code name 2.

(10) Another hydrogenation compound that may be used as the t'd component in the resin composition of the present invention is the above (4).
This is a polymer obtained by graft-polymerizing α,β-unsaturated carboxylic acid or its anhydride to the hydrogenated product shown in item (i).

In order to graft copolymerize an α,β-unsaturated carboxylic acid and its anhydride to such a hydrogen adduct, the copolymer and the graft monomer are mixed in a molten state or a solution state using a radical initiator, Or it is done without using it.

Grafting monomers selected from unsaturated carboxylic acids and their derivatives include acrylic acid, methacrylic acid, α-
Ethyl acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, endo-bicyclo(2,2,1)hept-5-ene-2°3-dicarboxylic acid (nadic acid) o)
, unsaturated carboxylic acids such as methyl-endocys-bicyclo(2,2,1)hept-5-ene-2,3-dicarboxylic acid (methylnadic acid), their acid halides, amides, imides, acid anhydrides Examples include derivatives of compounds, esters, etc., specifically malenyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate,
Examples include dimethyl maleate and glycidyl maleate. Among these, unsaturated dicarboxylic acids or their acid anhydrides are preferred, and maleic acid, nadic acid, and their acid anhydrides are particularly preferred.

The method of graft copolymerizing the graft monomer to the hydrogenated block copolymer is not particularly limited, but if the resulting modified copolymer contains undesirable components such as gel, It is desirable to avoid deterioration of processability due to a decrease in fluidity. For this purpose, when graft copolymerization is carried out by addition reaction under melt-mixing conditions using an extruder or the like, it is necessary to carry out the graft copolymerization in the presence of known stabilizers such as phenol-based, phosphorus-based, and amine-based stabilizers. desirable.

The reaction temperature for graft copolymerization is usually about 60 to about 35
It is carried out at 0°C, particularly preferably at about 100 to about 300°C. The addition ratio of the graft monomer is about 0,000 to about 2 parts by weight of the block copolymer.
0 parts by weight, especially preferably 0.01 to 10% by weight, and the addition ratio of the radical initiator is similarly 0.001 to 30% by weight, especially 0.01% by weight.
It is preferable to set it as 20 parts by weight. By performing graft copolymerization within such a range, the graft monomer can be efficiently grafted onto the copolymer.

The modified block copolymer prepared by the above method can be prepared by removing by-products such as gel-like substances as necessary, or by removing a copolymer consisting of a vinyl aromatic compound and a conjugated diene compound and/or its hydride. It is prepared by diluting it with etc.

The amount of the hydrogenated block copolymer or the modified block copolymer (component (d)) added is (a)
The amount is 5 to 40 parts by weight, preferably 10 to 30 parts by weight, based on a total of 100 parts by weight of components (b) and (c). If the amount added is less than 5 parts by weight, the impact strength will not be improved sufficiently, and if it is more than 40 parts by weight, the rigidity will be significantly reduced.
Undesirable.

(5) One or more metal compounds capable of supplying monovalent, divalent or trivalent metal ions (component (e)) The metal ions of component (e) are specifically Na'', K1 L11C
81 introduction, Cu1 Be 1 to 0, Ca++, Sr+
+, B a++, Cu++, Ca++, Hpr, S
n, PbXFe, CoXNi
.

Zn++, lvl"", Sc++", Fe+++, Y
+++ etc., and examples of metal compounds capable of supplying these ions include carboxylates, hydroxides, alkoxides, carbonates, and bicarbonates of these metals.

The amount of component (e) added is preferably 0.1 to 10 parts by weight per 100 parts by weight of the total of components (a) to 10) + (c) + (d).

If the amount is less than 0.1 part by weight, delamination may occur, and if it is more than 20 parts by weight, depending on the metal compound, foaming may occur during molding, which is not preferable.

In the present invention, in addition to the above-mentioned essential components, other additional components may be added as necessary to the extent that the effects of the present invention are not impaired, for example,
Antioxidants, weather resistance improvers, nucleating agents for polyolefins,
slip agents, inorganic or organic fillers and reinforcing agents, flame retardants,
Various colorants, antistatic agents, mold release agents, and small amounts of radical generators (organic peroxides, etc.) for controlling the molecular weight of polyolefins.
There is no problem in adding such things.

In particular, fillers such as glass fiber, wollastonite, potassium titanate whiskers, mica, talc, and calcium carbonate are effective in improving the balance of physical properties such as rigidity, and improving moldability, dimensional accuracy, and dimensional stability.

(Blending method) As a blending method for obtaining the resin composition according to the present invention, generally, resins are blended together or resins are mixed with stabilizers or colorants,
Furthermore, various methods of blending the resin and filler can be applied. For example, powdered or granular components are uniformly dispersed in a Henschel mixer, super mixer, ribbon blender, ■ blender, etc., and then a twin-screw mixed extruder, a two-screw mixed extruder, a roll , Banbury mixer, waste mill,
A Walabender Plastograph melt kneader can be used. The melting crosstalk temperature is usually in the range of 200°C to 350°C. The resin composition obtained as described above can be extruded into pellets after being melted and mixed.

The resin composition according to the present invention can be easily molded by molding methods generally applied to thermoplastic resins, such as injection molding, extrusion molding, and blow molding, among which injection molding is most preferred. Due to its good mechanical properties, it is suitable for automobile parts, specifically exterior parts such as pan bars, door panels, fenders, moldings, emblems, wheel covers, engine hoods, roofs, spoilers, instrument panels, and consoles. It is suitable for interior parts such as boxes and trims, and also for exterior parts of electrical equipment, specifically for parts such as televisions, refrigerators, and so-called office automation equipment.

2 Examples and Comparative Examples A resin composition consisting of components (a), (b), (+1) and (d) shown in Table 1 was used at 280°C in a PCM twin-screw extruder manufactured by Ikegai Iron Works. This pelletized resin was extruded into pellets using an N-100BII injection molding machine manufactured by Japan Steel Works, at a cylinder temperature of 270°C and an injection pressure cuff of 00n/ca.
A test piece was obtained by injection molding at a mold temperature of 60°C.

(1) Measurement and Evaluation Method The physical property values and properties in the Examples and Comparative Examples shown below were measured and evaluated under the following conditions.

1) Flexural modulus I S OR178-1974 Procedure 1
2 (JIS K7203) using an Instron testing machine. In addition, the value of the flexural modulus at 80°C was determined by installing a constant temperature bath so that the test piece, the support stand used for measurement, and the pressurizing wedge part were placed in a hot air type heating room at 80°C.
Measurements were carried out after conditioning in an atmosphere of ±1° C. for 20 minutes or more.

2) Izot impact strength - Measured using an Izot impact tester manufactured by Toyo Seiki Seisakusho in accordance with ISOR15o-1969 (JIS K7110) notched Izot impact strength.

3) Organic solvent resistance Bergen's 1 ellipse method (SPE Journal 667 (196
2)) Measured according to the method. Specifically, when a test piece with a thickness of 2-2 was fixed in a quarter oval jig with a major axis of 24 mm and a minor axis of 8 cm W1, and immersed in commercially available gasoline for 5 minutes, the occurrence of cracks was determined. The minimum strain was determined as the critical strain.

At this time, make sure that no cracks occur ◎ (extremely good)
, ○ (good) if the critical strain value is 1.5% or more, 1.
It was judged as 0 to 1.5% Δ (fair) and less than 1.0% × (poor).

Further, the raw materials used in this example are as follows.

(a) Component (a) Polyphenylene ether: manufactured by Mitsubishi Yuka ■, Rilf
f The intrinsic viscosity when measured in roform at 30°C is 0.
47 dt/f poly(2,6-cymethyl-1,4-
phenylene) ether (hereinafter abbreviated as PPE in the examples).

←) Styrenic polymers: homopolystyrene (f(F-77) (hereinafter abbreviated as PS) manufactured by Mitsubishi Monsanto ■ and rubber reinforced polystyrene (HT-76) (hereinafter abbreviated as HIPS) manufactured by Mitsubishi Monsanto.

(b) Component (a) Maleic anhydride-styrene copolymer: manufactured by ARCO Polymer Co., Ltd. (Dylark 232) (hereinafter abbreviated as DL).

(b) Modified polyphenylene ether: The above PPE5t was dissolved in 2001j tetrahydrofuran, and BuLi
After dropping the hexane solution, the reaction system was poured onto dry ice in the presence of diluted hydrochloric acid. By adding hexane to this and drying the precipitate, a modified PPE having a carboxyl group in the chain was obtained (hereinafter abbreviated as C-PPE). As a result of titration and infrared absorption (IR) measurement, the carboxyl group was
It was bound to 15 mol% of the repeating unit of PPE.

(c) Component (a) Polypropylene: Propylene-ethylene copolymer (Mitsubishi Polypro BC5D) manufactured by Mitsubishi Yuka (hereinafter abbreviated as PP).

(+:0 Polyethylene: Mitsubishi Polyethylene Y manufactured by Mitsubishi Yuka ■
K30 (hereinafter abbreviated as PE).

(c) Modified polypropylene: 100 parts of commercially available polypropylene (Mitsubishi Yuka brand name "Mitsubishi Polypro BC8D"),
After mixing 20 parts of maleic anhydride and 300 parts of chlorobenzene and heating and dissolving at 110°C, 10 parts of benzoyl peroxide was added.
1 part was added over 6 hours, and after the addition, the reaction was further carried out at the same temperature for 3 hours. A large excess of acetone was added to precipitate the polymer, which was then dried in an oven. The maleic anhydride content in the obtained maleic anhydride-added polypropylene was 8.2% (hereinafter abbreviated as M-PP in the examples).

B) Modified polyethylene: manufactured by Mitsubishi Yuka ■, ethylene-acrylic acid copolymer (acrylic acid content 6.6%) (Mitsubishi Polyethylene X-190) (hereinafter abbreviated as FAA).

(d) Component (a) Hydrogenated block copolymer Hydrogenated sterene-isoprene block copolymer sold by Shell Kagaku (trade name: Kraton GX)
-1701) and hydrogenated products of styrene-butadiene-styrene block copolymers. (Product name Clayton G
-1652) (b) Modified block copolymer In a stainless steel pressure-resistant reaction vessel equipped with a thermometer and a stirrer, 1t1 xylene 1t1 Hydrogenated styrene-butadiene-styrene block copolymer 1 from Shikuru Chemical Co., Ltd. Kraton G-16
52" 100f, replace the system with nitrogen gas, 12"
After raising the temperature to 5°C, a xylene solution of maleic anhydride and a xylene solution of dicumyl peroxide (
Maleic anhydride: 1 t/10'z dicumyl peroxide 0.15f/10d) was fed from separate conduits over a period of 6 hours and finally maleic anhydride 6. Of,
0.92 of dicumyl peroxide was fed into the system. After the reaction is completed, the system is cooled to around room temperature, acetone is added, the maleic anhydride grafted block copolymer is treated with F, and the precipitate is washed repeatedly with acetone. The washed precipitate was dried under reduced pressure at an elevated temperature to obtain a modified block copolymer in the form of a white powder. As a result of infrared absorption spectrum measurement and neutralization titration of this modified block copolymer, the content of maleic anhydride groups was 3.4% by weight (hereinafter, this modified block copolymer is abbreviated as "modified block"). do).

(Left below) Description of Examples The resin compositions of the present invention shown in Examples 1 to 11 have impact resistance,
It is clear that both heat-resistant rigidity and solvent resistance are excellent.

Claims (1)

[Scope of Claims] A resin composition comprising the following components (a), (b), (c), (d) and (e) (a) polyphenylene ether resin (b) carboxyl group or its anhydride group Aromatic polymer having: 5 to 900 parts by weight per 100 parts by weight of component (a)
Part by weight (c) Modified polyolefin alone having a carboxyl group or its anhydride group, or a blend consisting of this and a polyolefin: 5 to 900 parts by weight (d) per 100 parts by weight in total of components (a) and (b) A hydrogen adduct of a block copolymer having a vinyl aromatic compound polymerization block A and a conjugated diene compound polymerization block B, in which an α,β-unsaturated carboxylic acid or its anhydride may be graft-polymerized: ( 5 to 40 parts by weight based on a total of 100 parts by weight of a), (b) and (c) (e) One or more metal compounds capable of supplying monovalent, divalent or trivalent metal ions: (a) ), (b), (c) and (d) in a total of 100 parts by weight, from 0.1 to 20 parts by weight.