JP2570793B2 - Thermoplastic resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel thermoplastic resin composition that can be used for molded articles by injection molding or extrusion molding.

More specifically, heat resistance and impact resistance obtained by blending a rubber composition and a resin composition obtained by grafting a styrene-based monomer to a propylene polymer composition to a resin composition containing polyphenylene ether or polyphenylene ether. ,
The present invention relates to a novel thermoplastic resin composition having excellent rigidity and processability.

<Prior art> Polyphenylene ether is a resin with excellent properties such as heat resistance, chemical resistance, and mechanical and electrical properties, but has drawbacks such as poor moldability and low impact resistance. ing.

On the other hand, the propylene polymer composition has excellent properties such as moldability, toughness, water resistance, and chemical resistance.
Moreover, since it has a low specific gravity and is inexpensive, it has been widely used as various molded articles, films and sheets.

However, the propylene polymer composition has heat resistance, rigidity,
It has difficulties or needs improvement in impact resistance, paintability, adhesiveness, etc., and these are obstacles in cultivating new practical applications. In particular, improvements in heat resistance and impact resistance are strongly desired.

In order to improve the formability of polyphenylene ether, a method of blending an alkenyl aromatic polymer compatible with polyphenylene ether is well known.

For example, JP-A-57-135845, JP-B-56-22344
It is as described in the official gazette.

However, a resin composition having high impact resistance and excellent weather resistance while maintaining the excellent heat resistance of polyphenylene ether has been demanded from the market.

It is well known to incorporate and disperse a rubber-like substance in order to improve impact resistance.

Particularly, when an alkenyl aromatic polymer modified with rubber is blended with polyphenylene ether, it is advantageous because moldability and impact resistance can be simultaneously improved.

However, the alkenyl aromatic polymer modified with this rubber generally contains a diene rubber as a rubber component.
When exposed to high temperatures or outdoors for a long period of time, it has the disadvantage that it becomes brittle rapidly, which is a problem.

<Problem to be Solved by the Invention> From such a viewpoint, polyphenylene ether, a propylene polymer composition and a rubber-like substance are blended, and the characteristics of each component are improved, and the moldability and impact resistance are improved. If a resin composition is obtained, it is expected that the resin composition may be used for a wide variety of new applications.

<Means for solving the problems> In view of these points, as a result of extensive and detailed search to develop an effective technique for improving a resin composition comprising polyphenylene ether, a propylene polymer and a rubber-like substance, The present invention has been reached.

That is, the present invention provides (a) a resin composition containing polyphenylene ether or polyphenylene ether, (b) a resin composition obtained by grafting a styrene monomer to a propylene polymer composition, and (c) an ethylene content. 15-85% by weight, Mooney viscosity (ML
_{1 + 4} 121 ° C.) The present invention relates to a thermoplastic resin composition comprising an ethylene-α-olefin copolymer rubber having a glass transition point of -10 ° C. or lower and 5 to 120 ° C.

Further, (a) a resin composition containing polyphenylene ether or polyphenylene ether, (b) a resin composition obtained by grafting a styrene monomer to a propylene polymer composition, and (c) a styrene monomer Grafted with ethylene content
15 to 85% by weight, Mooney viscosity (ML _{1 + 4} 121 ° C) 5 to 120,
The present invention relates to a thermoplastic resin composition comprising an ethylene-α-olefin copolymer rubber having a glass transition point of −10 ° C. or lower.

The thermoplastic resin composition according to the present invention is a resin composition having a good balance of heat resistance and impact resistance, and excellent in moldability and impact resistance.

The polyphenylene ether of the component (a) used in the present invention has a general formula A polymer having a unit structure represented by or a copolymer having two or more types of the structural units as long as the basic performance of the polyphenylene ether, such as heat resistance and mechanical properties, is not reduced practically; More than 50. R ₁ , R ₂ , R ₃ and R ₄ are any of hydrogen, halogen, a hydrocarbon group or a substituted hydrocarbon group, a hydrocarbon oxy group or a substituted hydrocarbon oxy group. Specific examples of R ₁ , R ₂ , R ₃ and R ₄ are hydrogen; halogen atoms such as chlorine, bromine and iodine; methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, allyl, phenyl, benzyl, methylbenzyl And substituted hydrocarbon groups such as chloromethyl and bromomethyl; and groups such as hydrocarbonoxy groups and substituted hydrocarbonoxy groups such as methoxy, ethoxy, phenoxy and chloroethoxy. In particular,
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-isopropyl-1,4-phenylene ether, poly-2,6-dimethoxy-1,4-phenylene ether, poly-2,6-diphenyl-1,4-phenylene ether, poly-2,6-dichloro -1,4-phenylene ether,
Polymers such as poly-2,5-dimethyl-1,4-phenylene ether, copolymers of 2,6-dimethylphenol and 2,3,6-trimethylphenol, 2,6-dimethylphenol and 3-methyl- Copolymers such as a copolymer with 6-tert-butylphenol are exemplified.

Further, the polyphenylene ether of the present invention also includes a modified product of the above-mentioned polymer or copolymer. For example, in the presence of an ethylene-propylene-polyene terpolymer, Oxidative polymerization of polystyrene, formula in the presence of polystyrene Oxidative polymerization of styrene, polymerization of styrene in the presence of polyphenylene ether polymer or copolymer, and polymerization and reaction of polyphenylene ether polymer or copolymer and styrene with peroxide in an extruder. can give.

The (a) resin composition containing polyphenylene ether in the present invention means a resin composition comprising the above-mentioned polyphenylene ether and one or more other polymer compounds. Other polymer compounds include, for example, polyolefins such as polyethylene, propylene polymer, and polymethylpentene; polyvinyl chloride, polyvinyl methacrylate, polyvinyl acetate, polyvinyl pyridine, polyvinyl carbazole, polyacrylamide, polyacrylonitrile, ethylene- Homopolymers and copolymers of various vinyl compounds such as vinyl acetate copolymers and alkenyl aromatic resins; polycarbonate, polysulfone, polyethylene terephthalate, polybutylene terephthalate,
Examples thereof include polyarylene esters (for example, u-polymer of Unitika Ltd.), polyphenylene sulfides; polyamides such as 6-nylon, 6,6-nylon and 12-nylon; condensed polymer compounds such as polyacetal. Furthermore, silicone resin, fluorine resin, polyimide,
Polyamide-imide, phenolic resin, alkyd resin,
Various thermosetting resins such as unsaturated polyester resins, epoxy resins, and dapon resins are also included. The mixing ratio of polyphenylene ether and other polymer compounds is, for example,
It can be widely varied in the range of 1 to 99% by weight of polyphenylene ether and 99 to 1% by weight of other polymer compound. Among them, the optimum composition is determined according to each purpose and application.

Among the above other polymer compounds, preferred are polyolefin, polyamide, alkenyl aromatic resin, and rubber-modified alkenyl aromatic resin.

Most preferred are alkenyl aromatic resins, rubber-modified alkenyl aromatic resins and propylene polymers.

In the present invention, (a) the polyphenylene ether is
General formula, (However, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are any of hydrogen, halogen, a hydrocarbon group or a substituted hydrocarbon group, a hydrocarbon oxy group or a substituted hydrocarbon oxy group, and 1
One is always hydrogen. ) Groups, one of which is necessarily hydrogen. ) Can be obtained by subjecting one or more of the phenols represented by the formula to oxidative coupling polymerization.

The resin composition of the component (b) used in the present invention contains at least 1% by weight, preferably 2 to 90% by weight, more preferably 3 to 70% by weight of a styrene monomer in a propylene polymer.
It is a resin composition obtained by weight-% graft polymerization.

The propylene polymer as used herein means a propylene homopolymer, or a random or block copolymer of propylene and another α-olefin having 2 to 18 carbon atoms.

Here, the styrene monomer is represented by the general formula: (Where R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are any of hydrogen, halogen, hydrocarbon or substituted hydrocarbon group, hydrocarbonoxy group or substituted hydrocarbonoxy group, and R ₁₁ is Hydrogen, a lower alkyl group having 1 to 4 carbon atoms.)

Specific examples of R ₆ , R ₇ , R ₈ , R ₉ and R _{10 in} the above formula include halogen atoms such as hydrogen, chlorine, bromine and iodine, methyl, ethyl, propyl, vinyl, allyl, benzyl,
Hydrocarbon groups such as methylbenzyl; substituted hydrocarbon groups such as chloromethyl and bromomethyl; methoxy, ethoxy,
Includes hydrocarbon oxy groups such as phenoxy and monochloromethoxy or substituted hydrocarbon oxy groups.

Specific examples of R ₁₁ are hydrogen; methyl, such as a lower alkyl group such as ethyl.

Specific examples of styrene monomers include styrene, 2,4-
Dichlorostyrene, p-methoxystyrene, p-methylstyrene, p-phenylstyrene, p-divinylbenzene, p-
(Chloromethoxy) -styrene, n-methylstyrene, o-
Methyl-α-methylstyrene, m-methyl-α-methylstyrene, p-methyl-α-methylstyrene, p-methoxy-
α-methylstyrene and the like. These can be used alone or in combination of two or more.

In the present invention, the method of graft-polymerizing at least 1% by weight of a styrene monomer is a suspension polymerization method, an emulsion polymerization method,
It can be produced by any known polymerization method such as a solution polymerization method or a bulk polymerization method (including a method using an extruder in addition to a method using a polymerization tank).

The propylene polymer composition of the present invention contains a heat and light stabilizer, an antistatic agent, an acid inhibitor, carbon black,
All kinds of additives, such as pigments, softeners, etc., are added as required. Furthermore, other polymers such as low density polyethylone, high density polyethylene, polybutene, EP rubber and mica,
A filler such as talc or the like can be mixed and used.

In the present invention, the component (c) includes an ethylene content
15 to 85% by weight, Mooney viscosity (ML _{1 + 4} 121 ° C) 5 to 120,
Ethylene-α-olefin copolymer rubber having a glass transition point of −10 ° C. or lower, or a rubber obtained by grafting a styrene-based monomer to such an ethylene-α-olefin copolymer rubber is used. The ethylene-α-olefin copolymer rubber is preferably a modified ethylene-α-olefin copolymer rubber modified with an unsaturated dicarboxylic acid or the like.

The ethylene-α-olefin copolymer rubber used in the present invention includes ethylene and other α-olefins such as propylene, 1-butene, 1-pentene, 1-hexene, and 4-hexene.
Copolymers with methyl 1-pentene, 1-octene and the like, and terpolymer rubbers such as an ethylene-propylene-1-butene copolymer and the like are included. Among them, ethylene-propylene copolymer rubber, ethylene- 1-butene copolymer rubber is preferably used.

The ethylene content in the copolymer rubber is 15 to 85% by weight, preferably 40 to 80% by weight. That is, if the ethylene content is 85
Highly crystalline copolymers with a content of more than 15% by weight are difficult to process under normal rubber molding conditions, and those with an ethylene content of less than 15% by weight have an increased glass transition point (Tg) and deteriorated rubber properties. Not preferred. The glass transition point is below -10 ° C.

The number average molecular weight of the copolymer rubber is preferably one that can be kneaded in an extruder, and is 10,000 to 100,000. If the molecular weight is too small, handling when feeding to an extruder is difficult, and if the molecular weight is too large, the fluidity becomes small and processing is difficult. Mooney viscosity (ML _{1 +} 4,12
1 ° C) 5 to 120.

Although the molecular weight distribution is not particularly defined, a preferable range is a Q value (weight average molecular weight / number average molecular weight) of 1 to 30, more preferably 2 to 20.

Further, as the modified ethylene-α-olefin copolymer rubber which can be used in the present invention, an unsaturated dicarboxylic acid-modified ethylene-α-olefin obtained by grafting an unsaturated dicarboxylic acid from the aforementioned ethylene-α olefin rubber as a raw material is used. And copolymers.

The unsaturated dicarboxylic acids mentioned here include maleic anhydride, maleic acid, fumaric anhydride, citraconic anhydride and the like.

As a method for producing the maleic anhydride-modified ethylene-α-olefin copolymer rubber, any conventionally known method can be used.

That is, in a hydrocarbon solvent, maleic anhydride and a radical initiator are added together with an ethylene-α-olefin copolymer rubber, and the reaction is carried out at 60 ° C. to 150 ° C. for several minutes to several hours to contain the modified rubber. A solution is obtained. At this time, maleic anhydride can be half-esterified or half-amided by adding an alcohol, an amine or the like, if necessary. The solution thus obtained is put into a large amount of methanol, acetone or the like, and the modified rubber can be recovered.

It can also be obtained by kneading maleic anhydride and a radical initiator together with an ethylene-α-olefin copolymer rubber in an extruder. For example, 0.5 to 15 parts by weight of maleic anhydride is added to 100 parts by weight of rubber. , 0.005 to 1.0 parts by weight of radical initiator at 150 to 300 ° C for several minutes to several tens
It is obtained by kneading separately. At this time, if necessary, an anti-gelling agent, for example, a phenolic antioxidant such as BHT can be used in combination.

In the present invention, various modified ethylene-α-olefin copolymer rubbers can be used. For example, a monomer selected from methyl acrylate, methyl methacrylate, allyl glycidyl ether, glycidyl methacrylate and the like in addition to maleic anhydride described above. A modified ethylene-α-olefin copolymer rubber modified with a base compound is used.

A modified ethylene-α-olefin copolymer rubber using two or more of these monomer compounds at the same time can also be used.

Further, two or more rubbers selected from ethylene-α-olefin copolymer rubbers and various modified ethylene-α-olefin copolymer rubbers can be used simultaneously.

The styrene monomer-grafted ethylene-α-olefin copolymer rubber can be obtained by the following method in addition to the same method as described above.

That is, a shredded product or pellet of ethylene-α-olefin copolymer rubber is dispersed in pure water together with a dispersant,
After impregnating the copolymer rubber with the styrene monomer,
The reaction is carried out at 50 to 150 ° C. for 1 to 5 hours using a radical initiator to obtain an ethylene-α-olefin copolymer rubber grafted with a styrene monomer.

Accordingly, the following four types of the ethylene-α-olefin copolymer rubber as the component (c) in the present invention are available.

Ethylene-α-olefin copolymer rubber Styrene-grafted ethylene-α-olefin copolymer rubber Modified ethylene-α-olefin copolymer rubber such as unsaturated dicarboxylic acid Modified ethylene-α-olefin copolymer such as styrene-graft unsaturated dicarboxylic acid Combined Rubber In the present invention, the components (a) and (b) of the resin composition can be mixed in an arbitrary ratio, and the mixing ratio is such that the component (a) is 5 to 95% by weight and the component (b) is 95-5% by weight
Is appropriate. When the content of the component (b) is less than 5% by weight, the effect of improving processability is small, and the content of the component (b) is 95% by weight.
If the temperature exceeds the range, the thermal properties such as the heat distortion temperature are undesirably reduced.

In the present invention, the amount of the component (c) is not particularly specified, but the amount of the component (c) is 1 to 50 parts by weight based on 100 parts by weight of the total of (component (a) + component (b)). It is preferably in the range of parts.

If the amount of the component (c) is less than 1 part by weight, the effect of improving the impact resistance by the component (c) is small, and if it exceeds 50 parts by weight, the excellent properties inherent in polyphenylene ether are undesirably weakened.

In carrying out the present invention, reinforcing agents such as glass fibers and carbon fibers, inorganic and organic fillers such as carbon black, silica and TiO ₂ , plasticizers, stabilizers, flame retardants, dyes and pigments may be added. It is possible. More specifically, a reinforcing agent is a compound that increases the mechanical or thermal properties such as flexural strength, flexural modulus, tensile strength, tensile modulus, and heat deformation temperature by compounding it. For example, alumina fiber,
Examples include carbon fiber, glass fiber, highly elastic polyamide fiber, highly elastic polyester fiber, silicon carbide fiber, and titanate whisker.

It is sufficient that the amount of these toughening agents is at least an amount effective for strengthening, but in general, the amount is preferably in the range of about 5 to 100 parts by weight based on 100 parts by weight of the composition of the present invention.

A particularly preferred reinforcing filler is glass, the use of glass fiber filaments comprising lime-aluminum borosilicate glass which is relatively free of sodium. This is known as "Σ" glass. However, other glasses, such as the low sodium content glass known as "C" glass, are also useful when electrical properties are less important. Filaments are made by common methods such as, for example, steam or air blowing, flame blowing and mechanical pulling. Preferred filaments for plastic reinforcement are made by mechanical tension. Filament diameters are in the range of about 2-20 microns, but this is not critical in the present invention. The length of the glass filaments and whether they are bundled into aggregated fibers and whether these bundled aggregated fibers are further bundled as yarn, rope or roving, or woven on mats, etc. In the present invention, this is not strict. However, when the composition is made in the present invention, the length is about 0.3 cm to about 3 cm, preferably about 0.6 cm.
As a short cut strand shape of the following length,
It is convenient to use glass filaments.

To further illustrate the flame retardants, the flame retardants useful in the present invention include a class of compounds widely known to those skilled in the art.

In general, more important compounds among these are compounds containing these elements which can impart flame retardancy, such as, for example, bromine, chlorine, antimony, phosphorus and nitrogen. For example, halogenated organic compounds, antimony oxide, antimony oxide and halogenated organic compounds, antimony oxide and phosphorus compounds, phosphorus alone or phosphorus compounds,
Examples include a phosphorus compound or a compound having a phosphorus-nitrogen bond and a halogen-containing compound, or a mixture of two or more thereof.

The amount of the flame retardant additive is not critical, but may be any amount sufficient to impart flame retardancy. It is not advisable to increase the amount too much, because the physical properties such as the softening point are deteriorated. Suitable amounts of these are: (a) 0.5 to 50 parts by weight, preferably 1 to 25 parts by weight, more preferably 3 to 15 parts by weight of the flame retardant per 100 parts by weight of the polyphenylene ether or the resin composition containing the polyphenylene ether. Be blended.

Useful halogen-containing compounds include the following:

In the above formula, n is 1 to 10, and R is an alkylene, alkylidene or alicyclic bond (for example, methylene, ethylene,
Groups such as propylene, isopropylene, isopropylidene, butylene, isobutylene, amylene, cyclohexylene, cyclopentylidene, ether, carbonyl, amine, sulfur-containing bonds (eg, sulfide, sulfoxide, sulfone), carbonate, phosphorus-containing bonds, etc. Selected from the group consisting of

R may also consist of two or more alkylene or alkylidene linkages linked by groups such as aromatic, amino, ether, ester, carbonyl, sulfide, sulfoxide, sulfone, phosphorus containing linkages and the like. Ar and Ar 'are phenylene, biphenylene,
Monocyclic or polycyclic carbocyclic aromatic groups such as terphenylene and naphthylene.

 Ar and Ar 'may be the same or different.

Y is a substituent selected from the group consisting of organic, inorganic, and organometallic groups. The substituent represented by Y is (1) a halogen such as chlorine, bromine, iodine or fluorine, and (2) an ether of the general formula OE (where E is a monovalent hydrocarbon group similar to the following X). Group, (3) -OH group,
(4) a monovalent hydrocarbon group represented by R, or (5) another substituent such as a nitro group or a cyano group. When d is 2 or more, Y may be the same or different.

 X is, for example, the following monovalent hydrocarbon group.

Methyl, ethyl, propyl, isopropyl, butyl,
Alkyl groups such as decyl; aryl groups such as phenyl, naphthyl, biphenyl, xylyl, tolyl and the like; aralkyl groups such as benzyl, ethylphenyl and the like;
Cycloaliphatic groups such as cyclopentyl, cyclohexyl and the like; and monovalent hydrocarbon groups containing inert substituents therein. When two or more Xs are used, they may be the same or different.

d represents an integer from 1 to a maximum value equal to the maximum number of substitutable hydrogens on the aromatic ring consisting of Ar or Ar '. e represents an integer from o to the maximum determined by the number of replaceable hydrogens on R.

a, b and c each represent an integer including o. When b is not 0, neither a nor c is 0. Otherwise, either one of a or c may be 0. When b is 0, the aromatic groups are bonded to each other by a direct carbon-carbon bond. The hydroxyl group or substituent Y on the aromatic groups Ar and Ar 'can take any of the ortho, meta and para positions on the aromatic ring.

 The following are specific examples of the above formula.

2,2-bis- (3,5-dichlorophenyl) -propane, bis- (2-chlorophenyl) -methane, 1,2-bis- (2,6-dichlorophenyl) ethane, 1,1-bis- (4- Iodophenyl) ethane, 1,1-bis- (2-chloro-4-iodophenyl)-
Ethane, 1,1-bis- (2-chloro-4-methylphenyl)-
Ethane, 1,1-bis- (3,5-dichlorophenyl) -ethane 2,2-bis- (3-phenyl-4-bromophenyl)
-Ethane, 2,3-bis- (4,6-dichloronaphthyl) -propane, 2,2-bis- (2,6-dichlorophenyl) -pentane, 2,2-bis- (3,5-dichlorophenyl)- Hexane, bis- (4-chlorophenyl) -phenylmethane, bis- (3,5-dichlorophenyl) -cyclohexylmethane, bis- (3-nitro-4-bromophenyl) -methane bis- (4-oxy-2,6 -Dichloro-3-methoxyphenyl) -methane, 2,2-bis- (3,5-dibromo-4-oxyphenyl)
-Propane, 2,2-bis- (3,5-dichloro-4-oxyphenyl)
-Propane, 2,2-bis- (3-bromo-4-oxyphenyl)-
Bis aromatic compounds using sulfide, sulfoxy, etc. instead of propane and the two aliphatic groups in the above specific examples, tetrabromobenzene, hexachlorobenzene, hexabrumobenzene, 2,2′-dichlorobiphenyl, 2, 4'-
Dibromobiphenyl, 2,4'-dichlorobiphenyl, hexabromobiphenyl, octabromobiphenyl, decabromobiphenyl, halogenated diphenyl ether containing 2 to 10 halogen atoms, 2,2-bis- (3,5-dibromo-
Oligomer having a degree of polymerization of 1 to 20, which is heavy-bonded from 4-oxyphenyl) -propane and phosgene.

In the present invention, preferred halogen compounds are aromatic halogen compounds such as chlorinated benzene, brominated benzene, chlorinated biphenyl, chlorinated terphenyl, brominated biphenyl, and brominated terphenyl, or divalent alkylene groups. Compounds containing two phenyl nuclei and having at least two chlorine or bromine atoms per phenyl nucleus, or a mixture of at least two of the above. Particularly preferred are hexabromobenzene and chlorinated biphenyl or terphenyl or mixtures thereof with antimony oxide.

Representative of the preferred phosphorus compounds used in the present invention are those having the following general formula and nitrogen analogs.

In the above formula, each Q is the same or different and includes hydrocarbon groups such as alkyl, cycloalkyl, aral, alkyl-substituted aryl and aryl-substituted alkyl; halogen; hydrogen and combinations thereof. Representative examples of suitable phosphate esters include: Phenyl bisdodecyl phosphate, phenyl bisneopentyl phosphate, phenylethylene hydrogen phosphate, phenyl-bis- (3,5,5-trimethylhexyl) phosphate, ethyl diphenyl phosphate, 2-ethylxyl di-phosphate (p -Tolyl), diphenyl hydrogen phosphate,
Bath- (2-ethylhexyl) -p-tolyl, tritolyl phosphate, bis- (2-ethylhexal) phosphate
-Phenyl, tri (nonylphenyl) phosphate, phenylmethyl hydrogen phosphate, di (dodecyl) -p-tolyl phosphate, triphenyl phosphate, triphenyl phosphate, dibutyl phosphate phosphate, 2-phosphate phosphate Chloroethyl diphenyl, p-tolylbis- (2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, diphenyl hydrogen phosphate. The most preferred phosphate ester is triphenyl phosphate. It is also preferable to use triphenyl phosphate in combination with hexabromobenzene or triphenyl phosphate in combination with antimony oxide.

Other flame-retardant additives include phosphorus nitride chloride, phosphorus ester amide, phosphoric amide, phosphinic amide,
Compounds containing a phosphorus-nitrogen bond, such as tris (aziridinyl) phosphine oxide or tetrakis (oxymethyl) phosphonium chloride.

The method for producing the resin composition of the present invention is not particularly limited, and an ordinary known method can be used.

Mixing in a solution state and evaporating the solvent or precipitating in a non-solvent is also effective, but from an industrial point of view, a method of kneading in a molten state is actually used. For the melt kneading, kneading apparatuses such as a single-screw or twin-screw extruder and various kneaders which are generally used can be used. In particular, a biaxial high kneader is preferred.

When kneading, it is preferable that each resin component is uniformly mixed in a powder or pellet state in advance using a device such as a tumbler or a Hensiel mixer. Can also be used.

The kneaded resin composition is molded by injection molding, extrusion molding or other various molding methods. However, the present invention also does not pass through a kneading process in advance, but dry-blends during injection molding or extrusion molding and melts during the melt processing operation. It also includes a method of directly kneading to obtain a molded product.

In the present invention, the kneading order is not particularly limited, and the polyphenylene ether (a) and the propylene polymer composition (b) are used.
And the rubber-like substance (c) may be kneaded all at once. After kneading the polyphenylene ether (a) and the propylene polymer composition (b) to obtain a composition, the rubber-like substance (c) is kneaded. You may. Also, other kneading orders may be used.

The resin composition of the present invention is used for molded articles, sheets, tubes, films, fibers, laminates, coating materials and the like by injection molding or extrusion molding. In particular, automotive parts, such as interior and exterior materials such as bumpers, instrument panels, fenders, trims, door panels, wheel covers, side protectors, garnishes, trunk lids, bonnets, roofs, and mechanical parts that require heat resistance Used for It is used as a motorcycle component, for example, as a covering material, a muffler cover, a leg shield and the like. Further, it is used for electric and electronic parts for housings, chassis, connectors, printed circuit boards, pulleys, and other parts requiring strength and heat resistance.

<Examples> The present invention will be described below with reference to examples, but these are merely examples, and the present invention is not limited thereto.
The deflection temperature under load test (HDT) in the examples is based on JIS K7
207, Izod impact strength (thickness 3.2 mm) conformed to JIS K7110. The flexural modulus was measured according to ASTM D790-66 on a 5.0 mm thick sample press-formed according to JIS K6758.

The polyphenylene ether, propylene polymer, styrene-grafted propylene polymer, and styrene-grafted ethylone-propylene copolymer rubber used in the examples and comparative examples were obtained by the following formulation.

Polyphenylene ether In a 10-volume jacketed autoclave equipped with a stirrer, thermometer, condenser and air inlet tube reaching the bottom of the autoclave, 3,420 g of xylene, 1,3 methanol
66 g, 1,222 g (10 mol) of 2,6-dimethylphenol and 24 g (0.6 mol) of sodium hydroxide were charged to form a uniform solution, and then 31.5 g (0.3 mol) of diethanolamine and di-n-butylamine were added to the solution. 19.4 g (0.15 mol) and 0.99 g (0.005 mol) of manganese chloride tetrahydrate in methanol
A solution dissolved in 100 g was added.

Then, while stirring the contents vigorously, air was blown at a speed of 5 / min. The reaction temperature and pressure were maintained at 35 ° C. and 9 kg / cm ² respectively. After 7 hours from the start of air blowing, the supply of air was stopped, and the reaction mixture was poured into a mixture of 66 g (1.15 mol) of acetic acid and 4,900 g of methanol. The resulting slurry was filtered under reduced pressure to isolate wet polyphenylene ether. The isolated polyphenylene ether was washed with 7,200 g of methanol, and dried under reduced pressure at 150 ° C. overnight to obtain 1,179 g of dry polyphenylene ether. In chloroform 0.5 / dl concentration
The reduced viscosity measured at 25 ° C. was 0.54 dl / g.

 Styrene graft of propylene polymer composition Sumitomo Noblene AH561 (Melt index 3.0g / 10
Propylene-ethylene block containing 7% by weight of ethylene
1 kg of pellets of copolymer) in 10 autoclaves
Water 4, styrene monomer 200g, dispersant (Metroze
90SH-100) 6g, and peroxide (perbutyl) P
V) and at about 120 ° C while blowing nitrogen.
After reacting for 1 hour, cool and then with ethyl ethyl ketone
After extracting and removing polystyrene, graft with styrene
The recovered propylene polymer was recovered. For propylene polymer
The amount of grafted styrene was 176 g.

 Styrene-grafted ethylene-propylene rubber Ethylene-stainless steel autoclave with stirrer
Esprene as α-olefin copolymer rubber E-20
1 (EPM, ML manufactured by Sumitomo Chemical Co., Ltd.)_{1 + 4}121 ℃ = 27, ethylene
Content 47% by weight, Tg = -64 ° C) 100 parts by weight (shredded), pure water
350 parts by weight, tribasic calcium phosphate 4.0 parts by weight, pluroni
Check 4.0 parts by weight of F-68 (made by Asahi Denka Kogyo Co., Ltd.)
The mixture was sufficiently purged with nitrogen while stirring.

 After that, 30 parts by weight of styrene monomer, radical start
Samperox as an agent TO (Sanken Chemical) 0.75
Parts were added. 1 hour after heating to 110 ° C over 80 minutes
The reaction was continued. After cooling, styrene graft by filtration
Take out the copolymer rubber, wash it thoroughly with pure water, and vacuum
Drying was performed. The styrene content of the obtained graft is
When measured using an infrared absorption spectrum,
there were. Also ML_{1 + 4}The 121 ° C. was 53 and the Tg was −58 ° C.

Examples 1 to 4 and Comparative Examples 1 to 3 Polyphenylene ether, a propylene polymer, and the like were kneaded using a Labo Plastomill (manufactured by Toyo Seiki).
(Kneading temperature: 270 ° C.) Test pieces were prepared from the obtained composition by compression molding, and their physical properties were measured.

Table 1 shows the results of the composition ratio, Izod impact value, deflection temperature under load, and flexural modulus of each resin. As is clear from Examples 1 and 2 and Comparative Examples 1 and 2, the composition comprising polyphenylene ether, polypropylene and EPR rubber has a low deflection temperature under load and a low flexural modulus, whereas propylene grafted with styrene according to the present invention has The composition containing the polymer shows improvement in deflection temperature under load, Izod impact value and flexural modulus. Particularly when styrene-grafted ethylene-propylene rubber is blended, a remarkable improvement in physical properties is observed.

Also, from Comparative Example 2, it can be seen that the composition containing no rubber-like substance exhibited an extremely low Izod impact value.

Examples 5 to 6 and Comparative Examples 4 to 7 Various rubber-like substances were blended with polyphenylene ether and ethylene-grafted polypropylene, melt-kneaded in the same manner as in Example 1, using a Labo Plastomill, and the physical properties were measured. Shown in

Example 7 and Comparative Examples 8 to 10 Melt index: 1.0 g / 10 minutes, crystallization temperature: 121 ° C., bending
Elasticity is 14700kg / cm^Two10 kg of 1 kg of homopolypropylene
Water 4, styrene monomer 350 into the autoclave
g, Metrolse, a dispersant 90SH-100 6g, and Pau
Oxide (perbutyl PV) and blow nitrogen
After reacting at 120 ° C for about 1 hour while cooling,
Extracted and removed polystyrene with methyl ethyl ketone
After that, the propylene polymer grafted with styrene was recovered and
Was.

The amount of styrene grafted to homopolypropylene is 19
3g, the graft polymerization rate of this graft polymer is 55%
Met. Table 3 shows the composition of the composition containing the propylene polymer thus obtained and the physical properties thereof.

It can be seen that the composition containing the styrene-grafted propylene polymer is particularly superior in the deflection temperature under load and the flexural modulus to the composition containing the homopolypropylene not grafted with styrene.

<Effects of the Invention> As described above, according to the present invention, a polyphenylene ether, a propylene polymer composition grafted with styrene, and a rubber-like substance are formed, and the processability, heat resistance,
A thermoplastic resin composition having excellent impact resistance can be provided.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kouji Tsuji 5-1 Anesaki Beach, Ichihara-shi, Chiba Sumitomo Chemical Co., Ltd. 149351 (JP, A) JP-A-49-75663 (JP, A)

Claims (3)

(57) [Claims] 1. A resin composition comprising (a) a polyphenylene ether or a polyphenylene ether, (b) a resin composition obtained by grafting a styrene monomer to a propylene polymer composition, and (c) an ethylene content of 15%. ~ 85% by weight, Mooney viscosity (ML
_{1 + 4} 121 ° C.) A thermoplastic resin composition comprising an ethylene-α-olefin copolymer rubber having a glass transition point of −10 ° C. or lower, 5 to 120 ° C. 2. A resin composition containing (a) a polyphenylene ether or a polyphenylene ether, (b) a resin composition obtained by grafting a styrene monomer to a propylene polymer composition, and (c) a styrene monomer. Content of ethylene grafted monomer
15 to 85% by weight, Mooney viscosity (ML _{1 + 4} 121 ° C) 5 to 120,
A thermoplastic resin composition comprising an ethylene-α-olefin copolymer rubber having a glass transition point of −10 ° C. or lower. (3) The polyphenylene ether represented by the general formula (However, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are any of hydrogen, halogen, a hydrocarbon group or a substituted hydrocarbon group, a hydrocarbon oxy group or a substituted hydrocarbon oxy group, of which 3. The thermoplastic resin according to claim 1 or 2, which is a polyphenylene ether obtained by oxidative coupling polymerization of one or more phenols represented by the following formula: Resin composition.