JP2006328136A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition excellent in tensile strength, scratch resistance and flexibility.
The following (A), (B) and (C) are contained, the content of (A) is 10 to 70% by weight, the content of (B) is 5 to 50% by weight, A thermoplastic resin composition having a content of (C) of 1 to 40% by weight (provided that the total of (A), (B) and (C) is 100% by weight).
(A) Thermoplastic resin (B) Containing monomer units derived from at least two olefins selected from the group consisting of ethylene, propylene and α-olefins having 4 to 20 carbon atoms, and having a molecular weight distribution (Mw / Amorphous α-olefin copolymer with Mn) of 1 to 4 (C) Graft-modified polyolefin [Selection] None

Description

  The present invention relates to a thermoplastic resin composition having excellent tensile strength, scratch resistance and flexibility.

  A thermoplastic resin composition in which a thermoplastic resin, a modified resin, and an inorganic filler are mixed is excellent in flame retardancy and mechanical properties, and is used, for example, in home appliances and automobile parts that require flame retardancy. JP-A-7-331088 discloses a thermoplastic resin excellent in bleed resistance, flame resistance, cold resistance and impact resistance, which is obtained by melt-kneading a thermoplastic resin, a modified resin and a non-halogen flame retardant compound. A composition is described.

JP 7-331088 A

However, the thermoplastic resin composition of the present invention cannot be said to have sufficient flexibility, and it has been difficult to apply it to uses such as a flame-retardant wire covering material and a soft vibration damping sheet that require flexibility.
Under such circumstances, a problem to be solved by the present invention, that is, an object of the present invention is to provide a thermoplastic resin composition excellent in tensile strength, scratch resistance and flexibility.

That is, the present invention contains the following (A), (B) and (C), the content of (A) is 10 to 70% by weight, and the content of (B) is 5 to 50% by weight. The content of (C) is 1 to 40% by weight (provided that the total of (A), (B) and (C) is 100% by weight).
(A) Thermoplastic resin (B) Containing monomer units derived from at least two olefins selected from the group consisting of ethylene, propylene and α-olefins having 4 to 20 carbon atoms, and having a molecular weight distribution (Mw / Amorphous α-olefin copolymer (C) having a Mn) of 1 to 4 (C) Graft-modified polyolefin

  According to the present invention, a thermoplastic resin composition having excellent tensile strength, scratch resistance and flexibility is provided.

  (A) of the present invention is a thermoplastic resin. Examples of the thermoplastic resin include polyethylene resins such as high density polyethylene, medium density polyethylene, low density polyethylene, and linear low density polyethylene (LLDPE), ethylene-vinyl acetate copolymer resin, and ethylene-acrylic acid copolymer. Polymer resin, ethylene-acrylic acid ester copolymer resin, ethylene-methacrylic acid copolymer resin, ethylene-methacrylic acid ester copolymer resin, ethylene-glycidyl methacrylate copolymer resin, ethylene-acrylic acid ester-methacrylic acid Glycidyl copolymer resin, polypropylene resin, polybutene resin, poly (4-methyl-1-pentene) resin, polystyrene resin, polyester resin, polyamide resin, polyphenylene ether resin, polyacetal resin, polycarbonate resin resin Ethylene - and cyclic olefin copolymer resins. Preferred are polyolefin resins such as polyethylene resins, polypropylene resins, polybutene resins, poly (4-methyl-1-pentene) resins, and more preferably derived from aliphatic olefins having 2 or more carbon atoms. A polyolefin resin having a monomer unit as a main unit, and more preferably a polyolefin resin having a monomer unit derived from an aliphatic olefin having 3 or more carbon atoms as a main unit. From the viewpoint of enhancing the heat resistance of the thermoplastic resin composition of the present invention, a polypropylene resin is particularly preferable.

  As a general method for producing a polypropylene-based resin, for example, a Ziegler-Natta type catalyst comprising a titanium-containing solid transition metal component and an organometallic component, or a periodic table having at least one cyclopentadienyl skeleton is used. Using a metallocene catalyst comprising a transition metal compound of group 4 to group 6 and a promoter component as a polymerization catalyst, a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method, or a polymerization method combining these , A method of producing a propylene homopolymer by polymerizing propylene by a single-stage polymerization method or a multi-stage polymerization method, or at least one olefin selected from the group consisting of propylene and olefins having 2 to 12 carbon atoms (propylene And a method of producing a copolymer by copolymerization. Moreover, you may use a commercial item as a polypropylene resin.

  As the crystallinity of the polyolefin-based resin, from the viewpoint of enhancing the heat resistance of the thermoplastic resin composition of the present invention, the melting point is preferably 80 to 176 ° C., more preferably 120 to 176 ° C. Preferably it is 30-120 J / g, More preferably, it is 60-120 J / g.

  The number average molecular weight of the polyolefin resin is preferably 10,000 to 1,000,000. The number average molecular weight is measured by gel permeation chromatograph (GPC).

  (B) of the present invention is an amorphous α-olefin copolymer obtained by copolymerizing at least two olefins selected from the group consisting of ethylene, propylene and α-olefins having 4 to 20 carbon atoms. It is a coalescence. Examples of the α-olefin having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1- Linear olefins such as dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicocene, 3-methyl-1-butene, 3- Examples thereof include chain olefins such as branched olefins such as methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-hexene, and 2,2,4-trimethyl-1-pentene.

  As a specific combination of two or more of the olefins, the total number of carbon atoms of the olefins is preferably 6 from the viewpoint of the balance of tensile strength, scratch resistance and flexibility of the thermoplastic resin composition of the present invention. This is a combination. Specific combinations of two or more of the olefins include, for example, ethylene and 1-butene, ethylene and 1-hexene, ethylene and 1-octene, ethylene and 4-methyl-1-pentene, ethylene and propylene and 1- Butene, ethylene and propylene and 1-hexene, ethylene and 1-butene and 1-hexene, propylene and 1-butene, propylene and 1-hexene, propylene and 1-octene, propylene and 4-methyl-1-pentene, propylene Examples include 1-butene and 1-hexene, 1-butene and 1-hexene, 1-butene and 1-octene, 1-hexene and 1-octene, and the like.

  (B) of the present invention may be a copolymer obtained by further copolymerizing monomers other than ethylene, propylene, and α-olefin having 4 to 20 carbon atoms within the range not impairing the object of the present invention. Examples of the monomer include a cyclic olefin, a vinyl aromatic compound, and a polyene compound, and a cyclic olefin is preferable.

  Examples of the cyclic olefin include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, 1-methylnorbornene, 7-methylnorbornene, 5,5,6-trimethylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, 5-ethylidenenorbornene, 5-vinylnorbornene, 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1, 2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1 2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydro Naphthalene, 2-ethylidene-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano- 1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,5-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8, 8a-octahydronaphthalene, 2-cyclohexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dichloro-1, 4,5,8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphth 2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,2-dihydrodicyclopentadiene, 5-chloronorbornene, 5,5-dichloronorbornene, 5-fluoronorbornene, 5,5,6-trifluoro-6-trifluoromethylnorbornene, 5-chloromethylnorbornene, 5-methoxynorbornene, 5,6-dicarboxylnorbornene anhydrate, 5-dimethylaminonorbornene, 5-cyanonorbornene, cyclopentene, 3-methylcyclopentene, 4-methylcyclopentene, 3,4-dimethylcyclopentene, 3,5-dimethylcyclopentene, 3-chlorocyclopentene, cyclohexene, 3-methylcyclohexene Xene, 4-methylsic Examples include lohexene, 3,4-dimethylcyclohexene, 3-chlorocyclohexene, cycloheptene, and vinylcyclohexane.

  Examples of the vinyl aromatic compound include styrene, α-methylstyrene, p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-tert-butylstyrene, ethylstyrene, Examples include vinyl naphthalene.

  Examples of the polyene compound include conjugated polyene compounds and non-conjugated polyene compounds. Examples of the conjugated polyene compound include aliphatic conjugated polyene compounds such as linear aliphatic conjugated polyene compounds and branched aliphatic conjugated polyene compounds, and alicyclic conjugated polyene compounds. Non-conjugated polyene compounds include Examples thereof include an aliphatic nonconjugated polyene compound, an alicyclic nonconjugated polyene compound, and an aromatic nonconjugated polyene compound. These may have an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, and the like.

  Examples of the aliphatic conjugated polyene compound include 1,3-butadiene, isoprene, 2-ethyl-1,3-butadiene, 2-propyl-1,3-butadiene, 2-isopropyl-1,3-butadiene, 2- Hexyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 2-methyl-1,3- Hexadiene, 2-methyl-1,3-octadiene, 2-methyl-1,3-decadiene, 2,3-dimethyl-1,3-pentadiene, 2,3-dimethyl-1,3-hexadiene, 2,3- Examples include dimethyl-1,3-octadiene and 2,3-dimethyl-1,3-decadiene.

  Examples of the alicyclic conjugated polyene compound include 2-methyl-1,3-cyclopentadiene, 2-methyl-1,3-cyclohexadiene, 2,3-dimethyl-1,3-cyclopentadiene, 2,3- Dimethyl-1,3-cyclohexadiene, 2-chloro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, 1-fluoro-1,3-butadiene, 2-chloro-1,3-pentadiene 2-chloro-1,3-cyclopentadiene, 2-chloro-1,3-cyclohexadiene, and the like.

  Examples of the aliphatic non-conjugated polyene compound include 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 1,6-octadiene, 1,7-octadiene, 1,8-nonadiene, 1,9 -Decadiene, 1,13-tetradecadiene, 1,5,9-decatriene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4 -Ethyl-1,4-hexadiene, 3-methyl-1,5-hexadiene, 3,3-dimethyl-1,4-hexadiene, 3,4-dimethyl-1,5-hexadiene, 5-methyl-1,4 -Heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5-heptadiene 3-methyl-1,6-heptadiene, 4-methyl-1,6-heptadiene, 4,4-dimethyl-1,6-heptadiene, 4-ethyl-1,6-heptadiene, 4-methyl-1,4- Octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-octadiene, 5-methyl-1,5-octadiene, 6-methyl-1,5- Octadiene, 5-ethyl-1,5-octadiene, 6-ethyl-1,5-octadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6- Octadiene, 6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 4-methyl-1,4-nonadiene, 5-methyl-1,4-nonadiene, 4-ethyl-1 4-nonadiene, 5-ethyl-1,4-nonadiene, 5-methyl-1,5-nonadiene, 6-methyl-1,5-nonadiene, 5-ethyl-1,5-nonadiene, 6-ethyl-1, 5-nonadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 7-methyl-1, 7-nonadiene, 8-methyl-1,7-nonadiene, 7-ethyl-1,7-nonadiene, 5-methyl-1,4-decadiene, 5-ethyl-1,4-decadiene, 5-methyl-1, 5-decadiene, 6-methyl-1,5-decadiene, 5-ethyl-1,5-decadiene, 6-ethyl-1,5-decadiene, 6-methyl-1,6-decadiene, 6-ethyl-1, 6-decadiene, 7-methyl -1,6-decadiene, 7-ethyl-1,6-decadiene, 7-methyl-1,7-decadiene, 8-methyl-1,7-decadiene, 7-ethyl-1,7-decadiene, 8-ethyl -1,7-decadiene, 8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene, 8-ethyl-1,8-decadiene, 6-methyl-1,6-undecadiene, 9-methyl -1,8-undecadiene, 6,10-dimethyl-1,5,9-undecatriene, 5,9-dimethyl-1,4,8-decatriene, 4-ethylidene-8-methyl-1,7-nonadiene 13-ethyl-9-methyl-1,9,12-pentadecatriene, 5,9,13-trimethyl-1,4,8,12-tetradecadiene, 8,14,16-trimethyl-1,7 , 14-Hexadeca Lien, 4-ethylidene-12-methyl-1,11-penta decadiene, and the like.

  Examples of the alicyclic non-conjugated polyene compound include vinylcyclohexene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropenyl-2-norbornene, and cyclohexadiene. , Dicyclopentadiene, cyclooctadiene, 2,5-norbornadiene, 2-methyl-2,5-norbornadiene, 2-ethyl-2,5-norbornadiene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene -3-Isopropylidene-5-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 1,4-divinylcyclohexane, 1,3-divinylcyclohexane, 1,3-divinylcyclopentane, 1,5- Divinylcyclooctane, 1-allyl-4- Nylcyclohexane, 1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane, 1,5-diallylcyclooctane, 1-allyl-4-isopropenylcyclohexane, 1-isopropenyl-4-vinylcyclohexane, 1- Examples thereof include isopropenyl-3-vinylcyclopentane and methyltetrahydroindene.

  Examples of the aromatic non-conjugated polyene compound include divinylbenzene and vinylisopropenylbenzene.

  From the viewpoint of increasing the flexibility of the thermoplastic resin composition of the present invention, the amorphous property of (B) of the present invention is preferably that a crystal melting peak is not substantially observed by differential scanning calorimetry (DSC). is there. “A crystal melting peak is not substantially observed” means that a crystal melting peak having a heat of crystal melting of 1 J / g or more is not observed in a temperature range of −100 to 200 ° C. More preferably, neither a crystal melting peak with a heat of crystal melting of 1 J / g or more and a crystallization peak with a heat of crystallization of 1 J / g or higher are observed in the temperature range of −100 to 200 ° C.

When (B) of the present invention contains a monomer unit derived from ethylene, the following relational expression is preferably satisfied from the viewpoint of the balance of tensile strength, scratch resistance and flexibility of the thermoplastic resin composition. .
[Y / (x + y)] ≧ 0.5
More preferably,
[Y / (x + y)] ≧ 0.6,
More preferably,
[Y / (x + y)] ≧ 0.8.
In the above relational expression, x is the content (mol%) of the monomer unit derived from ethylene in the amorphous α-olefin copolymer, and y is the amorphous α-olefin copolymer. It is content (mol%) of the monomer unit derived from a C4-C20 alpha olefin in coalescence.

  The molecular weight distribution (Mw / Mn) of (B) of the present invention is 1 to 4 and more preferably 1 to 3 from the viewpoint of reducing the stickiness of the thermoplastic resin composition of the present invention. The molecular weight distribution is measured by gel permeation chromatograph (GPC).

  The intrinsic viscosity (B) of the present invention is preferably 0.1 dl / g or more, more preferably 0.3 dl / g, from the viewpoint of increasing the tensile strength and scratch resistance of the thermoplastic resin composition of the present invention. Or more, more preferably 0.5 dl / g or more, and particularly preferably 0.7 dl / g or more. In addition, the intrinsic viscosity is preferably 10 dl / g or less, more preferably 7 dl / g or less, still more preferably 5 dl / g from the viewpoint of improving processability during molding of the thermoplastic resin composition of the present invention. g or less, particularly preferably 4 dl / g or less. The intrinsic viscosity is measured using an Ubbelohde viscometer in 135 ° C. tetralin.

(B) of the present invention can be produced using a known Ziegler-Natta type catalyst or a known single-site catalyst (metallocene, etc.), but the viewpoint of improving the heat resistance of the thermoplastic resin composition of the present invention From the above, known single site catalysts (metallocene, etc.) are preferable. Examples of such single site catalysts include Japanese Patent Application Laid-Open Nos. 58-19309, 60-35005, and 60-35006. JP, 60-35007, JP, 60-35008, JP, 61-130314, JP, 3-163088, JP, 4-268307, JP, 9-12790. Metallocene catalysts described in JP-A-9-87313, JP-A-11-80233, JP10-508055, and the like; No. 10-316710, JP-A-11-1000039, JP-A-11-80228, JP-A-11-80227, JP-T-10-513289, JP-A-10-338706, JP-A-11 Non-metallocene complex catalysts described in Japanese Patent No. -71420 and the like. Among these, from the viewpoint of availability, it is preferably a metallocene catalyst, more preferably at least one cyclopentadiene-type anion skeleton, and a periodic table of Groups 3 to 12 having a C ₁ enantiomeric structure. It is a transition metal complex. Moreover, as a manufacturing method using a metallocene catalyst, the method of the European Patent Publication No. 12111287 is mentioned, for example.

  (C) of the present invention is a graft-modified polyolefin obtained by graft-modifying a polyolefin resin with a polar group-containing compound.

  Examples of the polyolefin resin include polyolefin resins such as polyethylene resin, polypropylene resin, polybutene resin, poly (4-methyl-1-pentene) resin exemplified in (A), and amorphous resin exemplified in (B). And an α-olefin copolymer, an ethylene-α-olefin copolymer rubber, an ethylene-α-olefin-nonconjugated diene copolymer rubber, and an olefin thermoplastic elastomer. Among these, from the viewpoint of increasing the flexibility of the thermoplastic resin composition of the present invention, linear low density polyethylene (LLDPE), amorphous α-olefin copolymer, and ethylene-α-olefin copolymer are preferable. Polymer rubber, more preferably an amorphous α-olefin copolymer.

  From the viewpoint of increasing the flexibility of the thermoplastic resin composition of the present invention, the crystallinity of the polyolefin-based resin is preferably 176 ° C. or less, more preferably 165 ° C. or less, and preferably 120 J or less as the heat of crystal fusion. / G or less, more preferably 60 J / g or less.

  The number average molecular weight of the polyolefin is preferably 10,000 to 1,000,000. The number average molecular weight is measured by gel permeation chromatograph (GPC).

As the polar group-containing compound, at least one compound selected from the group consisting of the following (I) and (II) is preferable.
(I) Compound having (i) at least one carbon-carbon unsaturated bond and (ii) at least one polar group in the same molecule (II) In the same molecule, (iii) General formula (OR) (R represents a hydrogen atom, an alkyl group, an aryl group, an acyl group or a carbonyldioxy group) and (iv) at least two functional groups containing the same or different carbon-oxygen double bonds. The carbon-carbon unsaturated bond of the compound (i) having a carbon is a carbon-carbon double bond or a carbon-carbon triple bond. As the polar group of (ii), a carbon-oxygen double bond-containing functional group (carboxyl group or a functional group derived from a carboxyl group, that is, various functional groups in which a hydrogen atom or a hydroxyl group of the carboxyl group is substituted, for example, Ester bond, amide bond, etc.), cyano group, epoxy group, amino group, hydroxyl group and the like.

  Examples of (I) include unsaturated carboxylic acids, unsaturated carboxylic acid derivatives, unsaturated epoxy compounds, unsaturated alcohols, unsaturated amines, and unsaturated isocyanate esters.

  Examples of the unsaturated carboxylic acid include maleic acid, fumaric acid, itaconic acid, acrylic acid, butenoic acid, crotonic acid, vinyl acetic acid, methacrylic acid, pentenoic acid, angelic acid, tiglic acid, 2-pentenoic acid, and 3-pentene. Acid, α-ethylacrylic acid, β-methylcrotonic acid, 4-pentenoic acid, 2-methyl-2-pentenoic acid, 3-methyl-2-pentenoic acid, α-ethylcrotonic 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-hexadi Acid, diallylacetic acid, geraniic acid, 2,4-decadienoic acid, 2,4-dodecadienoic acid, 9,12-hexadecadienoic acid, 9,12-octadecadienoic acid, hexadecatrienoic acid, eicosadienoic acid, icon Satrienoic acid, eicosatetraenoic acid, ricinoleic acid, eleostearic acid, oleic acid, eicosapentaenoic acid, erucic acid, docosadienoic acid, docosatrienoic acid, docosatetraenoic acid, docosapentaenoic acid, tetracosenoic acid, hexacosenoic acid, Examples include hexacodienoic acid, octacocenoic acid, and traacontenoic acid.

（ただし、Ｍはアルキレン基、アリーレン基を表す）で表される構造を有するもの等が挙げられる。 Examples of the unsaturated carboxylic acid derivative include esters, acid amides, and anhydrides of the above unsaturated carboxylic acids, and specifically include maleic anhydride, maleimide, maleic hydrazide, methyl nadic anhydride, and dichloro anhydride. Maleic acid, itaconic anhydride, a reaction product of maleic anhydride and diamine, such as the following formula

(However, M represents an alkylene group or an arylene group).

Unsaturated epoxy compounds include, for example, soybean oil, tung oil, castor oil, linseed oil, hemp seed oil, cottonseed oil, sesame oil, rapeseed oil, peanut oil, coconut oil, olive oil, palm oil, sardine oil, and other natural fats and oils Natural fats and oils, glycidyl (meth) acrylate, allyl glycidyl ether, etc. are mentioned.

Examples of the unsaturated alcohol include allyl alcohol, crotyl alcohol, methyl vinyl carbinol, allyl carbinol, methyl propenyl carbinol, 2-hydroxyethyl methacrylate, 4-penten-1-ol, 10-undecene-1. -Ol, propargyl alcohol, 1,4-pentadien-3-ol, 1,4-hexadien-3-ol, 3,5-hexadien-2-ol, 2,4-hexadien-1-ol, general formula C _n Unsaturated alcohol represented by H _2n-5 OH, C _n H _2n-7 OH, C _n H _2n-9 OH (where n represents a positive integer, respectively), 3-butene-1,2-diol 2,5-dimethyl-3-hexene-2,5-diol, 1,5-hexadiene-3,4-diol, 2,6-octadiene-4, - diol.

  Examples of the unsaturated amine include those in which the hydroxyl group of the unsaturated alcohol is replaced with an amino group.

  Examples of unsaturated isocyanate esters include allyl isocyanate. In addition, low molecular weight polymers such as butadiene and isoprene (for example, those having a number average average molecular weight of about 500 to 10,000) or high molecular weight (for example, those having a number average average molecular weight of 10,000 or more) are added to maleic anhydride, Those obtained by adding phenols or those introduced with an amino group, carboxyl group, hydroxyl group, epoxy group or the like may be used.

  The unsaturated carboxylic acid is preferably maleic acid, fumaric acid or itaconic acid. Preferred unsaturated carboxylic acid derivatives are maleic anhydride and itaconic anhydride. As the unsaturated epoxy compound, glycidyl (meth) acrylate is preferable. The unsaturated alcohol is preferably 2-hydroxyethyl methacrylate.

Examples of (II) include saturated aliphatic polycarboxylic acids represented by the general formula (Q ¹ O) _m Q (COOQ ² ) _n (CONQ ³ Q ⁴ ) _k and derivatives thereof. Here, Q is a linear, branched or cyclic saturated hydrocarbon having 2 to 20 carbon atoms, Q ¹ is hydrogen, an alkyl group, an aryl group, an acyl group, or a carbonyldioxy group, and Q ² Is hydrogen, an alkyl group or aryl group having 1 to 20 carbon atoms, Q ³ and Q ⁴ are hydrogen, or an alkyl group or aryl group having 1 to 10 carbon atoms, m is 1, n a is an integer of 0 or more, n + k is an integer of 2 or more, k is an integer of 0 or more, (Q ¹ O) is located in α-position or β-position of the carbonyl group, of at least two carbonyl groups There are 2 to 6 carbon atoms in between. Q is preferably a linear, branched or cyclic saturated hydrocarbon having 2 to 10 carbon atoms. Q ¹ is preferably hydrogen. Q ² is preferably hydrogen, an alkyl group having 1 to 10 carbon atoms, or an aryl group. Q ³ and Q ⁴ are preferably hydrogen, an alkyl group having 1 to 6 carbon atoms, or an aryl group. More preferably, they are hydrogen, a C1-C4 alkyl group, or an aryl group. n + k is preferably 2 or 3.

  Examples of (II) include citric acid, malic acid, agaricic acid and the like. Details of these compounds are disclosed in JP-B-6-68071.

  As a method of graft-modifying a polar group-containing compound to a polyolefin resin, a melt extrusion method in which a kneading extruder is used to react in a molten state, or a polyolefin resin and a polar group-containing compound are dissolved in a good solvent and reacted. It may be modified by a known method such as a solution method. In these methods, an organic peroxide or the like may be used as an initiator in the graft reaction, or irradiation with ultraviolet rays or radiation may be performed.

  The thermoplastic resin composition of the present invention contains (A), (B) and (C), the content of (A) is 10 to 70% by weight, and the content of (B) is 5 to 50. The content of (C) is 1 to 40% by weight (provided that the total of (A), (B) and (C) is 100% by weight).

  The content of (A) in the thermoplastic resin composition of the present invention is preferably 15% by weight or more, more preferably 20% by weight or more, from the viewpoint of increasing the heat resistance and tensile strength of the thermoplastic resin composition. More preferably, it is 25% by weight or more. In addition, the content of (A) in the thermoplastic resin composition is preferably 60% by weight or less, more preferably 55% by weight or less, from the viewpoint of increasing the flexibility of the thermoplastic resin composition. Preferably it is 50 weight% or less.

  The content of (B) in the thermoplastic resin composition of the present invention is preferably 10% by weight or more, more preferably 25% by weight or more, from the viewpoint of enhancing the flexibility of the thermoplastic resin composition. More preferably, it is 20 weight% or more. The content of (B) in the resin composition is preferably 45% by weight or less, more preferably 40% by weight or less, from the viewpoint of increasing the heat resistance and tensile strength of the thermoplastic resin composition. More preferably, it is 35% by weight or less.

  The content of (C) in the thermoplastic resin composition of the present invention is preferably 3% by weight or more, more preferably 5% by weight, from the viewpoint of increasing the scratch resistance and tensile strength of the thermoplastic resin composition. It is above, More preferably, it is 10 weight% or more. The content of (C) in the resin composition is preferably 35% by weight or less, more preferably 30% by weight or less, and still more preferably, from the viewpoint of increasing the heat resistance of the thermoplastic resin composition. 25% by weight or less.

  The thermoplastic resin composition of the present invention is (D) when the total of (A), (B) and (C) is 100 parts by weight from the viewpoint of enhancing scratch resistance, vibration damping and flame retardancy. It is preferable to contain 5 to 500 parts by weight of an inorganic filler. The content of (D) is more preferably 10 to 400 parts by weight, still more preferably 20 to 300 parts by weight.

  Examples of the inorganic filler include glass flake, glass fiber, barium sulfate, red lead, metal fiber, kaolin, clay, silica, glass balloon, glass bead, mica, talc, calcium carbonate, titanium oxide, potassium titanate whisker, Examples thereof include barium sulfate, shirasu balloon, aerosil, aluminum hydroxide, and magnesium hydroxide. The inorganic filler is preferably a metal hydroxide represented by aluminum hydroxide or magnesium hydroxide from the viewpoint of enhancing the flame retardancy of the thermoplastic resin composition of the present invention. One inorganic filler may be used alone, or two or more inorganic fillers may be used in combination. Moreover, the surface of the inorganic filler may be modified.

  The thermoplastic resin composition of the present invention may be used in combination with a known resin or elastomer other than the copolymer, if necessary, as long as the object of the present invention is not impaired.

  Examples of the elastomer include natural rubber, polybutadiene, liquid polybutadiene, styrene-butadiene random copolymer rubber, styrene-butadiene block copolymer rubber, styrene-butadiene-styrene block copolymer rubber, and styrene-isoprene block copolymer. Rubber, styrene-isoprene-styrene block copolymer rubber, hydrogenated styrene-butadiene-styrene block copolymer rubber, hydrogenated styrene-isoprene-styrene block copolymer rubber, polyacrylonitrile rubber, acrylonitrile-butadiene copolymer rubber Partially hydrogenated acrylonitrile-butadiene copolymer rubber, butyl rubber, chloroprene rubber, fluorine rubber, chlorosulfonated polyethylene, silicone rubber, urethane rubber, isobutylene-isoprene copolymer Body rubber, halogenated isobutylene - isoprene, copolymer rubber.

  The thermoplastic resin composition of the present invention can be subjected to crosslinking such as sulfur crosslinking, peroxide crosslinking, metal ion crosslinking, silane crosslinking, resin crosslinking, and electron beam crosslinking, if necessary, by a known method. Examples of the crosslinking agent include sulfur, phenol resin, metal oxide, metal hydroxide, metal chloride, p-quinonedioxime, and bismaleimide-based crosslinking agent. The crosslinking agent can be used in combination with a crosslinking accelerator in order to adjust the crosslinking rate. Examples of the crosslinking accelerator include oxidizing agents such as red lead and dibenzothiazoyl sulfide. The crosslinking agent can be used in combination with a dispersing agent such as a metal oxide or stearic acid. Examples of the metal oxide include zinc oxide, magnesium oxide, lead oxide, calcium oxide and the like, preferably zinc oxide and magnesium oxide. The thermoplastic composition may be dynamically crosslinked in the presence of a crosslinking agent.

  The method for producing the thermoplastic resin composition of the present invention is not particularly limited. Examples of the production method include a method in which each component is kneaded by an ordinary kneading apparatus such as a rubber mill, a Brabender mixer, a Banbury mixer, a pressure kneader, a single screw or a twin screw extruder. The kneading apparatus may be either a closed type or an open type, but is preferably a closed type apparatus that can be replaced with an inert gas. The kneading temperature is usually 120 to 250 ° C, preferably 140 to 240 ° C. The kneading time depends on the type and amount of the components used and the type of the kneading apparatus, but is usually about 3 to 10 minutes when a kneading apparatus such as a pressure kneader or a Banbury mixer is used. In the kneading step, a method of kneading each component in a lump may be adopted, or a multistage division kneading method in which a part of each component is kneaded and then the remainder is added to continue kneading may be adopted. Good.

  The thermoplastic resin composition of the present invention is, for example, a rosin resin, a polyterpene resin, a synthetic petroleum resin, a coumarone resin, a phenol resin, and a xylene resin, as necessary, within a range that does not impair the object of the present invention. Further, it can be used in combination with other resins such as a styrene resin and an isoprene resin.

  Examples of the rosin resin include natural rosin, polymerized rosin, partially hydrogenated rosin, fully hydrogenated rosin, esterified products of these rosins (for example, glycerin ester, pentaerythritol ester, ethylene glycol ester and methyl ester), rosin derivatives ( For example, disproportionated rosin, fumarized rosin and lime rosin).

  Examples of the polyterpene resin include homopolymers of cyclic terpenes such as α-pinene, β-pinene and dipentene, copolymers of cyclic terpenes, copolymers of cyclic terpenes and phenolic compounds such as phenol and bisphenol. (For example, terpene-phenol resins such as α-pinene-phenol resin, dipentene-phenol resin and terpene-bisphenol resin), and aromatic modified terpene resins that are copolymers of cyclic terpenes and aromatic monomers.

The synthetic petroleum resins, for example, C ₅ fraction naphtha cracked oil, C ₆ -C ₁₁ fraction, other olefinic fractions homopolymer or a copolymer, the water of these homopolymers and copolymers Examples thereof include aliphatic petroleum resins, aromatic petroleum resins, alicyclic petroleum resins, and aliphatic-alicyclic copolymer resins that are additives. Examples of the synthetic petroleum resin further include a copolymer of naphtha cracked oil and the above terpene, and a copolymer petroleum resin that is a hydrogenated product of the copolymer.

Preferably the C ₅ fraction of naphtha cracked oil, isoprene, cyclopentadiene, 1,3-pentadiene, 2-methyl-1-butene, methylbutene such as 2-methyl-2-butene, 1-pentene, 2-pentene And pentenes such as dicyclopentadiene. As the C _{6 to} C ₁₁ fraction, preferably, indene, styrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, methylstyrenes such as α-methylstyrene, β-methylstyrene, methylindene, ethylindene Vinyl xylene and propenylbenzene. Other preferred olefinic fractions are butene, hexene, heptene, octene, butadiene, and octadiene.

  Examples of the phenolic resin include alkylphenol resins, alkylphenol-acetylene resins obtained by condensation of alkylphenol and acetylene, and modified products of these resins. Here, the phenolic resin may be any of a novolac resin obtained by methylolation of phenol with an acid catalyst, or a resol resin obtained by methylolation of an alkali catalyst.

  Examples of the xylene-based resin include a xylene-formaldehyde resin composed of m-xylene and formaldehyde, and a modified resin obtained by adding and reacting a third component thereto.

  Examples of the styrene resin include a low molecular weight polymer of styrene, a copolymer resin of α-methylstyrene and vinyltoluene, a copolymer resin of styrene, acrylonitrile, and indene.

The isoprene-based resin, for example, resins obtained by copolymerizing a C ₁₀ alicyclic compound and C ₁₀ chain compound is a dimer product of isoprene.

  The thermoplastic resin composition of the present invention includes an anti-aging agent, an antioxidant, an ozone degradation inhibitor, an ultraviolet absorber, a stabilizer such as a light stabilizer, an antistatic agent, a slip agent, and an internal release agent as necessary. Used in combination with additives such as colorants, dispersants, antiblocking agents, lubricants and antifogging agents, organic fillers such as carbon fibers and aramid fibers, and mineral oil softeners such as naphthenic oils and paraffinic mineral oils. May be.

  The thermoplastic resin composition of the present invention may be used in combination with a flame retardant, if necessary, as long as the object of the present invention is not impaired. Examples of the flame retardant include inorganic compounds such as antimony flame retardant, zinc borate, guanidine flame retardant, zirconium flame retardant, ammonium polyphosphate, ethylenebistris (2-cyanoethyl) phosphonium chloride, tris (tribromo Phenyl) phosphates, tris (tribromophenyl) phosphates, phosphate esters and compounds such as tris (3-hydroxypropyl) phosphine oxide, chlorinated paraffins, chlorinated polyolefins, chlorinated flame retardants such as perchlorocyclopentadecane, hexa Odors such as bromobenzene, ethylenebisdibromonorbornanedicarboximide, ethylenebistetrabromophthalimide, tetrabromobisphenol A derivatives, tetrabromobisphenol S, tetrabromodipentaerythritol System flame retardant, and the like. These flame retardants may be used alone or in combination of two or more.

  The thermoplastic resin composition of the present invention may be a foam obtained in combination with a foaming agent, if necessary. Examples of the foaming agent include inorganic foaming agents such as sodium bicarbonate, ammonium bicarbonate and ammonium carbonate, nitroso compounds such as N, N′-dinitrosopentamethylenetetramine, azo compounds such as azocarbonamide and azoisobutyronitrile, Examples thereof include sulfonyl hydrazides such as benzenesulfonyl hydrazine, p, p′-oxybis (benzenesulfonyl hydrazide), toluenesulfonyl hydrazide, and toluenesulfonyl hydrazide derivatives. The foaming agent may be used in combination with a foaming aid such as salicylic acid, urea, urea derivatives and the like.

  The thermoplastic resin composition of the present invention may be used in combination with a high-frequency processing aid such as a polar group-containing polymer, if necessary. Examples of the high-frequency processing aid include a copolymer of ethylene and at least one comonomer. Examples of the comonomer include monocarboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, and crotonic acid, dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, and citraconic acid, monoesters of the above dicarboxylic acids, and methyl methacrylate. Examples thereof include acrylic acid esters such as methacrylic acid esters, methyl acrylate and ethyl acrylate, vinyl esters of saturated carboxylic acids such as vinyl acetate and vinyl propionate, and ionomers of these acids and esters.

  The thermoplastic resin composition of the present invention may be used in combination with a tackifier as necessary. Examples of the tackifier include natural rosin resins such as rosin and dammar, modified rosin and derivatives thereof, terpene resins and modified products thereof, aliphatic hydrocarbon resins, aromatic hydrocarbon resins, alkylphenol resins, coumarone- Examples thereof include resins such as indene resins. Among these, terpenes such as terpene phenol and α-polyterpene are preferable. As terpenes, “YS Resin TO-105” and “Clearon” (trade names manufactured by Yashara Chemical Co., Ltd.), “Arcon”, “Esthegam” and “Pencel” (trade names manufactured by Arakawa Chemical Industries, Ltd.) Is mentioned. Among these, by adding a hydrogenated petroleum resin or a hydrogenated terpene resin, the scratch resistance of the thermoplastic resin composition of the present invention can be further improved, and (A), (B), (C) and the When the total amount of hydrogenated resins is 100% by weight, the preferred amount of hydrogenated resin added is 3 to 10% by weight.

  The thermoplastic resin composition of the present invention includes, for example, an extrusion method, a profile extrusion method, a multicolor extrusion method, a coating (core) extrusion method, an injection molding method, a compression molding method, a foam molding method, and a hollow molding method. Various molded products can be obtained by known molding methods such as a method, a powder molding method, a calendar molding method, a blow molding method, and an inflation method.

  Examples of the powder molding method include slush molding, fluid dipping, electrostatic coating, powder spraying, and powder rotation molding.

  Examples of the calendar forming method include a sheeting method capable of continuously producing a smooth sheet having a high thickness accuracy, a doubling method capable of continuously producing a sheet having a high thickness accuracy without a pinhole, and bonding a cloth and a sheet. A topping process that can continuously produce composites, a friction process that rubs the thermoplastic elastomer composition into the fabric for the purpose of improving adhesion, and a profiling process that can continuously mold the engraved pattern on the roll surface onto the sheet surface. Can be mentioned.

  Examples of the primary processing that has been molded by the above molding method include molded products such as pipes and joints, and products such as films, sheets, hoses, and tubes. These molded bodies can be subjected to a known surface treatment such as painting or vapor deposition.

  The above primary processed products are further bent, cut, cut, cut, punched, drawn, engraved, pressed, hot stamped, high frequency processed, ultrasonic processed, laminated, sewing / winding / hand knitting, vacuum forming, compressed air A final product can be obtained through processes such as molding, adhesion, welding, flocking, lining, slitting, printing, and surface coating.

  The thermoplastic resin composition of the present invention utilizes its excellent characteristics, for example, vehicle parts, electric / electronic equipment parts, electric wires, building materials, agriculture / fishery / horticultural supplies, chemical industrial supplies, civil engineering materials, industrial -It can be used for applications such as industrial materials, furniture, stationery, daily and miscellaneous goods, clothes, containers and packaging supplies, toys, leisure goods, and medical supplies.

  Examples of vehicle parts include automobile interior skins such as instrument panels, doors, pillars, and air bag covers, automobile exterior parts such as over fenders, crowding panels, roof rails, side moldings, hoses, tubes, gaskets, packing, weather strips, Various seal sponges, washer liquid drain tubes, cushion materials for fuel tanks, and bicycle parts.

Examples of the electrical / electronic equipment parts include electrical / mechanical parts, electronic parts, weak electrical parts, home appliance members, refrigerator supplies, lighting fixtures, and electrical covers.
Examples of the electric wires include plastic cables, insulated electric wires, and electric wire protective materials.

  Building materials include, for example, wall and ceiling materials such as ribs, baseboards, panels, tarpaulins, roof materials such as corrugated plates, fences and roof base materials, floor materials such as sill materials and tiles, joints, Waterproofing applications such as joint rods and waterproof sheets, ducts, cable ducts, prefabricated members, equipment and equipment parts such as septic tanks, architectural edges, architectural gaskets, carpet restraints, angles, and louvers Applications include industrial materials such as joiners and curing sheets.

  Examples of agricultural / fishery / horticultural supplies include agricultural house use.

  Examples of industrial and industrial materials include machine covers, machine parts, packing, gaskets, flanges, leather canvases, bolts, nuts, valves, metal protective films, and uneven hoses.

  Examples of furniture include cabinets, stools, sofas, mats, curtains, and tablecloths.

  Stationery includes, for example, card cases, writing instrument cases, accessories, key cases, cash card cases, stickers, labels, book covers, notebook covers, binders, notebooks, covers, files, cards, regular items, underlays, holders, magazine trays , Album, template, writing instrument axis.

  Daily and miscellaneous goods include, for example, bath lids, slats, buckets, clothes covers, duvet cases, umbrellas, umbrella covers, blinds, sewing tools, shelf boards, shelf holders, picture frames, apron, trays, tapes, strings, belts Kind, moth.

  Examples of the clothes include raincoats, goggles, rain gear sheets, children's leather coats, shoes, shoe covers, footwear, gloves, ski wear, hats, and auxiliary materials for hats.

  Examples of containers and packaging products include food containers, clothing packaging, packaging and packaging materials, cosmetic bottles, cosmetic containers, chemical bottles, food bottles, physics and chemistry bottles, detergent bottles, containers, caps, food packs, laminated films, industrial Shrink film for business use and wrap film for business use.

  Examples of medical supplies include an infusion bag, a continuous carrying peritoneal dialysis bag, and a blood bag.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
[1] Measurement of physical properties The physical properties of the present invention were measured by the following methods.
(1) Monomer unit content of copolymer (1-1) Monomer unit content of crystalline thermoplastic resin ¹ H using a nuclear magnetic resonance apparatus (trade name AC-250 manufactured by Bruker) -It calculated based on the measurement result of the NMR spectrum. The composition ratio of the ethylene monomer unit and the propylene monomer unit was calculated from the ratio between the spectral intensity of hydrogen derived from the methine unit and the methylene unit and the spectral intensity of hydrogen derived from the methyl unit.
(1-2) Monomer Unit Content of Amorphous α-Olefin Copolymer Using a nuclear magnetic resonance apparatus (trade name AC-250 manufactured by Bruker), ¹ H-NMR spectrum, ¹³ C-NMR Calculation was performed based on the measurement result of the spectrum. Specifically, in the ¹³ C-NMR spectrum, from the ratio of the spectral intensity of methyl carbon derived from the propylene monomer unit to the spectral intensity of methyl carbon derived from the 1-butene monomer unit, the propylene monomer unit and 1 -The composition ratio of the butene monomer unit was calculated, and then in the ¹ H-NMR spectrum, the ethylene unit was determined from the ratio of the spectral intensity of hydrogen derived from the methine unit and the methylene unit and the spectral intensity of hydrogen derived from the methyl unit The composition ratio of the body unit, the propylene monomer unit and the 1-butene monomer unit was calculated.
(2) Intrinsic viscosity [η]
The measurement was performed at 135 ° C. using an Ubbelohde viscometer. Adjusting the tetralin solution of the amorphous α-olefin polymer in which the concentration c of the amorphous α-olefin polymer per unit volume of the tetralin is 0.6, 1.0, 1.5 mg / ml, The intrinsic viscosity at 135 ° C. was measured. The measurement was repeated three times at each concentration, the average value of the three values obtained was taken as the specific viscosity (η _sp ) at that concentration, and the value obtained by extrapolating c of η _sp / c to zero was used as the intrinsic viscosity [η ]
(3) Molecular weight distribution It measured on the following conditions by the gel permeation chromatograph (GPC) method.
Equipment: 150C ALC / GPC manufactured by Waters
Column: Shodex Packed Column A-80M manufactured by Showa Denko KK Temperature: 140 ° C
Solvent: o-dichlorobenzene elution solvent flow rate: 1.0 ml / min Sample concentration: 1 mg / ml
Measurement injection volume: 400 μl
Molecular weight standard substance: Standard polystyrene detector: Differential refraction (4) Crystal melting peak and crystallization peak Measurement was carried out under the following conditions using a differential scanning calorimeter (DSC220C: input compensation DSC manufactured by Seiko Denshi Kogyo Co., Ltd.).
(I) About 5 mg of the sample was heated from room temperature to 200 ° C. at a rate of temperature increase of 30 ° C./min, and held for 5 minutes after completion of the temperature increase.
(Ii) Next, the temperature was decreased from 200 ° C. to −100 ° C. at a temperature decreasing rate of 10 ° C./min, and held for 5 minutes after completion of the temperature decrease. The peak observed in (ii) was a crystallization peak, and the presence or absence of a crystallization peak having a peak area of 1 J / g or more was confirmed.
(Iii) Next, the temperature was increased from −100 ° C. to 200 ° C. at a temperature increase rate of 10 ° C./min. The peak observed in (iii) is the melting peak of the crystal, and the presence or absence of a melting peak having a peak area of 1 J / g or more was confirmed.
(5) Melt flow rate (MFR)
According to JIS-K-7210, the measurement was performed under the conditions of a load of 21.18 N and a temperature of 230 ° C.
(6) Hardness A sheet having a thickness of 2 mm was prepared by press molding in accordance with JIS-K-6758. The Shore D hardness of the sheet was measured according to ASTM-D-2240.
(7) Tensile test Tensile strength (TB) and cutting of a dumbbell-shaped No. 3 type test piece prepared from a press sheet having a thickness of 2 mm in accordance with JIS-K-6251 at a tensile speed of 200 mm / min. The time elongation (EB) was measured.
(8) Scratch resistance test It tested in the following procedures.
(I) The surface of a press sheet having a thickness of 2 mm is subjected to a condition of a speed of 150 mm / min with a scratching needle applied with a load of 2N or 5N using a surface property measuring machine having a trade name of Tribogear manufactured by Shinto Kagaku. Scratched and scratched.
(Ii) The residual scratch depth after 24 hours from the operation of (i) was measured with a contact-type surface roughness meter whose name is Surfcom manufactured by Tokyo Seimitsu Co., Ltd.

[2] Material (1) Crystalline polypropylene-based resin PP-1 Crystalline propylene-ethylene copolymer (MFR = 2.5 g / 10 min, ethylene monomer unit content = 0.5 wt%) (hereinafter, (Referred to as resin A-1)
PP-2 crystalline propylene-ethylene copolymer (MFR = 1.5 g / 10 min, ethylene monomer unit content = 5 wt%) (hereinafter referred to as resin A-2)
PP-3 block polypropylene Sumitomo Noblen AD571 (manufactured by Sumitomo Chemical Co., Ltd., hereinafter referred to as Resin A-3)

(2) Amorphous ethylene-propylene-1-butene copolymer In a 100 L SUS polymerizer equipped with a stirrer, hydrogen was used as a molecular weight regulator, and ethylene, propylene and 1-butene were continuously used in the following manner. Thus, an ethylene-propylene-1-butene copolymer corresponding to the component (B) of the present invention was obtained.
From the bottom of the polymerization vessel, hexane as a polymerization solvent at a feed rate of 239 L / hr, ethylene at a feed rate of 3.27 kg / hr, propylene at a feed rate of 0.70 kg / hr, and 6.23 kg of 1-butene Each was continuously fed at a feed rate of / hour.
From the upper part of the polymerization vessel, the reaction mixture is continuously withdrawn so that the reaction mixture in the polymerization vessel maintains an amount of 100 L. From the lower part of the polymerization vessel, dimethylsilylene (tetramethylcyclopenta) is used as a component of the polymerization catalyst. Dienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride at a feed rate of 0.017 g / hr and triphenylmethyltetrakis (pentafluorophenyl) borate at a feed rate of 0.967 g / hr The triisobutylaluminum was continuously fed at a feeding rate of 1.984 g / hour.
The copolymerization reaction was carried out at 42 ° C. by circulating cooling water through a jacket attached to the outside of the polymerization vessel.
A small amount of ethanol is added to the reaction mixture continuously withdrawn from the top of the polymerization vessel to stop the polymerization reaction, followed by demonomerization and water washing, and then the solvent is removed by steam in a large amount of water. Thus, an ethylene-propylene-1-butene copolymer was obtained, and this was dried under reduced pressure at 80 ° C. for 1 day. The production rate of the copolymer was 3.06 kg / hour.
Table 1 shows the physical property evaluation results of the obtained ethylene-propylene-1-butene copolymer (hereinafter referred to as polymer B-1).

(3) Amorphous ethylene-propylene-1-butene copolymer In a 100 L SUS polymerizer equipped with a stirrer, hydrogen was used as a molecular weight regulator, and ethylene, propylene and 1-butene were continuously produced in the following manner. Thus, an ethylene-propylene-1-butene copolymer corresponding to the component (B) of the present invention was obtained.
From the lower part of the polymerization vessel, hexane was continuously supplied at a rate of 33.9 liter / hour, ethylene at 1.03 kg / hour, propylene at 13.26 kg / hour, and 1-butene at 8.02 kg / hour. On the other hand, the polymerization solution was continuously extracted from the upper portion of the polymerization vessel so that the polymerization solution in the polymerization vessel became 100 liters. As components of the polymerization catalyst, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and tri Isobutylaluminum was continuously fed into the polymerization vessel from the bottom of the polymerization vessel at a rate of 0.0201 g / hour, 0.1670 g / hour, and 6.1783 g / hour, respectively. The copolymerization reaction was performed at 54 ° C. by circulating cooling water through a jacket attached to the outside of the polymerization vessel. A small amount of ethanol is added to the polymerization solution extracted from the polymerization vessel to stop the polymerization reaction, and after demonomer removal and water washing, the solvent is removed with steam in a large amount of water, and the copolymer is taken out. Dried. By the above operation, ethylene-propylene-1-butene copolymer was obtained at a rate of 2.45 kg / hour.
Table 1 shows the physical property evaluation results of the obtained ethylene-propylene-1-butene copolymer (hereinafter referred to as polymer B-2).

(4) Amorphous propylene-1-butene copolymer In a 100 L SUS polymerizer equipped with a stirrer, hydrogen was used as a molecular weight regulator, and propylene and 1-butene were continuously copolymerized by the following method. Thus, a propylene-1-butene copolymer corresponding to the component (B) of the present invention was obtained.
From the lower part of the polymerization vessel, hexane as a polymerization solvent was continuously supplied at a supply rate of 100 L / hour, propylene was supplied at a supply rate of 24.00 kg / hour, and 1-butene was supplied at a supply rate of 1.81 kg / hour. Supplied to.
From the top of the polymerization vessel, the reaction mixture was continuously withdrawn so that the reaction mixture in the polymerization vessel maintained an amount of 100 L.
From the lower part of the polymerization vessel, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride as a component of the polymerization catalyst was fed at a feed rate of 0.005 g / hour. Triphenylmethyltetrakis (pentafluorophenyl) borate was continuously fed at a feed rate of 0.298 g / hr and triisobutylaluminum was fed at a feed rate of 2.315 g / hr.
The copolymerization reaction was carried out at 45 ° C. by circulating cooling water through a jacket attached to the outside of the polymerization vessel.
By adding ethanol to the reaction mixture continuously withdrawn from the top of the polymerization vessel to stop the polymerization reaction, followed by demonomer and water washing, and then removing the solvent with steam in a large amount of water, A propylene-1-butene copolymer was obtained and dried under reduced pressure at 80 ° C. for 1 day. The production rate of the copolymer was 7.10 kg / hour.
Table 1 shows the physical property evaluation results of the obtained propylene-1-butene copolymer (hereinafter referred to as polymer B-3).

(5) Graft-modified polyolefin 1
Polymer B-1 100 parts by weight, maleic anhydride 2.0 parts by weight, 1,3-bis (t-butylperoxyisopropyl) benzene 0.15 parts by weight, dicetylperoxydicarbonate 0.50 parts by weight Using a kneader Rabo plast mill (manufactured by Toyo Seiki Seisakusho) R-100, the mixture was kneaded at 230 ° C. for 5 minutes at a screw rotation speed of 100 rpm to obtain a graft-modified polyolefin. The polyolefin had an MFR of 13 g / 10 min and a maleic anhydride bond content of 0.4% by weight (hereinafter referred to as polymer C-1).
(6) Graft-modified polyolefin 2
A graft-modified polyolefin was obtained by the same method as (5) except that the polymer B-2 was used instead of the polymer B-1. The graft-modified polyolefin had an MFR of 43 g / 10 min and a maleic anhydride bond content of 0.4% by weight (hereinafter referred to as polymer C-2).
[Examples 1 to 4] and [Comparative Example 1]
Resin A, polymer B, polymer C, inorganic filler D, and optionally blended hydrogenated terpene resin with the blending amounts shown in Table 2 and hindered phenolic antioxidants (Irga manufactured by Ciba Specialty Chemicals) Noboru 1010) 0.1 part by weight and 0.1 part by weight of an aromatic phosphite antioxidant (Irgaphos 168, manufactured by Ciba Specialty Chemicals) Rabo plast mill (manufactured by Toyo Seiki Seisakusho) R-100 And kneading at 200 ° C. for 5 minutes at a screw rotation speed of 100 rpm to obtain a thermoplastic resin composition. The physical property measurement results of the obtained resin composition are shown in Table 2.

無機充填剤Ｄ キスマ５Ｂ（協和化学社製 水酸化マグネシウム）
水添テルペン樹脂 クリアロンＰ１３５（ヤスハラケミカル社製 水添テルペン樹脂）

Inorganic filler D Kisuma 5B (magnesium hydroxide manufactured by Kyowa Chemical Co., Ltd.)
Hydrogenated terpene resin Clearon P135 (hydrogenated terpene resin manufactured by Yashara Chemical Co., Ltd.)

Claims (5)

The following (A), (B) and (C) are contained, the content of (A) is 10 to 70% by weight, the content of (B) is 5 to 50% by weight, A thermoplastic resin composition having a content of 1 to 40% by weight (provided that the total of (A), (B) and (C) is 100% by weight).
(A) Thermoplastic resin (B) Containing monomer units derived from at least two olefins selected from the group consisting of ethylene, propylene and α-olefins having 4 to 20 carbon atoms, and having a molecular weight distribution (Mw / Amorphous α-olefin copolymer (C) having a Mn) of 1 to 4 (C) Graft-modified polyolefin The thermoplastic resin composition according to claim 1, wherein the amorphous α-olefin copolymer (B) satisfies the following requirements (1), (2), and (3).
(1) No melting peak is substantially observed by differential scanning calorimetry.
(2) The intrinsic viscosity is 0.1 to 10 dl / g.
(3) The total number of carbon atoms of the olefin is 6 or more, and the following relational expression is satisfied.
[Y / (x + y)] ≧ 0.5
(In the above relational expression, x represents the content (mol%) of the monomer unit derived from ethylene contained in (B), and y represents α having 4 to 20 carbon atoms contained in (B). -Represents the content (mol%) of monomer units derived from olefins, provided that the entire amorphous α-olefin copolymer (B) is 100 mol%. The graft-modified polyolefin (C) is a polyolefin obtained by graft-modifying the amorphous α-olefin copolymer (B) with at least one compound selected from the group consisting of (I) and (II). Item 3. The thermoplastic resin composition according to Item 1 or 2.
(I) Compound having (i) at least one carbon-carbon unsaturated bond and (ii) at least one polar group in the same molecule (II) In the same molecule, (iii) General formula (OR) (R represents a hydrogen atom, an alkyl group, an aryl group, an acyl group or a carbonyldioxy group) and (iv) at least two functional groups containing the same or different carbon-oxygen double bonds. Compound with The thermoplastic resin composition according to any one of claims 1 to 3, wherein the content of (D) below is 5 to 500 parts by weight with respect to a total of 100 parts by weight of (A), (B) and (C). object.
(D) Inorganic filler The thermoplastic resin composition according to claim 4, wherein the inorganic filler is a metal hydroxide.