JP4698135B2 - Olefin resin composition - Google Patents

Description

  The present invention relates to a novel olefin resin composition having an excellent balance between impact resistance and rigidity, comprising an olefin polymer component, a modified polymer component to which a functional group-containing atomic group is bonded, and an inorganic filler component.

  Olefin resins generally take advantage of their excellent moldability, mechanical strength, and economic characteristics, such as automobile parts such as bumpers, instrument panels, and glove boxes, and various home appliance parts such as televisions, VTRs, and washing machines. It is used in a wide range of fields as molding material. However, in recent years, functions and product sizes have been increasing more and more in various applications, and accordingly, there has been a demand for improvement in a high balance of physical properties (high rigidity, impact strength and molded product surface hardness).

  Attempts have been made to blend a hydrogenated product of a styrene-conjugated diene block copolymer with a polyolefin resin for the purpose of modifying the olefin resin. For example, as a method for obtaining a composition excellent in impact resistance, surface hardness, etc., it is described that two types of hydrogenated styrene-butadiene block copolymer and an inorganic filler are blended with a polypropylene resin. (For example, refer to Patent Document 1). Moreover, the composition formed by mix | blending the hydrogenated product of two types of styrene-conjugated diene block copolymers from which polypropylene resin and vinyl bond content differ as a composition excellent in impact resistance and heat-resistant deformation is described. (See, for example, Patent Document 2).

  In addition, a composition combining a modified olefin resin, an olefin resin, an elastomer, and an inorganic filler in order to obtain a highly rigid and high impact olefin resin is also known (see, for example, Patent Document 3). In addition, attempts have been made to improve the balance between the rigidity and impact strength of polypropylene using a composite filler of calcium carbonate and talc produced under specific conditions (see, for example, Patent Document 4). However, even in the composition obtained by the above method, the balance between impact strength and rigidity was not satisfactory.

Japanese Patent Laid-Open No. 4-170452 JP-A-6-32947 JP-A-7-118462 Japanese Patent Laid-Open No. 2002-80631

  An object of the present invention is to provide a resin composition having a further excellent balance between impact resistance and rigidity in a composition comprising an olefin polymer, a modified polymer and an inorganic filler.

  As a result of intensive studies on the improvement of the properties of a polymer comprising a conjugated diene or a copolymer comprising a vinyl aromatic hydrocarbon and a conjugated diene, or a composition of these hydrogenated product and olefin polymer. By combining an inorganic filler with a composition comprising an olefin polymer and a modified polymer to which a specific functional group has been added, and making the entire amount or part of the inorganic filler present in the modified polymer, The inventors have found that an olefin resin composition having an excellent balance between physical properties of impact and rigidity can be obtained, and the present invention has been completed.

That is, the present invention is as follows.
1. Component (1) 100 parts by weight of olefin polymer, Component (2) Conjugated diene polymer consisting of conjugated diene or hydrogenated product thereof, Random copolymer consisting of conjugated diene and vinyl aromatic hydrocarbon or hydrogenated product thereof 3 to 100 wt% of a modified polymer in which at least one functional group-containing atomic group is bonded to at least one polymer selected from block copolymers consisting of conjugated dienes and vinyl aromatic hydrocarbons or hydrogenated products thereof Part and component (3) In the resin composition comprising 1 to 60 parts by weight of the inorganic filler, the total amount of component (3) or a part thereof is present in component (2), and the component (2) in component (2) ( The volume fraction of 3) is 1 to 40%, and the olefin-based resin composition.

2. 2. The olefin resin composition as described in 1 above, comprising 0.01 to 20 parts by weight of a compound having reactivity with the functional group of component (2) and component (3) as component (4).
3. 2. The component (2) is a secondary modified polymer obtained by reacting the component (4) with 0.3 to 10 mol per equivalent of the functional group bonded to the component (2). Olefin-based resin composition.
4). 4. The olefin resin composition as described in 1 or 3 above, obtained by further melt-kneading a component (2) and component (3) in advance with a component (1).

5. 3. The olefin resin composition as described in 2 above, obtained by further melt-kneading a component (2), component (3) and component (4) in advance with a component (1).
6). 1 to 5 above, wherein the functional group-containing atomic group of component (2) is an atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group. The olefin resin composition in any one.
7). Component (4) is a compound having a functional group selected from a carboxyl group, an acid anhydride group, an isocyanate group, an epoxy group, a silanol group, and an alkoxysilane group. Resin composition.
8). The olefin system according to any one of 1 to 6 above, wherein the component (2) which is a modified polymer is a modified polymer in which at least one atomic group selected from the following formulas (1) to (14) is bonded. Resin composition.

(In the above formula, R ^{1 to} R ⁴ are carbon atoms having 1 to 24 carbon atoms having hydrogen or a hydrocarbon group having 1 to 24 carbon atoms, or a functional group selected from a hydroxyl group, an epoxy group, a silanol group, and an alkoxysilane group. R ⁵ is a hydrocarbon chain having 1 to 48 carbon atoms, or a hydrocarbon chain having 1 to 48 carbon atoms having a functional group selected from a hydroxyl group, an epoxy group, a silanol group, and an alkoxysilane group, and R ⁶ is hydrogen or C1-C8 alkyl group)

9. 4. The method for producing an olefin-based resin composition as described in 1 or 3 above, wherein a composition obtained by previously melt-kneading component (2) and component (3) is further melt-kneaded with component (1).
10. 3. The olefin-based resin composition as described in 2 above, wherein a composition obtained by previously melt-kneading the component (2), the component (3) and the component (4) is further melt-kneaded with the component (1). Manufacturing method.

  The olefin-based resin composition of the present invention modified with a specific modified polymer and an inorganic filler is excellent in the physical property balance between impact strength and rigidity.

The present invention will be specifically described below.
Although the kind of olefin resin which is the component (1) which comprises the olefin resin composition of this invention is not specifically limited, Ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4- An α-olefin homopolymer represented by methyl-1-pentene, 1-hexene, or the like, a mutual copolymer of these α-olefins, or a graft polymer onto the olefin resin can be used. Although it does not restrict | limit especially about the melt flow rate (MFR) of this polymer, The value measured based on ASTM-D238 is 0.001-200 g / 10min normally, Preferably it is the range of 0.01-100 g / 10min. It is best to be within.

  Examples of the olefin resin include polyethylene resins such as so-called low pressure polyethylene, medium pressure polyethylene, high pressure polyethylene, linear low density polyethylene, polypropylene, poly 1-butene, poly 3-methyl-1-butene, poly Examples thereof include poly α-olefin resins such as 4-methyl-1-pentene and ethylene-propylene block copolymers. Among these, for example, propylene-based resins such as homopolypropylene, random polypropylene, and block polypropylene are preferable. The above resins can be used alone or as a mixture in which a plurality of types are mixed, and can be used by appropriately selecting from commercially available resins.

  Component (2) constituting the olefin resin composition of the present invention is a conjugated diene polymer composed of a conjugated diene or a hydrogenated product thereof, a random copolymer composed of a conjugated diene and a vinyl aromatic hydrocarbon, or a hydrogenated product thereof. A modified polymer in which at least one functional group-containing atomic group is bonded to at least one polymer selected from a block copolymer consisting of a product, a conjugated diene and a vinyl aromatic hydrocarbon, or a hydrogenated product thereof.

  The modified polymer of a conjugated diene polymer comprising a conjugated diene or a hydrogenated product thereof used in the present invention is a conjugated diene homopolymer or a modified polymer having a vinyl aromatic hydrocarbon content of less than 5 wt%. The random copolymer composed of a conjugated diene and a vinyl aromatic hydrocarbon or a modified polymer thereof is a random copolymer having a vinyl aromatic hydrocarbon content of 5 to 95 wt%, preferably 10 to 90 wt%. The modified polymer. The vinyl bond in the conjugated diene polymer or random copolymer is not particularly limited, but is generally 5 to 90%, preferably 10 to 80%. Here, the vinyl bond content is a 1,2-bond among conjugated diene compounds incorporated in a polymer in a 1,2-bond, 3,4-bond and 1,4-bond bond mode. And the ratio of those incorporated by 3,4-bonds. The vinyl bonds in the modified polymer may be uniformly distributed in the polymer chain, may be distributed in a tapered shape, or two or more polymer blocks having different vinyl bonds may exist.

  The vinyl bond content can be arbitrarily changed by using a polar compound described later. Even if two or more random copolymer blocks having different vinyl aromatic hydrocarbon contents are present in the polymer chain in the modified copolymer of the random copolymer or its hydrogenated product, the conjugated diene weight is further increased. One or more combined blocks or hydrogenated products thereof may be present. The structure of the conjugated diene polymer or the hydrogenated product thereof and the random copolymer or the modified polymer of the hydrogenated product thereof may be linear or branched, and any mixture thereof. May be. A modified polymer of a conjugated diene polymer or a modified polymer of a random copolymer can be obtained by addition reaction of a modifying agent described later to the living terminal of the conjugated diene polymer or random copolymer.

The vinyl aromatic hydrocarbon content in the block copolymer consisting of a conjugated diene and vinyl aromatic hydrocarbon used in the present invention or a modified polymer thereof is preferably 5 wt% or more from the viewpoint of rigidity, impact resistance From the point of the improvement effect of property, it is 95 wt% or less, More preferably, it is 10-90 wt%, More preferably, it can be used in 15-85 wt%. When the vinyl aromatic hydrocarbon content in the block copolymer or a modified polymer of its hydrogenated product is 60 wt% or more, preferably 65 wt% or more, it has resin-like properties and is less than 60 wt%, preferably 55 wt%. The following cases have elastic properties.
Examples of the method for producing the block copolymer include Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-17879, Japanese Patent Publication No. 46-32415, Japanese Patent Publication No. 49-36957, Japanese Patent Publication No. 48-2423. And the methods described in JP-B-48-4106, JP-B-56-28925, JP-B-51-49567, JP-A-59-166518, JP-A-60-186777, and the like. It is done.

A modified polymer of the block copolymer used in the present invention can be obtained by addition reaction of the modifying agent described later to the living terminal of the block copolymer obtained by these methods. For example, as represented by the following general formula It has a simple structure.
(AB) _n -X, A- (BA) _n -X,
B- (A-B) _n -X, X- (A-B) _n ,
X- (AB) _n -X, XA- (BA) _n -X,
X-B- (AB) _n -X, [(BA) _n ] _m -X,
[(AB) _n ] _m- X, [(BA) _n- B] _m- X,
[(AB) _n -A] _m -X

(In the above formula, A is a polymer block mainly composed of vinyl aromatic hydrocarbons, and B is a polymer mainly composed of conjugated dienes. The boundary between the A block and the B block is always clearly distinguished. In addition, n is an integer of 1 or more, preferably an integer of 1 to 5. m is an integer of 2 or more, preferably an integer of 2 to 11. X is an atom having a functional group described later. The residue of the denaturing agent to which the group is bonded is bonded to the side chain of the A block and / or B block when X is added by the metallation reaction described below. The polymer chain structure may be the same or different.)

In the above, the polymer block A mainly composed of vinyl aromatic hydrocarbons preferably contains 50% by weight or more, more preferably 70% by weight or more of vinyl aromatic hydrocarbons and conjugated dienes. A polymer block and / or a vinyl aromatic hydrocarbon homopolymer block, the polymer block B mainly comprising a conjugated diene is preferably a conjugated diene containing more than 50 wt%, more preferably 60 wt% or more. A copolymer block of a diene and a vinyl aromatic hydrocarbon and / or a conjugated diene homopolymer block are shown.
The vinyl aromatic hydrocarbons in the copolymer block may be uniformly distributed or tapered. Further, in the copolymer part, a plurality of parts where the vinyl aromatic hydrocarbons are uniformly distributed and / or a part where the vinyl aromatic hydrocarbons are distributed in a tapered shape may coexist. The block copolymer used in the present invention may be an arbitrary mixture of block copolymers represented by the above general formula.

  In the present invention, the microstructure (ratio of cis, trans, vinyl) of the conjugated diene moiety in the block copolymer can be arbitrarily changed by using a polar compound or the like described later, and 1,3-butadiene as the conjugated diene Is used, the vinyl bond amount is preferably 5 to 90%, more preferably 10 to 80%. When isoprene is used as the conjugated diene or when 1,3-butadiene and isoprene are used in combination, The vinyl bond amount, which is the sum of the 1,2-vinyl bond and 3,4-vinyl bond, is preferably 3 to 80%, more preferably 5 to 70%. However, in the case of using a hydrogenated product as the block copolymer, the microstructure is preferably 10 to 80%, more preferably 25 to 25% when 1,3-butadiene is used as the conjugated diene. When isoprene is used as the conjugated diene or when 1,3-butadiene and isoprene are used in combination, the amount of vinyl bonds, which is the sum of 1,2-vinyl bonds and 3,4-vinyl bonds, is preferable. It is recommended to be 5 to 70%.

In the present invention, the conjugated diene is a diolefin having a pair of conjugated double bonds, such as 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3. -Butadiene, 1,3-pentadiene, 1,3-hexadiene and the like, and particularly common ones include 1,3-butadiene and isoprene. These may be used alone or in combination of two or more in the production of the polymer.
Examples of vinyl aromatic hydrocarbons include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, and vinylanthracene. However, styrene is a particularly common one. These may be used alone or in combination of two or more in the production of the polymer.

  In the present invention, when isoprene and 1,3-butadiene are used in combination as the conjugated diene of the conjugated diene polymer, random copolymer, or block copolymer, the mass ratio of isoprene and 1,3-butadiene is preferably 95. / 5 to 5/95, more preferably 90/10 to 10/90, still more preferably 85/15 to 15/85. In particular, when obtaining a resin composition excellent in low-temperature impact resistance, the mass ratio of isoprene and 1,3-butadiene is preferably 49/51 to 5/95, more preferably 45/55 to 10/90, More preferably, 40/60 to 15/85 is recommended. When isoprene and 1,3-butadiene are used in combination, a composition having a good balance between appearance characteristics and mechanical characteristics can be obtained even in molding at high temperatures.

  In the present invention, the ratio of the vinyl aromatic hydrocarbon polymer block incorporated in the block copolymer (referred to as the block ratio of vinyl aromatic hydrocarbon) is less than 50 wt%, preferably 5 when impact resistance is important. To 45 wt%, more preferably 10 to 40 wt%, and 50 wt% or more, preferably 50 to 97 wt%, more preferably 60 to 95 wt%, particularly preferably 70 to 92 wt% from the viewpoint of maintaining the rigidity of the molded product. It is recommended to adjust to%.

The block ratio of the vinyl aromatic hydrocarbon incorporated in the block copolymer is measured by a method of oxidatively decomposing the block copolymer with tertiary butyl hydroperoxide using osmium tetroxide as a catalyst (IM KOLTHOFF, et al., J. Polym. Sci. 1, 429 (1946)), a vinyl aromatic hydrocarbon polymer block component (however, an average degree of polymerization of about 30 or less vinyl aromatic hydrocarbon polymer component) Can be obtained from the following equation:
Vinyl aromatic hydrocarbon block ratio (wt%)
= (Mass of vinyl aromatic hydrocarbon polymer block in block copolymer / mass of total vinyl aromatic hydrocarbon in block copolymer) × 100

  In the present invention, the solvent used for producing the polymer includes aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane, octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, etc. Or a hydrocarbon solvent such as aromatic hydrocarbon such as benzene, toluene, ethylbenzene, and xylene. These may be used alone or in combination of two or more.

The organic lithium compound used in the production of the polymer is a compound in which one or more lithium atoms are bonded in the molecule, such as ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl. Examples include lithium, tert-butyl lithium, hexamethylene dilithium, butadienyl dilithium, isoprenyl dilithium, and amido lithium. These may be used alone or in combination of two or more. Further, the organolithium compound may be added in one or more divided portions during the polymerization in the production of the block copolymer.
In the present invention, polar compounds and randomization for the purpose of adjusting the polymerization rate during production of the polymer, changing the microstructure of the polymerized conjugated diene moiety, adjusting the reactivity ratio between the conjugated diene and the vinyl aromatic hydrocarbon, etc. Agents can be used. Examples of polar compounds and randomizing agents include ethers, amines, thioethers, phosphoramides, potassium or sodium salts of alkylbenzene sulfonic acids, potassium or sodium alkoxides, and the like.

Examples of suitable ethers are dimethyl ether, diethyl ether, diphenyl ether, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether. As amines, tertiary amine, trimethylamine, triethylamine, tetramethylethylenediamine, and other cyclic tertiary amines can be used. Examples of phosphine and phosphoramide include triphenylphosphine and hexamethylphosphoramide.
In the present invention, the polymerization temperature for producing the polymer is preferably −10 to 150 ° C., more preferably 30 to 120 ° C. The time required for the polymerization varies depending on the conditions, but is preferably within 48 hours, particularly preferably 0.5 to 10 hours. The polymerization atmosphere is preferably an inert gas atmosphere such as nitrogen gas. The polymerization pressure is not particularly limited as long as the polymerization pressure is in a range sufficient to maintain the monomer and solvent in a liquid phase within the above polymerization temperature range. Furthermore, it is preferable that impurities such as water, oxygen, carbon dioxide gas, etc. that inactivate the catalyst and living polymer are not mixed in the polymerization system.

  The modified polymer used in the present invention is obtained by adding a functional group-containing modifier to the living terminal of a polymer obtained by using an organolithium compound as a polymerization catalyst, and the polymer is subjected to hydroxyl group, carboxyl group, carbonyl group, thiocarbonyl. Group, acid halide group, acid anhydride group, carboxylic acid group, thiocarboxylic acid group, aldehyde group, thioaldehyde group, carboxylic acid ester group, amide group, sulfonic acid group, sulfonic acid ester group, phosphoric acid group, phosphoric acid Ester group, amino group, imino group, nitrile group, pyridyl group, quinoline group, epoxy group, thioepoxy group, sulfide group, isocyanate group, isothiocyanate group, silanol group, alkoxysilane, halogenated silicon group, tin halide group, Raw material having at least one functional group selected from an alkoxytin group, a phenyltin group, and the like Dan is modified polymer or its hydrogenated product is bound.

A method for obtaining a polymer or a hydrogenated product in which an atomic group having such a functional group is bonded is obtained by adding at least a functional group selected from the above functional groups to the polymer by an addition reaction with the living terminal of the polymer. Addition of a modifying agent having a functional group that generates a modified polymer to which one atomic group is bonded or a hydrogenated product thereof, or a modifying agent to which an atomic group protected by a known method is bonded It can be obtained by a reaction method.
As another method, a method in which an organic alkali metal compound such as an organic lithium compound is reacted (metalation reaction) with a polymer, and the above modifier is added to a polymer in which an organic alkali metal is added to the polymer. It is done. In the latter case, after obtaining a hydrogenated product of the polymer, a metallation reaction may be carried out, and the above modifier may be reacted. Depending on the type of modifier, the hydroxyl group or amino group may be an organometallic salt at the stage of reaction with the modifier, but in that case, treatment with a compound having active hydrogen such as water or alcohol is required. Thus, a hydroxyl group or an amino group can be obtained.

In the present invention, when the modifying agent is reacted with the living terminal of the polymer, a partially unmodified polymer may be mixed in the modified polymer of component (2). It is recommended that the proportion of the unmodified polymer mixed in the modified polymer of component (2) is preferably 70 wt% or less, more preferably 60 wt% or less, and even more preferably 50 wt% or less.
In the olefin resin composition of the present invention, the atomic group bonded to the modified polymer or the hydrogenated product thereof has at least one functional group selected from the above functional groups, and therefore has an affinity for an inorganic filler. The interaction is effectively expressed by physical affinity such as chemical bonds between functional groups present on the surface of the inorganic filler and hydrogen bonds between the mutual functional groups. An olefin-based resin composition having excellent properties intended by the present invention can be obtained by producing a chemical bond or physical affinity with the component (4).

Particularly preferred as the modified polymer used in the present invention or a hydrogenated product thereof is a modification in which an atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group is bonded. A polymer or a hydrogenated product thereof.
In the present invention, preferred atomic groups as atomic groups having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group are represented by the following general formulas (1) to (14). An atomic group selected from those indicated by.

(In the above formula, R ^{1 to} R ⁴ are carbon atoms having 1 to 24 carbon atoms having hydrogen or a hydrocarbon group having 1 to 24 carbon atoms, or a functional group selected from a hydroxyl group, an epoxy group, a silanol group, and an alkoxysilane group. R ⁵ is a hydrocarbon chain having 1 to 48 carbon atoms, or a hydrocarbon chain having 1 to 48 carbon atoms having a functional group selected from a hydroxyl group, an epoxy group, a silanol group, and an alkoxysilane group, and R ^{1 to} R. ^In the hydrocarbon group of ^{4 and} the hydrocarbon chain of R ⁵ , elements such as oxygen, nitrogen, and silicon may be bonded in a bonding mode other than a hydroxyl group, an epoxy group, a silanol group, and an alkoxysilane group. R ⁶ is hydrogen or an alkyl group having 1 to 8 carbon atoms)

In the present invention, in order to obtain a modified polymer having at least one atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group, or a hydrogenated product thereof. Examples of the modifier used are as follows.
For example, tetraglycidylmetaxylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl-p-phenylenediamine, tetraglycidyldiaminodiphenylmethane, diglycidylaniline, diglycidylorthotoluidine.

  Also, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxy Silane, γ-glycidoxypropyl tributoxysilane, γ-glycidoxypropyltriphenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldi Ethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycine Sidoxypropi Dimethylmethoxysilane, γ-glycidoxypropyldiethylethoxysilane, γ-glycidoxypropyldimethylethoxysilane, γ-glycidoxypropyldimethylphenoxysilane, γ-glycidoxypropyldiethylmethoxysilane, γ-glycidoxypropyl Methyldiisopropeneoxysilane, bis (γ-glycidoxypropyl) dimethoxysilane, and bis (γ-glycidoxypropyl) diethoxysilane.

  Furthermore, bis (γ-glycidoxypropyl) dipropoxysilane, bis (γ-glycidoxypropyl) dibutoxysilane, bis (γ-glycidoxypropyl) diphenoxysilane, bis (γ-glycidoxypropyl) ) Methylmethoxysilane, bis (γ-glycidoxypropyl) methylethoxysilane, bis (γ-glycidoxypropyl) methylpropoxysilane, bis (γ-glycidoxypropyl) methylbutoxysilane, bis (γ-glycid) Xylpropyl) methylphenoxysilane, tris (γ-glycidoxypropyl) methoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxymethyltrimethoxysilane, γ-methacryloxy Ethyltriethoxysilane, bis .gamma.-methacryloxypropyl) dimethoxysilane, tris (.gamma.-methacryloxypropyl) methoxy silane.

  Furthermore, β- (3,4-epoxycyclohexyl) ethyl-trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-triethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-tripropoxysilane, β- (3,4-epoxycyclohexyl) ethyl-tributoxysilane, β- (3,4-epoxycyclohexyl) ethyl-triphenoxysilane.

  Furthermore, β- (3,4-epoxycyclohexyl) propyl-trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-ethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-ethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldipropoxysilane , Β- (3,4-epoxycyclohexyl) ethyl-methyldibutoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldiphenoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylmethoxysilane , Β- (3,4-epoxycyclohex E) Ethyl-diethylethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylpropoxysilane, β- (3,4-epoxycyclohexyl) Ethyl-dimethylbutoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylphenoxysilane.

Further, β- (3,4-epoxycyclohexyl) ethyl-diethylmethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldiisopropeneoxysilane, 1,3-dimethyl-2-imidazolidinone, , 3-diethyl-2-imidazolidinone, N, N′-dimethylpropylene urea, N-methylpyrrolidone and the like.
By reacting the above modifier, the residue of the modifier to which an atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group is bonded is bonded. A modified polymer is obtained. When a functional group-containing modifier is added to the living end of the block copolymer, the living end of the block copolymer may be either the polymer block A or the polymer block B, but the balance between mechanical strength and impact resistance. In order to obtain an excellent composition, it is preferably bonded to the end of the polymer block A.

  In the present invention, the hydrogenated product of the modified polymer can be obtained by hydrogenating the modified polymer obtained above. The hydrogenation catalyst is not particularly limited and is conventionally known (1) A supported heterogeneous hydrogenation in which a metal such as Ni, Pt, Pd, or Ru is supported on carbon, silica, alumina, diatomaceous earth, or the like. A catalyst, (2) a so-called Ziegler-type hydrogenation catalyst using an organic acid salt such as Ni, Co, Fe, Cr or a transition metal salt such as acetylacetone salt and a reducing agent such as organic aluminum, (3) Ti, Ru, A homogeneous hydrogenation catalyst such as a so-called organometallic complex such as an organometallic compound such as Rh or Zr is used.

  Specific examples of the hydrogenation catalyst include Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-337970, Japanese Patent Publication No. 1-53851, The hydrogenation catalyst described in Japanese Utility Model Publication No. 2-9041 can be used. A preferred hydrogenation catalyst is a mixture with a titanocene compound and / or a reducing organometallic compound. As the titanocene compound, compounds described in JP-A-8-109219 can be used. Specific examples thereof include (substitution) such as biscyclopentadienyl titanium dichloride and monopentamethylcyclopentadienyl titanium trichloride. Examples thereof include compounds having at least one ligand having a cyclopentadienyl skeleton, an indenyl skeleton, or a fluorenyl skeleton. Examples of the reducing organometallic compound include organic alkali metal compounds such as organolithium, organomagnesium compounds, organoaluminum compounds, organoboron compounds, and organozinc compounds.

The hydrogenation reaction is preferably carried out in a temperature range of 0 to 200 ° C, more preferably 30 to 150 ° C. The pressure of hydrogen used for the hydrogenation reaction is preferably 0.1 to 15 MPa, more preferably 0.2 to 10 MPa, and still more preferably 0.3 to 5 MPa. The hydrogenation reaction time is preferably 3 minutes to 10 hours, more preferably 10 minutes to 5 hours. The hydrogenation reaction can be any of a batch process, a continuous process, or a combination thereof.
In the hydrogenated product of the modified polymer used in the present invention, the total hydrogenation rate of the unsaturated double bond based on the conjugated diene compound can be arbitrarily selected according to the purpose and is not particularly limited. 70% or more, preferably 80% or more, more preferably 90% or more of the unsaturated double bond based on the conjugated diene compound in the polymer may be hydrogenated, or only a part thereof is hydrogenated. Also good. When only a part is hydrogenated, the hydrogenation rate is preferably 10% or more and less than 70%, or 15% or more and less than 65%, or more preferably 20% or more and less than 60%.

Furthermore, in the present invention, in the hydrogenated polymer, the hydrogenation rate of the vinyl bond based on the conjugated diene before hydrogenation is preferably 85% or more, more preferably 90% or more, and still more preferably 95% or more. However, it is recommended for obtaining a resin composition having excellent thermal stability. Here, the hydrogenation rate of vinyl bonds refers to the proportion of vinyl bonds that are hydrogenated out of vinyl bonds based on conjugated dienes that are incorporated in the polymer before hydrogenation.
In addition, although there is no restriction | limiting in particular about the hydrogenation rate of the aromatic double bond based on the vinyl aromatic hydrocarbon in a random copolymer or a block copolymer, Preferably it is 50% or less, More preferably, it is 30% or less, More preferably, 20% or less is recommended. The hydrogenation rate can be known by a nuclear magnetic resonance apparatus (NMR).

The weight average molecular weight of the modified polymer used in the present invention is 30,000 or more from the viewpoint of mechanical strength and impact resistance of the olefin resin composition, and 1,000,000 or less from the viewpoint of workability and compatibility with the olefin resin. More preferably, it is 40,000 to 800,000, and more preferably 5 to 600,000.
In the present invention, the amount of vinyl bonds based on the conjugated diene compound in the modified polymer can be known using a nuclear magnetic resonance apparatus (NMR). The hydrogenation rate can also be known using the same apparatus. The weight average molecular weight of the modified polymer was measured by gel permeation chromatography (GPC), and the molecular weight of the peak of the chromatogram was determined from a standard polystyrene measurement curve (the peak molecular weight of standard polystyrene was used). Can be determined using).

In the modified polymer solution obtained as described above, the catalyst residue can be removed if necessary, and the modified polymer can be separated from the solution. Solvent separation methods include, for example, a method in which a polar solvent that is a poor solvent for a polymer such as acetone or alcohol is added to a solution after polymerization or hydrogenation to precipitate and recover the polymer, or a solution of a modified polymer Can be added to hot water with stirring and the solvent removed by steam stripping, or the polymer solution can be heated directly to distill off the solvent.
In addition, stabilizers, such as various phenol type stabilizers, phosphorus type stabilizers, sulfur type stabilizers, and amine type stabilizers, can be added to the modified polymer or hydrogenated product thereof used in the present invention.

In the olefin resin composition of the present invention, the modified polymer of the component (2) is added to 100 parts by weight of the olefin polymer of the component (1) in terms of the balance between rigidity and impact resistance of the resin composition. 3 to 100 parts by weight, preferably 5 to 80 parts by weight, more preferably 10 to 60 parts by weight.
As the inorganic filler used as the component (3) of the present invention, any inorganic filler can be used, and the shape thereof may be plate, spherical, fibrous, or indefinite. Specifically, natural silica, synthetic silica produced by a wet method or dry method, kaolin, mica, talc, clay, wollastonite, montmorillonite, zeolite, natural silicate, calcium silicate, aluminum silicate and other synthetic silicates, Metal hydroxides such as magnesium hydroxide, aluminum hydroxide, calcium hydroxide and barium hydroxide, metal oxides such as alumina, titanium oxide, magnesium oxide and zinc oxide, metal carbonates such as calcium carbonate and magnesium carbonate, Hydrate of inorganic metal compounds such as calcium carbonate and talc composite filler, basic magnesium carbonate, hydrotalcite, hydrated aluminum silicate, hydrated magnesium silicate, aluminum and bronze Metal powder such as carbon black It is. Among these, calcium carbonate and calcium carbonate / talc composite filler are preferable.

These filler components which are the component (3) may be those subjected to surface treatment with an organic carboxylic acid such as stearic acid, a surfactant, a silane coupling agent or the like. The filler component may be used alone or in combination of two or more. Various fillers can be appropriately selected from commercially available products.
In the olefin resin composition of the present invention, the amount of the inorganic filler of component (3) is 100 parts by weight of the olefin polymer of component (1) in terms of the balance between rigidity and impact resistance of the resin composition. 1 to 60 parts by weight, preferably 3 to 50 parts by weight, more preferably 5 to 40 parts by weight.

In the present invention, the compound of component (4) is a compound having a functional group having reactivity with the terminal functional group of component (2) which is a modified polymer or a hydrogenated product thereof and component (3) which is an inorganic filler. Preferably, it is a compound having a functional group selected from a carboxyl group, an acid anhydride group, an isocyanate group, an epoxy group, a silanol group, and an alkoxysilane group. The compounding amount of the component (4) is 0.01 parts by mass or more from the viewpoint of impact resistance of the olefinic resin composition with respect to 100 parts by mass of the olefin resin, and 20 parts by mass or less from the viewpoint of the effect of increasing the weight. is there. Preferably it is 0.02-10 mass parts, More preferably, it is 0.05-7 mass parts.
Specific examples of the compound of component (4) include carboxylate-containing compounds such as maleic acid, oxalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, carbaryl acid, cyclohexanedicarboxylic acid, Examples include aliphatic carboxylic acids such as cyclopentanedicarboxylic acid, aromatic carboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, trimesic acid, trimellitic acid, and pyromellitic acid.

Examples of the compound having an acid anhydride group include maleic anhydride, styrene-maleic anhydride oligomer, itaconic anhydride, pyromellitic anhydride, cis-4-cyclohexane-1,2-dicarboxylic anhydride, 1,2,4 , 5-benzenetetracarboxylic dianhydride, 5- (2,5-dioxytetrahydroxyfuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, and the like.
Examples of the compound having an isocyanate group include toluylene diisocyanate, diphenylmethane diisocyanate, polyfunctional aromatic isocyanate and the like. Examples of the compound having alkoxysilane include bis- (3-triethoxysilylpropyl) -tetrasulfane and ethoxysiloxane oligomer.

Examples of the compound having an epoxy group include tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl-m-xylenediamine, diglycidylaniline, ethylene glycol diglycidyl, propylene glycol diglycidyl, and terephthalic acid diglycidyl ester acrylate. is there.
Particularly preferred component (4) is a carboxylic acid having two or more carboxyl groups or an acid anhydride thereof, or a compound having two or more acid anhydride groups, isocyanate groups, epoxy groups, silanol groups, and alkoxysilane groups. For example, maleic anhydride, maleic anhydride-styrene oligomer, pyromellitic anhydride, 1,2,4,5-benzenetetracarboxylic dianhydride, toluylene diisocyanate, tetraglycidyl-1,3-bisaminomethylcyclohexane Etc.

In the present invention, a secondary modified polymer obtained by reacting the component (2) with the component (4) in advance can be blended with the component (1) to obtain an olefin resin composition. When the component (2) is reacted in advance with the component (2), the component (4) is 0.3 to 10 mol, preferably 0.4 to 5 mol per equivalent of the functional group bonded to the component (2). More preferably, it is 0.5-4 mol. Examples of the method of reacting the component (2) and the component (4) in advance include a melt kneading method described later and a method of reacting each component by dissolving or dispersing them in a solvent.
When the secondary modified polymer thus obtained is blended with the component (1) to form an olefin resin composition, the total amount of the secondary modified polymer and the component (1) is 100 parts by mass, Furthermore, 0.01-20 mass parts of a component (2) can be mix | blended.

  The olefin resin composition of the present invention is characterized by the total amount of component (3) or a part thereof in the modified polymer of component (2), particularly in terms of the balance between rigidity and impact resistance. The volume fraction of the component (3) in (2) is 1 to 40%, preferably 3 to 20%, more preferably 5 to 15%. The volume fraction of component (3) in component (2) is determined by measuring the number and size of component (2) and component (3) from an electron micrograph of the olefin resin composition, olefin resin The component (2) and the component (3) present in the component (2) are dissolved and eluted from the composition, and the ratio of the component (3) in the obtained dissolved and eluted component is measured, for example. can do. When the olefin-based resin composition of the present invention is obtained by melt-kneading a component (1) with a component (2) and component (3) previously melt-kneaded, the component (2) and component previously melt-kneaded The volume fraction may be grasped at the rate of (3).

  In the present invention, other optional additives can be blended as necessary. The type of additive is not particularly limited as long as it is generally used for blending thermoplastic resins and rubber-like polymers. Lubricants such as stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, ethylene bisstearamide, mold release agent, paraffinic process oil, naphthenic process oil, aromatic process oil, paraffin, organic poly Softeners and plasticizers such as siloxane and mineral oil, hindered phenolic antioxidants, antioxidants such as phosphorus heat stabilizers, hindered amine light stabilizers, benzotriazole UV absorbers, flame retardants, antistatic agents , Reinforcing agents such as organic fibers, glass fibers, carbon fibers, metal whiskers, colorants, other additives, or mixtures thereof, such as those described in “Rubber / Plastic Compounding Chemicals” (edited by Rubber Digest Co., Ltd.) .

The manufacturing method of the olefin resin composition of the present invention is not particularly limited, and a known method can be used. For example, a melt kneading method using a general blender such as a Banbury mixer, a single screw extruder, a twin screw extruder, a kneader, a multi-screw extruder, etc. A method of removing by heating is used. In the present invention, a melt kneading method using an extruder is preferred from the viewpoint of productivity and good kneading properties.
In addition, in the production of the olefin resin composition of the present invention, there is no restriction on the order of addition of each component, a method of mixing all components at once, a premix of arbitrary components, and then adding the remaining components, etc. Can be used. A particularly preferred method is a method in which component (2) and component (3) are melt-kneaded to prepare a masterbatch, and then component (1) and masterbatch are melt-kneaded, component (2), component (3) and component ( In this method, a master batch is prepared by melt kneading 4), and then the component (1) and the master batch are melt kneaded.

In the present invention, the melt-kneading temperature is generally preferably from 100 to 300 ° C, more preferably from the viewpoint of the melt viscosity of the polyolefin resin and the thermal deterioration of the modified block copolymer of component (2) or its hydrogenated product. It is 150-300 degreeC, More preferably, it is 180-300 degreeC.
The melt kneading time (or the average residence time of the melt kneading process) is the degree of kneading (dispersibility) and productivity, and the deterioration of the modified block copolymer of component (2) or its hydrogenated product or olefin resin. In general, the time is preferably 0.2 to 60 minutes, more preferably 0.5 to 30 minutes, and still more preferably 1 to 20 minutes.

The present invention will be described based on examples, but the present invention is not limited to these examples.
In the following examples, the properties of the polymer and its hydrogenated product were measured as follows.
(1) Styrene content It computed from the absorption intensity of 262 nm using the ultraviolet spectrophotometer (Hitachi UV200).
(2) Amount of vinyl bond and hydrogenation rate Measured using a nuclear magnetic resonance apparatus (manufactured by BRUKER, DPX-400).

(3) Molecular weight Measured by GPC (apparatus: LC10 manufactured by Shimadzu Corporation, column: Shimpac GPC805 + GPC804 + GPC804 + GPC803 manufactured by Shimadzu Corporation). Tetrahydrofuran was used as the solvent, and the measurement was performed at a temperature of 35 ° C. The molecular weight is a weight average molecular weight obtained by using a calibration curve (created using the peak molecular weight of standard polystyrene) obtained by measuring the molecular weight of the peak of the chromatogram from measurement of commercially available standard polystyrene.

(4) Ratio of unmodified polymer For the sample solution containing the modified polymer and the low-molecular-weight internal standard polystyrene by applying the property that the modified component is adsorbed on the GPC column using silica-based gel as a filler, the above (3) The ratio of the modified polymer with respect to the standard polystyrene in the chromatogram measured in the above and the ratio of the modified polymer with respect to the standard polystyrene in the chromatogram measured with the silica-based column GPC [DuPont: Zorbax] were compared. The amount of adsorption onto the silica column was measured from the difference between the two. The proportion of the unmodified polymer is the proportion that was not adsorbed on the silica column.

Moreover, the various measurements of the olefin resin composition followed the following measurements.
(1) Flexural modulus (MPa)
It measured based on JIS-K-7113.
(2) Izod impact strength with notch Measured according to JIS-K-7110.
(3) Measurement of volume fraction Using a photograph of the sample surface obtained by a scanning electron microscope (S4700, manufactured by Hitachi), the number and size of fillers present in the elastomer can be calculated using image analysis software (Image Pro Plus, Planetron). The volume fraction was determined by analyzing the product.

Moreover, the hydrogenation catalyst used for the hydrogenation reaction was prepared by the following method.
Hydrogenation catalyst I
Charge 1 liter of dried and purified cyclohexane to a nitrogen-substituted reaction vessel,
Bis (η5-cyclopentadienyl) titanium dichloride (100 mmol) was added, and an n-hexane solution containing 200 mmol of trimethylaluminum was added with sufficient stirring, followed by reaction at room temperature for about 3 days.
In the following examples, the following components were used as the respective components.
(1) Propylene resin (may be abbreviated as PP)
Homopolypropylene: PM600A (Sun Aroma)
Block polypropylene: K7014 (Chisso)
(2) Inorganic filler Calcium carbonate (Calsees: Kamijima Chemical) (Specific gravity: 2.8)
Composite filler (calcium carbonate / talc = 75/25% by weight)

[Example 1]
The autoclave with a stirrer and jacket was washed, dried, and purged with nitrogen, and a cyclohexane solution (concentration 20 wt%) containing 15 parts by mass of styrene purified in advance was added. Next, after adding n-butyllithium and tetramethylethylenediamine and polymerizing at 70 ° C. for 1 hour, a cyclohexane solution containing 80 parts by mass of butadiene purified in advance (concentration 20 wt%) is added and polymerized at 70 ° C. for 1 hour, A cyclohexane solution containing 15 parts by mass of styrene was added and polymerized at 70 ° C. for 1 hour.

  Thereafter, 1,3-dimethyl-2-imidazolidinone as a modifying agent was equimolarly reacted with n-butyllithium used for polymerization. The obtained block copolymer had a styrene content of 30 wt%, a vinyl bond content of the polybutadiene part of 42%, and a weight average molecular weight of 69,000. To the block copolymer obtained above, 100 ppm of a hydrogenation catalyst as Ti was added, and a hydrogenation reaction was performed for 1 hour at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. Thereafter, methanol was added, and then 0.3 parts by mass of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by mass of the block copolymer. Thus, a block copolymer (block copolymer-1) was obtained. In addition, the ratio of the unmodified block copolymer mixed in the block copolymer-1 was 20%.

Block copolymer-1 is blended with 1.5 moles of maleic anhydride per equivalent of functional group bonded to the block copolymer, and melt kneaded at 230 ° C. with a 30 mmφ twin screw extruder at a screw rotation speed of 100 rpm. Then, a secondary modified block copolymer (secondary modified block copolymer-1) of block copolymer-1 was obtained. The specific gravity of the secondary modified block copolymer-1 was 0.93.
75 parts by mass of secondary modified block copolymer-1 and 25 parts by mass of calcium carbonate were dry blended and kneaded in a twin screw extruder (TEX30) to prepare a block copolymer / calcium carbonate master batch. Next, 70 wt% of the block PP and 30 wt% of the master batch were kneaded with a twin screw extruder (TEX30) to obtain a resin composition. The obtained resin composition was injection-molded to measure notched Izod impact strength and bending strength. The physical properties of the resulting composition are shown in Table 1.

[Example 2]
75 parts by mass of secondary modified block copolymer-1 and 25 parts by mass of calcium carbonate were dry blended and kneaded in a twin screw extruder (TEX30) to prepare a block copolymer / calcium carbonate master batch. Next, 80 wt% of homo PP and 20 wt% of the master batch were kneaded with a twin screw extruder (TEX30) to obtain a resin composition. The obtained resin composition was injection-molded to measure notched Izod impact strength and bending strength. The physical properties of the resulting composition are shown in Table 1.

[Example 3]
75 parts by mass of secondary modified block copolymer-1 and 25 parts by mass of composite filler were dry blended and kneaded by a twin screw extruder (TEX30) to prepare a block copolymer / composite filler master batch. Next, 70 wt% of homo PP and 30 wt% of the master batch were kneaded with a twin screw extruder (TEX 30) to obtain a resin composition. The obtained resin composition was injection-molded to measure notched Izod impact strength and bending strength. The physical properties of the resulting composition are shown in Table 1.
Preparation of the composite filler was performed using calcium carbonate (average particle size 1.4 μm (Sankyo Seisaku # 2300)) and talc (particle size 3.2 μm (Katsumiyama Mining Co., Ltd. SK-2)). For the mixing of fillers (mixing weight ratio: calcium carbonate / talc = 3/1), a Henschel mixer was used, and a mixed filler was prepared using stearic acid as a surface modifier.

[Comparative Example 1]
A resin composition was obtained in the same manner as in Example 1 except that EPDM (X3012P: Mitsui Chemicals) was used instead of the secondary modified block copolymer-1. The physical properties of the resulting composition are shown in Table 1.
[Comparative Example 2]
Instead of the secondary modified block copolymer-1, a hydrogenated product of the unmodified block copolymer obtained in the same manner as in Example 1 except that no modifier is reacted (block copolymer-2) A resin composition was obtained in the same manner as in Example 2 except that was used. The physical properties of the resulting composition are shown in Table 1.
From the results of Examples 1 to 3 and Comparative Examples 1 and 2, it can be seen that the olefin-based resin composition of the present invention has an excellent balance between flexural modulus and impact resistance.

  The olefin resin composition of the present invention is excellent in the balance between rigidity and impact resistance. The resin composition of the present invention can be processed into molded products of various shapes by injection molding, extrusion molding, etc., taking advantage of these characteristics, and various containers such as automobile parts (automobile interior materials, automotive exterior materials), food packaging containers, etc. It can be used for household appliances, medical equipment parts, industrial parts, toys and the like.

Claims (2)

Component (1) 100 parts by weight of an olefin polymer,
Component (2) Conjugated diene heavy polymer comprising conjugated diene or hydrogenated product thereof, random copolymer comprising conjugated diene and vinyl aromatic hydrocarbon or hydrogenated product thereof, and block copolymer comprising conjugated diene and vinyl aromatic hydrocarbon At least one atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group is bonded to at least one polymer selected from a polymer or a hydrogenated product thereof. in the method for manufacturing the modified polymer 3-100 weight parts and <br/> component (3) inorganic filler resin composition comprising 1 to 60 parts by weight and,
The manufacturing method of the olefin resin composition which melt-kneads component (2) and component (3) previously, produces a masterbatch, and also melt-kneads with component (1). Component (1) 100 parts by weight of an olefin polymer,
Component (2) Conjugated diene heavy polymer comprising conjugated diene or hydrogenated product thereof, random copolymer comprising conjugated diene and vinyl aromatic hydrocarbon or hydrogenated product thereof, and block copolymer comprising conjugated diene and vinyl aromatic hydrocarbon At least one atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group is bonded to at least one polymer selected from a polymer or a hydrogenated product thereof. 3 to 100 parts by weight of the modified polymer
Component (3) Inorganic filler 1 to 60 parts by weight and <br/> component (4) a carboxyl group, acid anhydride group, an isocyanate group, an epoxy group, a compound having a functional group selected from a silanol group and an alkoxysilane group 0 In the manufacturing method of the resin composition which consists of 0.01-20 weight part,
A method for producing an olefin-based resin composition in which component (2), component (3) and component (4) are previously melt-kneaded to prepare a master batch, and further melt-kneaded with component (1).