JP2007056145A - Thermoplastic resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which comprises an elastomer/a finely dispersed laminar clay mineral/a thermoplastic resin, uses a modified elastomer having one or more functional group-containing atom groups at one or more polymer terminals as the elastomer, and has excellent rigidity and impact resistance. <P>SOLUTION: This thermoplastic resin composition is characterized by comprising (a) 100 pts.wt. of a thermoplastic resin, (b) 1 to 100 pts.wt. of a modified elastomer produced by binding at least one functional group-containing atom group to the terminal of a polymer selected from conjugated dienic polymers comprising conjugated dienes or their hydrogenation products, random conjugated dienic polymers comprising conjugated dienes and vinyl aromatic hydrocarbons or their hydrogenation products, and block conjugated dienic polymers comprising conjugated dienes and vinyl aromatic hydrocarbons or their hydrogenation products, (c) a laminar clay mineral in an amount of 1 to 30 pts.wt. per 100 pts.wt. of the component (b), (d) an olefinic rubbery polymer, and (e) at least one elastomer polymer selected from block copolymers comprising conjugated dienes and vinyl aromatic hydrocarbons, and their hydrogenation products. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a thermoplastic resin composition, and more particularly to a thermoplastic resin composition comprising an elastomer / layered clay mineral / thermoplastic resin in which a layered clay mineral is exfoliated and finely dispersed. The present invention relates to a thermoplastic resin composition having excellent rigidity and impact resistance, obtained by using a specific modified elastomer having a functional group added to the terminal portion and a layered viscosity mineral.

Conventionally, attempts have been made to mix various elastomers and inorganic fillers in order to improve various properties such as mechanical strength and impact resistance of thermoplastic resins. When a conventionally used inorganic filler is used, the resulting thermoplastic resin composition has problems such as high specific gravity, lower fluidity, and lower interfacial strength with rubber. Improvement is needed. In recent years, a composition having a sufficient modification effect even by a small addition amount by delaminating a layered clay mineral and finely dispersing a nanolayered mineral having a high aspect ratio has been studied. When using the above lamellar clay mineral, it is a technical problem to delaminate the lamellar clay mineral to the nano-order, but simply by mixing the lamellar clay mineral with a nonpolar elastomer such as a styrene elastomer, No delamination of the layered clay mineral occurs.
As a method for finely dispersing the layered clay mineral, for example, Patent Documents 1, 2, 3, and 4 describe an organic clay method in which inorganic ions of the layered clay mineral are substituted with organic ammonium ions, and Patent Document 5 describes an organophosphonium cation modification. A quality clay method has been proposed. However, a sufficient modification effect cannot be obtained only by organically treating the layered clay mineral and improving the affinity with the polymer.

  Various improvements have also been made on the polymer side to enhance the interaction with the layered clay mineral. For example, Patent Document 6 uses a polymer containing a functional group in the polymer main chain, a cross-linking agent and an organic layered clay mineral, Patent Document 7 uses rubber having an epoxy group in the polymer main chain, and Patent Document 8 uses a main polymer. Use of halogenated butyl rubber in the chain polymer, Patent Document 9 grafted with maleic anhydride on the main chain, Patent Documents 10, 11, 12, and 13 grafted maleic anhydride on the main chain Techniques using styrenic elastomers are disclosed. However, when a functional group is introduced into the polymer main chain, delamination of the layered clay mineral becomes insufficient because the functional group cannot enter between layers of the layered clay mineral due to steric hindrance of the main polymer main chain. . In addition, when a functional group is introduced into the polymer main chain, it is necessary to introduce a large amount of functional group into the polymer main chain. As a result, coloring of the composition, deterioration of thermal stability, odor, gel formation, etc. Quality issues arise and complex manufacturing processes are required to tune such modified polymers.

Japanese Patent Laid-Open No. 10-81785 JP-A-1-198645 JP 2004-250245 A JP 2004-155848 A JP-T-2001-523278 Japanese Patent Laid-Open No. 11-181309 JP 2004-250473 A JP 2004-155912 A JP 2004-204204 A Japanese Patent Application Laid-Open No. 2004-039459 JP 2004-83612 A JP 2004-75992 A JP-A-8-12883

  The present invention relates to a thermoplastic resin composition, and more particularly to a thermoplastic resin composition composed of elastomer / finely dispersed layered clay mineral / thermoplastic resin. Specifically, an object of the present invention is to provide a thermoplastic resin composition having excellent rigidity and impact resistance by using a modified elastomer having a functional group-containing atomic group at the polymer terminal.

The present inventors include a conjugated diene polymer comprising a conjugated diene or a hydrogenated product thereof, a random copolymer comprising a conjugated diene and a vinyl aromatic hydrocarbon or a hydrogenated product thereof, and a conjugated diene and a vinyl aromatic hydrocarbon. The layered clay mineral is delaminated by using a modified elastomer in which at least one functional group-containing atomic group is bonded to a terminal portion of a polymer selected from a block copolymer or a hydrogenated product thereof and a layered viscosity mineral The inventors have found that the dispersion is finely dispersed, and that the thermoplastic resin composition has excellent properties in various properties, and has completed the present invention.
That is, the present invention is as follows.
(A) 100 parts by weight of thermoplastic resin (b) Conjugated diene polymer comprising conjugated diene or hydrogenated product thereof, random copolymer comprising conjugated diene and vinyl aromatic hydrocarbon or hydrogenated product thereof, conjugated diene 1 to 100 parts by weight of a modified elastomer in which at least one functional group-containing atomic group is bonded to a terminal part of a polymer selected from a block copolymer made of vinyl aromatic hydrocarbon or a hydrogenated product thereof (c) layered The clay mineral is (b) 1 to 60 parts by weight per 100 parts by weight (d) 100 parts by weight or less of an olefin-based rubbery polymer (e) a block copolymer consisting of a conjugated diene and a vinyl aromatic hydrocarbon or its water The present invention provides a thermoplastic resin composition comprising 100 parts by weight or less of at least one elastomer polymer selected from the additives.

  The thermoplastic resin composition of the present invention has excellent mechanical properties, heat resistance, impact resistance and the like, and can be used as a wide range of materials.

Hereinafter, the present invention will be described in detail.
Component (a) thermoplastic resin constituting the present invention is an aromatic resin such as styrene resin, olefin resin, polyester such as polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyphenylene ether (PPE), polyphenylene sulfide (PPS), etc. Examples thereof include resin, polyamide such as 6.6 nylon and 6 nylon, methacrylic resin, acrylic resin, and ethylene vinyl acetate copolymer (EVA).
Styrene resins include polystyrene, rubber reinforced polystyrene (high impact polyester), block copolymer resins of conjugated diene compounds and vinyl aromatic compounds and their hydrogenated products, acrylonitrile / styrene copolymers (AS resins), styrene / Styrene / methacrylic acid ester copolymer such as methyl methacrylate copolymer (MS resin), acrylonitrile / butadiene / styrene terpolymer (ABS resin), rubber reinforced MS resin, maleic anhydride / styrene copolymer, Examples thereof include maleic anhydride / acrylonitrile / styrene terpolymer, acrylonitrile / α-methylstyrene copolymer, methacrylonitrile / styrene copolymer, methyl methacrylate / acrylonitrile / styrene terpolymer.

  Examples of olefin resins include homopolymers such as polyethylene (PE) and polypropylene (PP), blocks with butene, hexene, octene, etc., random copolymers, polymethylpentene, polybutene-1, and propylene / butene-1. Examples thereof include polymers, chlorinated polyolefins, ethylene / methacrylic acid and ester copolymers thereof, styrene / acrylic acid and ester copolymers thereof, and ethylene / propylene copolymers (EPR). Examples of the methacrylic resin include polymethyl methacrylate (PMMA), methyl methacrylate / methacrylic acid copolymer, and the like. Of the above, styrene resins and olefin resins are preferable, and polyolefin resins are particularly preferable.

  Examples of the polyolefin resin include polypropylene resin. The polypropylene-based resin is mainly composed of propylene, and if necessary, at least one selected from ethylene, an α-olefin having 4 to 12 carbon atoms, such as 1-butene, 1-octene, isobutylene, 4-methyl-1-pentene and the like. Resin obtained by polymerizing with a monomer, including propylene homopolymer, propylene block copolymer, propylene random copolymer, or a mixture thereof, and those having different molecular weights and compositions. It may be a mixture. Moreover, it is preferable that the melt flow rate (JIS K7210 L condition) of the polypropylene resin used for this invention exists in the range of 0.1-200 g / 10min.

Component (b) constituting the thermoplastic resin composition of the present invention is a modified elastomer in which at least one functional group-containing atomic group is bonded to a terminal portion of a polymer having a specific structure. In the case of a linear elastomer, the “end portion of the polymer” used in the present invention is one end or both ends, and in the case of a branched elastomer, all ends of each end of the branch, or at least one end. Part.
As the first type of modified elastomer in the present invention, a modification in which at least one functional group-containing atomic group is bonded to a terminal portion of a conjugated diene polymer composed of a conjugated diene or a hydrogenated polymer thereof. It is an elastomer. The vinyl bond content in the conjugated diene polymer is not particularly limited, and the vinyl bonds may be uniformly distributed in the polymer chain, distributed in a tapered shape, or polymer blocks having different vinyl bonds. There may be two or more. In the present invention, the “vinyl bond content” is a conjugated diene compound that is incorporated in a polymer in a 1,2-bond, 3,4-bond, or 1,4-bond bond mode. It is the ratio of those incorporated by 2-bond and 3,4-bond.

  As the second type of modified elastomer in the present invention, at least one functional group-containing atomic group is bonded to the end of a random copolymer composed of a conjugated diene and a vinyl aromatic hydrocarbon or a hydrogenated polymer thereof. Modified elastomer. The modified elastomer preferably has a vinyl aromatic hydrocarbon content of 5 to 95 wt%, more preferably 10 to 90 wt%. The amount of vinyl bonds in the modified elastomer is not particularly limited, but is generally 5 to 90 wt%, preferably 10 to 80 wt%. When it is less than 5 wt%, when it is used as a hydrogenated product, crystals are generated in the modified elastomer, and the performance as the elastomer tends to decrease. When it exceeds 90 wt%, the resulting thermoplastic resin The thermal stability of the composition tends to decrease.

  As the third type of modified elastomer in the present invention, at least one functional group-containing atomic group is bonded to the terminal portion of the block copolymer composed of conjugated diene and vinyl aromatic hydrocarbon or hydrogenated product thereof. It is a modified block copolymer. The vinyl aromatic hydrocarbon content in the modified block copolymer is preferably 5 to 90 wt%, more preferably 7 to 80 wt%, and most preferably 10 to 75 wt%. The vinyl bond in the modified block copolymer is not particularly limited, but is generally 5 to 90 wt%, preferably 7 to 80 wt%. If it is less than 5%, when it is used as a hydrogenated product, crystals are generated in the modified block copolymer, and the performance as an elastomer tends to be reduced. If it exceeds 90 wt%, the thermal stability of the composition is low. It tends to decrease. 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. The modified block copolymer used in the present invention has a structure represented by, for example, the following general formula.

(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. 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 a functional group having a functional group described later. (Indicates a basic atomic group. The structure of the polymer chain bonded to X 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. In addition, the modified block copolymer portion may coexist with a plurality of portions where vinyl aromatic hydrocarbons are uniformly distributed and / or portions where tapes are distributed. The modified block copolymer used in the present invention may be an arbitrary mixture of block copolymers represented by the above general formula.

In particular, the modified block copolymer used in the present invention includes an SBS type composed of styrene block-conjugated butadiene block-styrene block, SBBS obtained by partially hydrogenating the conjugated diene block portion of the SBS type, or fully hydrogenated SEBS. The type of modified block copolymer is preferable in terms of balance of various physical properties.
In particular, a modified block copolymer in which a functional group-containing atomic group is bonded to a terminal portion of a block portion mainly composed of styrene has a block portion mainly composed of styrene having a high interaction with the layered clay mineral, And since the functional group-containing atomic group is bonded to the end of the block part, the end part of the modified block copolymer is easily inserted between the layers of the layered clay mineral, facilitating delamination of the layered clay mineral. Is done. Such an elastomer composition of a modified block copolymer and a layered clay mineral has a layered clay in which a phase mainly composed of styrene and a phase composed of a conjugated diene or a hydrogenated product thereof are microphase-separated and exfoliated. It is a hybrid elastomer composition in which the mineral is peeled to a thickness of about the microphase and the styrene-based phase interacts with the nano-layered clay mineral, and is an extremely excellent machine for compositions with thermoplastic resins. Balance of mechanical strength and impact resistance.

  The conjugated diene in the present invention 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, Examples of 3-butadiene, 1,3-pentadiene, and 1,3-hexadiene are 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.

  The modified elastomer used in the present invention is a modified elastomer in which at least one functional group-containing atomic group is bonded to the terminal portion of the polymer. Specifically, a hydroxyl group, a carboxyl group, a carbonyl group, a thiocarbonyl group, an acid halide group, an acid anhydride group, a carboxylic acid group, a thiocarboxylic acid group, an aldehyde group, a thioaldehyde group, a carboxylic acid at the end of the polymer Ester group, amide group, sulfonic acid group, sulfonic acid ester group, phosphoric acid group, phosphoric ester group, amino group, imino group, nitrile group, pyridyl group, quinoline group, epoxy group, thioepoxy group, sulfide group, isocyanate group Modified elastomer having bonded thereto a functional group having at least one functional group selected from an isothiocyanate group, a silanol group, an alkoxysilane group, a halogenated silicon group, a halogenated tin group, an alkoxytin group, a phenyltin group, etc. In particular, amino groups, imino groups, hydroxyl groups, carboxyl groups, acid anhydrides , Epoxy group, silanol group, alkoxysilane group, preferred from the viewpoint of affinity with the layered clay mineral.

Next, a method for producing the modified elastomer which is the component (b) in the present invention will be described.
Solvents used for the polymerization of the modified elastomer in the present invention include aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane, octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane. Hydrocarbon solvents such as alicyclic hydrocarbons such as aromatic hydrocarbons such as benzene, toluene, ethylbenzene, and xylene can be used. These may be used alone or in combination of two or more.

  As a catalyst used for polymerization of the modified elastomer, an organolithium compound is preferable. When the organolithium compound is a conjugated diene or vinyl aromatic hydrocarbon in the present invention as a monomer, the terminal portion of the polymer has a living property, and the functional group is contained in the terminal portion, which is a feature of the present invention. Bonds of atomic groups are easily generated. The organolithium compound 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 lithium, tert-butyl lithium, Hexamethylene dilithium, butadienyl dilithium, isoprenyl dilithium, amido lithium and the like can be mentioned. These may be used alone or in combination of two or more. The organolithium compound may be added in one or more divided portions during the polymerization of the modified elastomer.

During polymerization of the modified elastomer used in the present invention, adjustment of the polymerization rate during production of the polymer, change of the microstructure of the polymerized conjugated diene moiety, adjustment of the reactivity ratio of the conjugated diene and the vinyl aromatic hydrocarbon, etc. Polar compounds and randomizing agents can be used for the purpose. 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 the phosphine and phosphoramide include triphenylphosphine and hexamethylphosphoramide, and tetrahydrofuran and tetramethylethylenediamine are particularly preferred in the purification process in the production process.

  In the present invention, the polymerization temperature for producing the modified elastomer 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 elastomer used in the present invention includes, for example, a hydroxyl group, a carboxyl group, a carbonyl group, a thiocarbonyl group, an acid halide group, an acid anhydride group, a carboxylic acid at the living terminal of a polymer obtained using an organolithium compound as a polymerization catalyst. 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, nitrile group, pyridyl group, quinoline group A functional group selected from an epoxy group, a thioepoxy group, a sulfide group, an isocyanate group, an isothiocyanate group, a silanol group, an alkoxysilane group, a halogenated silicon group, a halogenated tin group, an alkoxytin group, a phenyltin group, and / or the like. An atomic group having at least one of these derivatives That by adding a functional group-containing modifier obtained. In the present invention, the modified elastomer obtained by this method is defined as a primary modified elastomer.

In the modified elastomer used in the present invention, when the functional group modifier is reacted with the living terminal of the polymer, an unmodified elastomer polymer that is not partially modified may be mixed. It is recommended that the proportion of elastomer is preferably 60 wt% or less, more preferably 50 t% or less. Examples of the functional group-containing modifier used in the method for producing a primary modified elastomer in the present invention include amino group, imino group, hydroxyl group, carboxyl group, acid anhydride group, epoxy group, silanol group, alkoxysilane group, and / or their It is particularly preferable to use a modifying agent that is a derivative.
The following are mentioned as a modifier used in order to obtain the primary modified elastomer used by this invention. For example, tetraglycidyl metaxylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl-p-phenylenediamine, tetraglycidyldiaminodiphenylmethane, diglycidylaniline, diglycidylorthotoluidine, 4,4'-diglycidyl Polyepoxy compounds such as diphenylmethylamine, 4,4′-diglycidyldibenzylmethylamine, and diglycidylaminomethylcyclohexane.

  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, N- (1,3-dimethylbutylidene) -3 -(Triethoxysilyl) -1-propanamine. Furthermore, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N, N′-dimethylpropyleneurea, 1,3-diethyl-2-imidazolidinone, 1,3 -Dipropyl-2-imidazolidinone, 1-methyl-3-ethyl-2-imidazolidinone, 1-methyl-3-propyl-2-imidazolidinone, 1-methyl-3-butyl-2-imidazolidinone 1-methyl-3- (2-methoxyethyl) -2-imidazolidinone, 1-methyl-3- (2-ethoxyethyl) -2-imidazolidinone, 1,3-di- (2-ethoxyethyl) ) -2-imidazolidinone, 1,3-dimethylethylenethiourea, N, N′-diethylpropyleneurea, N-methyl-N′-ethylpropyleneurea and the like. 1-methyl-2-pyrrolidone, 1-cyclohexyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1-propyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, 1-isopropyl-2-pyrrolidone, 1,5-dimethyl-2-pyrrolidone, 1-methoxymethyl-2-pyrrolidone, 1-methyl-2-piperidone, 1,4-dimethyl-2-piperidone, 1-ethyl-2-piperidone, 1-isopropyl-2 -Piperidone, 1-isopropyl-5,5-dimethyl-2-piperidone and the like.

In the present invention, the hydrogenated product of the primary modified elastomer can be obtained by hydrogenating the primary modified elastomer 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 elastomer 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, and is based on the conjugated diene compound. 70% or more, preferably 80% or more, more preferably 90% or more of the unsaturated double bonds may be hydrogenated, or only a part may be hydrogenated. When only a part of the conjugated diene compound is hydrogenated, the hydrogenation rate is preferably 10% or more and less than 90%, or 15% or more and less than 85%, and preferably 20% or more and less than 80%. . Furthermore, in the hydrogenated product of the modified elastomer used in the present invention, the hydrogenation rate of vinyl bonds based on the conjugated diene before hydrogenation is preferably 85% or more, more preferably 90% or more, and still more preferably 95. % Or more is recommended for obtaining a 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. The hydrogenation rate of the aromatic double bond based on the vinyl aromatic hydrocarbon in the modified random copolymer or modified block copolymer is not particularly limited, but is preferably 50% or less, more preferably 30%. Hereinafter, more preferably 20% or less is recommended. The hydrogenation rate can be known by a nuclear magnetic resonance apparatus (NMR).

  Further, the modified elastomer in the present invention may be further added with a modifying agent to the primary modified elastomer. The modified elastomer obtained by this method is called secondary modified elastomer. The modifying agent here is a modifying agent capable of reacting with a functional group bonded to the terminal portion of the primary modified elastomer. For example, when the terminal group of the primary modified elastomer has an amino group, it is further reacted with a modifier containing an acid anhydride or an epoxy group in a solution or in a molten state to convert the functional group at the terminal. Using a modifier having two or more acid anhydrides and epoxy groups, a modified elastomer having a large amount of functional groups introduced into the terminal portion can be produced. The amount used for the modifier here is 0.3 to 10 mol, preferably 0.4 to 5 mol, more preferably 0.5 to 4 mol, per equivalent of the functional group bonded to the primary modified elastomer. It is recommended that

  The method for obtaining the secondary modified elastomer is not particularly limited, and a known method can be used. Examples thereof include a melt kneading method described later and a method of reacting each component by dissolving or dispersing in a solvent or the like. In the method of reacting each component dissolved or dispersed in a solvent or the like, the solvent is not particularly limited as long as it dissolves or disperses each component, and aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic carbonization. In addition to hydrocarbon solvents such as hydrogen, halogen-containing solvents, ester solvents, ether solvents and the like can be used. In such a method, the temperature at which each component is reacted is generally −10 to 150 ° C., preferably 30 to 120 ° C. The time required for the reaction varies depending on conditions, but is generally within 3 hours, preferably several seconds to 1 hour. A particularly preferable method is a method in which a secondary modified elastomer is obtained by adding a modifier to the solution in which the primary modified elastomer is produced and reacting it.

Examples of the modifier used in the production of the secondary modified elastomer include a carboxyl group-containing modifier such as maleic acid, oxalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, carbaryl acid, and cyclohexanedicarboxylic acid. Acid, aliphatic carboxylic acid such as cyclopentanedicarboxylic acid, aromatic carboxylic acid such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, trimesic acid, trimellitic acid, pyromellitic acid, etc. .
Examples of the modifier having an acid anhydride group include maleic anhydride, itaconic anhydride, pyromellitic anhydride, cis-4-cyclohexane-1,2-dicarboxylic anhydride, 1,2,4,5-benzenetetracarboxylic acid. And acid dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, and the like.
Examples of the modifier having an isocyanate group include tolylene diisocyanate, diphenylmethane diisocyanate, polyfunctional aromatic isocyanate and the like.

Examples of the modifier having an epoxy group include tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl-m-xylenediamine, diglycidylaniline, ethylene glycol diglycidyl, propylene glycol diglycidyl, terephthalic acid diglycidyl ester acrylate, etc. In addition, the epoxy compound described as a modifier used in order to obtain a primary modified elastomer or a hydrogenated product thereof may be used.
Examples of the modifying agent having a silanol group include hydrolysates of alkoxysilane compounds described as modifying agents used in primary modified elastomers. As a crosslinking agent having an alkoxysilane group, bis- (3-triethoxysilylpropyl) -tetrasulfane, bis- (3-triethoxysilylpropyl) -disulfane, ethoxysiloxane oligomer, etc. are used in primary modified elastomers. And silane compounds described as the modifying agents.

The weight average molecular weight of the modified elastomer used in the present invention is not particularly limited, but is preferably 30,000 to 1,000,000, more preferably 40,000 to 500,000, and still more preferably 5 from the balance of mechanical properties and moldability of the elastomer composition. It is about ~ 400,000.
The vinyl bond amount based on the conjugated diene compound in the modified elastomer in the present invention 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 obtained from a standard polystyrene measurement curve (using the standard polystyrene peak molecular weight). Can be determined using).

The amount of component (b) of the present invention is 1 to 100 parts by weight, preferably 1 to 70 parts by weight, more preferably 2 to 50 parts by weight per 100 parts by weight of the thermoplastic resin of component (a). is there.
Another component (c) constituting the present invention is a layered clay mineral. Examples of layered clay minerals include smectites such as montmorillonite, sapotite, hydelite, nontrite, hectorite, and stevensite, and vermiculite, halloysite, and swellable mica. Any of the minerals can be used. In particular, in the present invention, the organically layered clay mineral is preferable in terms of the layer peelability and fine dispersibility of the layered clay mineral. Further, the cation exchange capacity of the layered clay mineral is preferably 50 to 200 meq / 100 g. When the cation exchange capacity is less than 50 meq / 100 g, the organication by the organic onium ion exchange is performed. As a result, delamination of the layered clay mineral becomes insufficient, and when the cation exchange capacity exceeds 200 meq / 100 g, the bonding between the layers of the layered clay mineral is strong, Intervention between layers by ion exchange of onium ions becomes difficult, and as a result, delamination of layered clay minerals tends to be insufficient.

  Examples of organic onium ions used for organizing layered clay minerals include stearyl ammonium ion, hexyl ammonium ion, octyl ammonium ion, 2-ethylhexyl ammonium ion, dodecyl ammonium ion, octadecyl ammonium ion, dioctyl dimethyl ammonium ion, trioctyl ammonium ion. Ions, distearyl ammonium ions, 1-hexenyl ammonium ions, 1-dodecenyl ammonium ions, 9-octadecel ammonium ions, 9,12-octadecel ammonium ions, ammonium salts consisting of 12-aminododecanoic acid and hydrochloric acid, Ammonium ion such as ammonium salt consisting of alkylpropylenediamine and hydrochloric acid, tetraethylphosphonium ion, triethyl Emissions Jill Foss phosphonium ion, tetra -n-- butyl phosphonium ion, and phosphonium ions such as tri -n- butyl hexadecyl phosphonium ion. In the present invention, one or more layered clay minerals may be used.

  The layered clay mineral added in the composition of the present invention is finely dispersed and present in a state where part or all of the layered clay mineral is separated. Specifically, in the composition, each unit layer of layered clay minerals, or several or dozens of layers in a layered state within a range where the physical properties of the material do not deteriorate are sufficiently sufficient for each other. The interlaminar distance is preferably dispersed, and preferably 20% or more of the layered clay mineral is present in a thickness of 50 nm or less. In the present invention, when layer peeling of the layered clay mineral is insufficient, a sufficient physical property modification effect cannot be obtained. The ratio of the layered clay mineral present at 50 nm or less is determined by cutting the layered clay mineral perpendicularly to the flow direction of the molded article of the elastomer composition, observing the layered clay mineral with a transmission electron microscope, and determining the thickness and width of the layered clay mineral. A value obtained by dividing the total value of the cross-sectional areas of the components having a thickness of 50 nm or less by the total value of the cross-sectional areas of all layered clay mineral components is expressed in%.

In the thermoplastic resin composition of the present invention, the layered clay mineral of the component (c) is 1 to 60 parts by weight, preferably 2 parts per 100 parts by weight of the component (b) modified elastomer from the viewpoint of balance of physical properties and moldability. It is -55 weight part, More preferably, it is 3-50 weight part. When the amount is less than 1 part by weight, the effect of modifying the layered clay mineral is small, and when it exceeds 60 parts by weight, the resulting thermoplastic resin composition is inferior in moldability.
Examples of the olefinic rubbery polymer that is the component (d) constituting the present invention include ethylene-α-olefin copolymer rubber. The ethylene-α-olefin copolymer may be any copolymerized ethylene and α-olefin having 3 to 12 carbon atoms, such as propylene, 1-butene, isobutylene, octene, etc. From the viewpoint of rigidity, ethylene-octene copolymers are preferable, and those having an octene content of 15 wt% or more are particularly preferable. These ethylene-α-olefin copolymers are not particularly limited in polymerization method, but are preferably those polymerized with a metallocene catalyst having a uniform active site because of low specific gravity and the like. As the polymerization system, either a solution uniform system or a slurry system may be used.

The amount of component (d) of the present invention is 100 parts by weight or less, preferably 1 to 70 parts by weight, more preferably 2 to 50 parts by weight per 100 parts by weight of the thermoplastic resin of component (a).
Moreover, this invention mix | blends a component (e) depending on the case. Component (e) is at least one elastomeric polymer selected from block copolymers consisting of conjugated dienes and vinyl aromatic hydrocarbons, or hydrogenated products thereof. Examples of the method for producing the elastomer polymer include Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-17799, 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. In addition, the block copolymer used in the present invention is not particularly limited to a linear shape, a radial shape or the like, and is represented by, for example, the following general formula.

(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. 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 a functional group having a functional group described later. (Indicates a basic atomic group. The structure of the polymer chain bonded to X 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.

  In addition, the modified block copolymer portion may coexist with a plurality of portions where vinyl aromatic hydrocarbons are uniformly distributed and / or portions where tapes are distributed. The block copolymer used in the present invention may be an arbitrary mixture of block copolymers represented by the above general formula. In particular, as the block copolymer of the component (e) used in the present invention, a block copolymer composed of a styrene block and a butadiene block, a block copolymer composed of a styrene block and an isoprene block, or the block copolymer A block copolymer obtained by partial hydrogenation of the conjugated diene block part or a block copolymer obtained by further complete hydrogenation is preferred in terms of balance of various physical properties. The amount of component (e) is 100 parts by weight or less per 100 parts by weight of the thermoplastic resin of component (a). When excellent impact resistance is required, 1 part by weight or more is preferably blended.

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, elastomers and rubbers. For example, inorganic fillers and organic fillers such as metal hydroxides, silica-based inorganic fillers, and metal oxides can be added. It is recommended that these inorganic fillers and organic fillers be added to such an extent that the physical properties of the thermoplastic resin composition of the present invention are not impaired.
Metal hydroxide is a hydrated inorganic filler, such as aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, hydrated aluminum silicate, hydrated magnesium silicate, basic magnesium carbonate, hydrotalcite, calcium hydroxide, Barium hydroxide, tin oxide hydrate, inorganic metal compound hydrate such as borax, and the like can be used. A mixture of two or more kinds of metal hydroxides, and a mixture of a metal hydroxide and an inorganic filler other than the metal hydroxide can also be used.

Examples of the silica-based inorganic filler include solid particles having a chemical formula SiO ₂ or Si ₃ Al as a main component, such as silica, talc, kaolin clay, wollastonite, bentonite, zeolite, diatomaceous earth, synthetic silica, and glass beads. Inorganic fibrous materials such as glass balloons, glass flakes, and glass fibers can be used. Further, a silica-based inorganic filler having a hydrophobic surface, a mixture of two or more types of silica-based inorganic fillers, and a mixture of a silica-based inorganic filler and a non-silica inorganic filler can also be used. As silica, dry process white carbon, wet process white carbon, synthetic silicate-based white carbon, and what is called colloidal silica can be used.

Examples of the metal oxide include solid particles having a chemical formula M _x O _y (M is a metal atom, x and y are integers of 1 to 6) as a main component, such as alumina, titanium oxide, magnesium oxide, and zinc oxide. Iron oxide or the like can be used. A mixture of two or more kinds of metal oxides and a mixture of metal oxides and inorganic fillers other than metal oxides can also be used.
These inorganic fillers can be used alone or in combination of two or more. Other inorganic fillers include calcium carbonate, magnesium carbonate, barium carbonate, calcium silicate, calcium sulfate, calcium sulfite, titanium oxide, potassium titanate, barium sulfate, barium titanate, zinc oxide, asbestos, slug wool, etc. An agent can be added.

Moreover, organic fillers, such as carbon black, acetylene black, and furnace black, can be added. As carbon black, carbon black of each class such as FT, SRF, FEF, HAF, ISAF, and SAF can be used, and carbon black having a nitrogen adsorption specific surface area of 50 mg / g or more is preferable.
In the present invention, the surface of the inorganic filler is treated with a fatty acid such as stearic acid, oleic acid, or palmitic acid or a metal salt thereof; paraffin, wax, polyethylene wax, or a modified product thereof; an organic metal such as organic borane or organic titanate. Compound: A surface treated with a silane coupling agent or the like may be used.

  As the silane coupling agent, those generally used for inorganic fillers such as silica can be used. For example, 3-mercaptopropyl-trimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, vinyltrimethoxysilane, vinyl Examples include triethoxysilane. Particularly preferred silane coupling agents in the present invention are those having a silanol group or an alkoxysilane group and simultaneously having a polysulfide bond in which two or more mercapto groups and / or sulfur are linked. Examples of such silane coupling agents include: 3-mercaptopropyl-trimethoxysilane, 3-aminopropyltriethoxysilane, bis- [3- (triethoxysilyl) -propyl] -tetrasulfide, bis- [3- (triethoxysilyl) -propyl] -disulfide Bis- [3- (triethoxysilyl) -propyl] -trisulfide, bis- [2- (triethoxysilyl) -ethyl] -tetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyltetra Sulfide, 3-trimethoxysilyl group Piru N, N over-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl benzothiazole tetrasulfide, 3-trimethoxysilylpropyl benzothiazole tetrasulfide and the like. The blending amount of the silane coupling agent is 0.1 to 20 wt% of the blending amount with respect to the filler, more preferably 0.5 in order to sufficiently exert the reinforcing effect by the filler such as the inorganic filler. -18 wt%, more preferably 1-15 wt% is recommended. In addition, when using a silane coupling agent, you may use together sulfur and an organic peroxide.

In the present invention, a rubber softener can be added to improve processability. Mineral oils or liquid or low molecular weight synthetic softeners are suitable as rubber softeners, and are generally used as process oil or extender oil for softening, increasing volume and improving processability of rubber. Alternatively, softening agents such as polybutene, low molecular weight polybutadiene, liquid paraffin, mineral oil, organic polysiloxane, castor oil, and linseed oil can be used. These softening agents may be included in the polymer in advance when the polymer is produced.
In the present invention, as other additives, antioxidants, ultraviolet absorbers and light stabilizers, lubricants such as stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, ethylene bisstearamide, release agents It is described in “rubber / plastic compounding chemicals” (edited by Rubber Digest Co., Ltd.) such as molds, paraffin, plasticizers, flame retardants, antistatic agents, reinforcing agents such as organic fibers, carbon fibers and metal whiskers, pigments and coloring agents. Can be mentioned.

The method for producing the thermoplastic 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 mixer such as a Banbury mixer, a single screw extruder, a two screw extruder, a conider, a multi-screw extruder, etc. A method of removing the solvent by heating after dispersion and the like is used, and a melt kneading method using an extruder is particularly preferred from the viewpoint of productivity and good kneading properties.
At that time, a method of melt kneading the thermoplastic resin as component (a) and optionally components (d) and (e) after kneading the modified elastomer of component (b) and the layered clay mineral of component (c) in advance Alternatively, a method of melting and kneading the component (a), the component (b), the component (c), and optionally the components (d) and (e) at the same time is used. Alternatively, the component (b), the component (c) and optionally the components (d) and (e) may be previously kneaded and then melt kneaded with the component (a). In addition, a layered clay mineral dispersed in water is added in a state in which the modified elastomer is dissolved in a hydrocarbon solvent, and then the elastomer composition from which water vapor has been stripped and the hydrocarbon solvent has been removed is passed through an extruder and water is added. A method of mixing an elastomer composition obtained by melt mixing while devolatilizing a thermoplastic resin and the like can also be used. Moreover, it can also be directly molded after melt-kneading.

  The thermoplastic resin composition of the present invention can be used for various applications. The thermoplastic resin composition of the present invention is a conventional method such as extrusion molding, injection molding, two-color injection molding, sandwich molding, hollow molding, compression molding, as it is or as a composition containing various additives. It can be processed into a practically useful molded product by vacuum molding, rotational molding, powder slush molding, foam molding, laminate molding, calendar molding, blow molding, and the like. Moreover, you may process foaming, powder, extending | stretching, adhesion | attachment, printing, painting, plating, etc. as needed. By this molding method, various types of molded products such as sheets, films, injection molded products of various shapes, hollow molded products, compressed air molded products, vacuum molded products, extrusion molded products, foam molded products, nonwoven fabrics and fibrous molded products, etc. Can be used. These molded articles can be used for food packaging materials, medical instrument materials, home appliances and parts thereof, electronic devices and parts thereof, automobile parts, industrial parts, household goods, materials such as toys, footwear materials, and the like.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited at all by these examples.
1. Characteristics of Component (b) Modified Elastomer (1) Styrene Content Calculated from the absorption intensity at 262 nm using an ultraviolet spectrophotometer (Hitachi UV200).
(2) Vinyl content 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 number 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.

2. Preparation of hydrogenation catalyst The hydrogenation catalyst used in the hydrogenation reaction was prepared by the following method.
(1) Hydrogenation catalyst 1 liter of dried and purified cyclohexane was charged into 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.

3. Preparation of Component (b) Modified Elastomer An autoclave with a stirrer and a jacket was washed, dried and purged with nitrogen, and a cyclohexane solution (concentration 20 wt%) containing 16 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 (concentration 20 wt%) containing 68 parts by mass of butadiene purified in advance is added and polymerized at 70 ° C. for 1 hour, A cyclohexane solution containing 16 parts by mass of styrene was added and polymerized at 70 ° C. for 1 hour to obtain a living polymer of a block copolymer. 1-fold mol of 1,3-dimethyl-2-imidazolidine is added to the polymer-terminated lithium in the living polymer solution of the obtained block copolymer and reacted at 70 ° C. for 20 minutes to give a primary modified elastomer. Got.

  The hydrogenated primary modified elastomer was prepared by adding 100 ppm of a hydrogenation catalyst to the above solution of the primary modified block copolymer and reacting the hydrogenation reaction at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. for 1 hour. did. Methanol was added to the hydrogenated solution of the primary modified elastomer at a 10-fold molar ratio to n-butyllithium used for polymerization, and then carbonated water was added to adjust the pH to 8 or less. Drying treatment was performed to obtain a hydrogenated product of a primary modified elastomer. The obtained primary modified elastomer is an SBS type block copolymer type composed of styrene-1,3-butadiene-styrene, with an amino group bonded to one end, a styrene content of 32 wt%, and a vinyl bond. They were 32 wt% and the number average molecular weight 51000. The hydrogenation rate of the hydrogenated primary modified elastomer was 75%, and it was a SBBS type block copolymer in which the vinyl bond was completely hydrogenated. The concentration of one end portion of the obtained primary modified elastomer was calculated from the number average molecular weight, and 2 times mole of maleic anhydride was added to the one end portion, 220 ° C. with a 30 mmφ twin screw extruder, screw rotation speed 100 rpm. To obtain a hydrogenated modified elastomer in which maleic anhydride was added to the terminal end of the amino group.

4). Preparation of unmodified elastomer All operations were performed in the same manner as in 3 above, except that 1,3-dimethyl-2-imidazolidine was not added. The resulting unmodified elastomer had a styrene content of 32 wt%, a vinyl bond of 32 wt%, and a number average molecular weight of 51,000. The hydrogenation rate of the unmodified elastomer as the hydrogenated product was 95%, and it was a SEBS type modified block copolymer (hereinafter, unmodified elastomer) in which the unsaturated bond portion was completely hydrogenated. .

5. Performance evaluation of thermoplastic resin composition
(A) Flexural modulus Measured according to JIS K7203 at a bending speed of 2 mm / min.

(I) Izod impact strength Measured at 23 ° C. in accordance with JIS K7110.

[Example 1]
Component a) is 75 parts by weight of polypropylene (PM600A: manufactured by Sun Allomer), Component b) is 12.5 parts by weight of modified elastomer, and Component (c) is dimethyldialkyl (C18) ammonium / synthetic mica (trade name; Somasif MAE, 5 parts by weight (manufactured by Coop Chemical Co., Ltd.) and 12.5 parts by weight of an ethylene-octene copolymer (engage 8150: manufactured by Dow) as the component (d) are 220 ° C. and screw rotation speed by a 30 mmφ twin screw extruder. Melt kneading was performed at 100 rpm. The obtained thermoplastic resin composition was injection molded to obtain a test piece, and the physical properties were measured.

[Example 2]
Component a) is 75 parts by weight of polypropylene (PM600A: manufactured by Sun Allomer), Component b) is 6.25 parts by weight of modified elastomer, and Component (c) is dimethyldialkyl (C18) ammonium / synthetic mica (trade name; Somasif MAE, 2 parts by weight of Coop Chemical Co., Ltd., 12.5 parts by weight of an ethylene-octene copolymer (engaged 8150 Dow) as component (d), and 6.25 parts by weight of unmodified elastomer as component (e) The mixture was melt kneaded at 220 ° C. and a screw rotation speed of 100 rpm with a 30 mmφ twin screw extruder. The obtained thermoplastic resin composition was injection molded to obtain a test piece, and the physical properties were measured.

[Comparative Example 1]
A thermoplastic resin composition was prepared in the same manner as in Example 1 except that the component (c) was omitted, and a test piece was obtained by injection molding, and the physical properties were measured.

[Comparative Example 2]
As component a), 75 parts by weight of polypropylene (PM600A: manufactured by Sun Allomer), 12.5 parts by weight of Engagement 8150 (manufactured by Dow) as component (d), and 12.5 parts by weight of unmodified elastomer as component (e), The mixture was melt-kneaded with a 30 mmφ twin screw extruder at 220 ° C. and a screw rotation speed of 100 rpm. The obtained thermoplastic resin composition was injection molded to obtain a test piece, and the physical properties were measured.
As shown in Table 1, the resin composition containing the component (b) and the component (c) has a significantly improved bending elastic modulus and improved impact strength, that is, the stiffness and the impact resistance are extremely balanced. It turns out that a thermoplastic resin composition is obtained.

Claims (8)

(A) 100 parts by weight of thermoplastic resin (b) Conjugated diene polymer comprising conjugated diene or hydrogenated product thereof, random copolymer comprising conjugated diene and vinyl aromatic hydrocarbon or hydrogenated product thereof, conjugated diene 1 to 100 parts by weight of a modified elastomer in which at least one functional group-containing atomic group is bonded to a terminal part of a polymer selected from a block copolymer made of vinyl aromatic hydrocarbon or a hydrogenated product thereof (c) layered The clay mineral is (b) 1 to 60 parts by weight per 100 parts by weight. (D) 0 to 100 parts by weight of an olefinic rubbery polymer (e) a block copolymer consisting of a conjugated diene and a vinyl aromatic hydrocarbon or its A thermoplastic resin composition comprising 0 to 100 parts by weight of at least one elastomer polymer selected from hydrogenated products. The functional group-containing atomic group of the component (b) is an atomic group having at least one functional group selected from an amino group, an imino group, a hydroxyl group, a carboxyl group, an acid anhydride group, an epoxy group, a silanol group, and an alkoxysilane group. The thermoplastic resin composition according to claim 1, wherein: Polymer in which component (b) is selected from conjugated diene polymers comprising conjugated dienes, random copolymers comprising conjugated dienes and vinyl aromatic hydrocarbons, and block copolymers comprising conjugated dienes and vinyl aromatic hydrocarbons A primary modified elastomer having an amino group, an imino group, a hydroxyl group, a carboxyl group, an acid anhydride group, an epoxy group, a silanol group, an alkoxysilane group, and / or a derivative thereof added to the terminal portion of The thermoplastic resin composition according to claim 1, wherein: Polymer in which component (b) is selected from conjugated diene polymers comprising conjugated dienes, random copolymers comprising conjugated dienes and vinyl aromatic hydrocarbons, and block copolymers comprising conjugated dienes and vinyl aromatic hydrocarbons A primary modifier that is an amino group, an imino group, a hydroxyl group, a carboxyl group, an acid anhydride group, an epoxy group, a silanol group, an alkoxysilane group, and / or a derivative thereof is added to the terminal portion of The thermoplastic resin composition according to claim 1, which is a primary modified elastomer obtained. The thermoplastic resin composition according to claim 1, wherein the component (b) is a secondary modified elastomer obtained by further adding a modifier to the primary modified elastomer. The thermoplastic resin composition according to any one of claims 1 to 5, wherein component (b) has at least one functional group-containing atomic group bonded to an end of a block mainly composed of styrene. object. The thermoplastic resin composition according to any one of claims 1 to 6, wherein the layered clay mineral is an organically treated layered clay mineral. Component (a) is an olefin type thermoplastic resin, The thermoplastic resin composition of Claims 1-7 characterized by the above-mentioned.