WO2006137134A1

WO2006137134A1 - Thermoplastic resin composition

Info

Publication number: WO2006137134A1
Application number: PCT/JP2005/011454
Authority: WO
Inventors: Masanobu Urakami; Taizo Aoyama
Original assignee: Kaneka Corporation
Priority date: 2005-06-22
Filing date: 2005-06-22
Publication date: 2006-12-28

Abstract

A thermoplastic resin composition that excels in low hardness, oil resistance, transparency, etc. There is provided a thermoplastic resin composition characterized in that per 100 parts by weight of the total amount of a composition consisting of 5 to 95 wt.% of isobutylene block copolymer (a) composed of a polymer block whose main component is isobutylene and a polymer block from a monomer component wherein isobutylene is not a main component and 5 to 95 wt.% of thermoplastic polyurethane (b), there is contained 0.1 to 50 parts by weight of styrene polymer or olefinic polymer (c) having at least one functional group selected from the group consisting of an epoxy group, an amino group, a hydroxyl group, an acid anhydride group, a carboxyl group or its salt and a carboxylic ester.

Description

Specification

Thermoplastic resin composition

Technical field

[0001] The present invention relates to a thermoplastic resin containing a specific isobutylene block copolymer, a thermoplastic polyurethane resin, and an olefin polymer or a styrene polymer containing a specific functional group. Relates to the composition.

Background art

[0002] In recent years, a thermoplastic elastomer which is a rubber-like soft material and does not require a vulcanization step and has a moldability similar to that of a thermoplastic resin has attracted attention. As such thermoplastic elastomers, various polymers such as polyolefins, polyurethanes, polyesters, and polystyrenes have been developed and are commercially available. Among these thermoplastic elastomers, polystyrene-based thermoplastic elastomers (see Patent Document 1) are widely used in terms of processability and cost, but they are all satisfactory in terms of low hardness, oil resistance, transparency, etc. Patent Document 1: Japanese Patent Laid-Open No. 11-293083

Disclosure of the invention

Problems to be solved by the invention

[0003] An object of the present invention is to provide a thermoplastic resin composition excellent in low hardness, oil resistance, transparency and the like.

Means for solving the problem

[0004] As a result of intensive studies to solve the above problems, the present inventors have found that a specific isobutylene block copolymer, a thermoplastic polyurethane resin, and an olefin containing a specific functional group. The present inventors have found that a thermoplastic resin composition containing a styrene polymer or a styrene polymer solves the above problems, and has led to the present invention.

[0005] That is, the present invention relates to (a) an isobutylene block copolymer composed of a polymer block containing isobutylene as a main component and a polymer block having a monomer component not containing isobutylene as a main component. 5 to 95% by weight, (b) thermoplastic polyurethane 5 to 95% by weight (C) at least one functional group selected from the group consisting of an epoxy group, an amino group, a hydroxyl group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylate ester card The present invention relates to a thermoplastic resin composition comprising 0.1 to 50 parts by weight of an olefin polymer or a styrene polymer.

[0006] As a preferred embodiment, the monomer component (a) which is not mainly composed of isobutylene as a main component is a monomer component mainly composed of an aromatic buyl monomer. The present invention relates to a plastic resin composition.

[0007] A preferred embodiment relates to a thermoplastic resin composition in which the aromatic vinyl monomer is at least one selected from the group force consisting of styrene, p-methylstyrene, a-methylstyrene, and indene force.

[0008] As a preferred embodiment, (a) an isobutylene-based block copolymer power, a polymer block mainly composed of an aromatic butyl monomer, and a polymer block aromatic bulla monomer based on isobutylene. A triblock copolymer having a polymer block force comprising, as a main component, a polymer block comprising an aromatic butyl monomer as a main component, a diblock copolymer comprising a polymer block force comprising isobutylene as a main component, and A polymer block composed mainly of an aromatic vinyl monomer and a polymer block composed mainly of isobutylene. It is related with the thermoplastic resin composition characterized by being.

[0009] A preferred embodiment is characterized in that the olefin polymer or styrene polymer of component (c) is a styrene ethylene butylene styrene copolymer (MAH-SEBS) having an acid anhydride group. The present invention relates to a thermoplastic rosin composition.

The invention's effect

[0010] The thermoplastic resin composition of the present invention is excellent in low hardness, oil resistance and transparency, and also in heat resistance stability and mechanical strength. It can be used for toys, moving equipment, stationery, automotive interior / exterior, civil engineering, construction, home appliances, clothing, footwear, medical use, sanitary goods, packaging and transport materials, and electric wires. In particular, it is suitable for daily goods that require oil resistance and low hardness.

BEST MODE FOR CARRYING OUT THE INVENTION [0011] The present invention is described in detail below.

[0012] The (a) isobutylene block copolymer of the present invention has a polymer block composed of a polymer block containing isobutylene as a main component and a monomer block not containing isobutylene as a main component. For example, any of block copolymers, diblock copolymers, triblock copolymers, multiblock copolymers, etc. having a linear, branched, or star structure can be selected. is there. As a preferred block copolymer, from the viewpoint of the balance of physical properties and the absorbability of the softener described below, which is used as needed, a polymer block having a monomer component that does not contain isobutylene as the main component is composed of isobutylene as the main component. Polymer block consisting of a polymer block with a monomer component that does not contain isobutylene as the main component, a polymer block consisting of a monomer component that does not contain isobutylene as the main component, and a block consisting of isobutylene as the main component Diblock copolymer with combined block strength, polymer block composed of monomer components that do not contain isobutylene as the main component, and polymer block force with three or more arms that form polymer block force with isobutylene as the main component Examples include coalescence. These can be used alone or in combination of two or more in order to obtain the desired physical properties and moldability.

The monomer component not containing isobutylene as a main component of the present invention is a monomer component having an isobutylene content of 30% by weight or less. The main component is isobutylene. The content of isobutylene in the monomer component is preferably 10% by weight or less, more preferably 3% by weight or less.

[0014] The monomer other than isobutylene in the monomer component not containing isobutylene as a main component of the present invention is not particularly limited as long as it is a monomer component that can be cationically polymerized. Examples thereof include monomers such as group bulls, gens, vinyl ethers, silane compounds, vinyl carbazole, 13-vinene, and acenaphthylene. These are used alone or in combination of two or more.

[0015] Aliphatic olefin monomers include ethylene, propylene, 1-butene, and 2-methyl.

Examples include 1-butene, 3-methyl-1-butene, pentene, hexene, cyclohexene, 4-methyl pentene, butylcyclohexane, otaten, norbornene, and the like.

[0016] Aromatic bulle monomers include styrene, o-methylstyrene, m-methylstyrene. , P-methylstyrene, α-methylstyrene, β-methylenostyrene, 2,6 dimethylstyrene, 2,4 dimethylstyrene, α-methyl-ο-methylstyrene, α-methyl-m-methylstyrene, α-methyl-ρ— Methyl styrene, j8-methyl-o-methyl styrene, β-methyl-m-methyl styrene, 13-methyl-p-methyl styrene, 2, 4, 6 trimethyl styrene, α-methyl-2, 6 dimethyl styrene, α-methyl-2, 4 dimethyl styrene , 13-methyl-2,6 dimethylstyrene, 13-methyl-2,4 dimethylstyrene, ο chlorostyrene, m-chlorostyrene, p chlorostyrene, 2,6 dichlorostyrene, 2,4 dichlorostyrene, α chlorostyrene, chlorostyrene, α-black mouth m chlorostyrene, chloro-p-chlorostyrene, 8-chloro o-chlorostyrene, beta - click Lolo _m - chlorostyrene, beta-chloro ρ- chlorostyrene, 2, 4, 6-trichloro styrene emission, alpha-chloro 2, 6-dichloro styrene, alpha-chloro 2, 4-dichloro styrene, / 3- black port 1, 2, 6-dichlorostyrene, / 3--black 1, 2-4-dichlorostyrene, o-t-butinostyrene, m-t butylstyrene, p-t-butylstyrene, o-methoxystyrene, m-methoxystyrene, ρ —Methoxy styrene, o chloromethyl styrene, m-chloromethyl styrene, p chloro methino styrene, o bromo methino styrene, m-bromo methino styrene, p bromomethyl styrene, styrene derivatives substituted with silyl groups, indene, urnaphthalene, etc. Is mentioned.

[0017] Examples of the gen-based monomer include butadiene, isoprene, hexagen, cyclopentagen, cyclohexagen, dicyclopentagen, divinylbenzene, ethylidene norbornene, and the like.

[0018] Examples of the butyl ether monomer include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, sec butyl vinyl ether, tert butyl vinyl ether, isobutyl vinyl etherate, methinorepropenoline etherol. Ethenorepropenenoreatenore and the like.

[0019] Examples of the silane compound include butyltrichlorosilane, butylmethyldichlorosilane, butyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyltrimethylsilane, dibutyldichlorosilane, divininoresimethoxymethoxy, divininoresimethinolessilane, 1,3 dibi- Nore -1, 1, 3, 3-tetramethyldisiloxane, trivinylmethylsilane, γ-methacryloyloxypropyltrimethoxysilane, _Ί -methacryloyloxypropylmethyldimethoxysilane, and the like.

[0020] The monomer component not mainly composed of isobutylene of the present invention is preferably a monomer component mainly composed of an aromatic vinyl monomer from the balance of physical properties and polymerization characteristics. ,. The monomer component mainly composed of the aromatic bur monomer of the present invention is a monomer component having an aromatic vinyl monomer content of 60% by weight or more, preferably 80% by weight or more. Show. As the aromatic bur monomer, it is preferable to use one or more monomers selected from styrene, α-methyl styrene, ρ-methyl styrene, and indene group power. From the viewpoint of cost, styrene, α —It is particularly preferable to use methylstyrene or a mixture thereof.

[0021] The monomer component mainly composed of isobutylene of the present invention may or may not contain a monomer other than isoprene. Usually, isobutylene is contained in an amount of 60% by weight or more. The monomer component is preferably 80% by weight or more. The monomer other than isoprene is not particularly limited as long as it is a monomer capable of cationic polymerization, and examples thereof include the above-mentioned monomers.

[0022] The ratio of the polymer block containing isobutylene as the main component and the polymer block containing isobutylene as the main component is not particularly limited, but from the viewpoint of various physical properties, isobutylene is used. Polymer block strength containing 0 to 95% by weight of the main component, and polymer block containing 5 to 60% by weight of the polymer block having the monomer component strength not containing isobutylene is preferred. It is particularly preferred that the block is from 50 to 85% by weight and the polymer block having a monomer component power not containing isobutylene as a main component is from 15 to 50% by weight.

[0023] The number average molecular weight of the isobutylene block copolymer is not particularly limited, but the surface strength such as fluidity, calorific properties, physical properties, etc. is preferably 30000-500000. Especially preferred to be between 50000 and 40 0000! /. When the number average molecular weight of the isobutylene block copolymer is lower than 30000, the softening agent used as necessary tends to bleed out, and the mechanical properties are not fully expressed. If it exceeds It is disadvantageous in terms of mobility and workability. The above number average molecular weight is a value measured using a gel permeation chromatography (GPC) system manufactured by Waters (column: Shodex K-804 (polystyrene gel) manufactured by Showa Denko KK, mobile phase: black mouth form). .

[0024] The production method of the isobutylene block copolymer is not particularly limited! For example, isobutylene is the main component in the presence of the compound represented by the following general formula (1). It is obtained by polymerizing the monomer component and the monomer component not containing isobutylene as a main component.

(CR'R'X) R ³ (1)

[Wherein X represents a halogen atom, an alkoxy group having 1 to 6 carbon atoms or an acyloxy group having 1 to 6 carbon atoms.

R ² represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and R ² may be the same or different. R ³ is a polyvalent aromatic hydrocarbon group or a polyvalent aliphatic hydrocarbon group, and n is a natural number of 1-6. ].

[0025] The compound represented by the general formula (1) serves as an initiator, and is considered to generate a carbon cation in the presence of a Lewis acid or the like and serve as a starting point for cationic polymerization. Examples of the compound of the general formula (1) used in the present invention include the following compounds.

(1-Chloro-1-methylethyl) benzene [C H C (CH) Cl], 1, 4 Bis (1-chloro

6 5 3 2

Ru- 1-methylethyl) benzene [1, 4 Cl (CH) CC H C (CH) Cl], 1, 3 bis

3 2 6 4 3 2

(1-Chloro-1-methylethyl) benzene [1, 3-Cl (CH) CC H C (CH) Cl], 1

3 2 6 4 3 2

, 3, 5 Tris (1-chloro-1-methylethyl) benzene [1, 3, 5— (CIC (CH)) C

3 2 3 6

H], 1, 3 bis (1-chloro-1-methylethyl) -5- (tert-butyl) benzene [1,

Three

3— (C (CH) C1) -5-(C (CH)) C H].

3 2 2 3 3 6 3

[0026] Particularly preferred among these! / Is bis (1-chloro-1-methylethyl) benzene [C

6

H (C (CH) C1)], tris (1 chloro 1-methylethyl) benzene [(C1C (CH))

4 3 2 2 3 2 3

C H]. Note that bis (1-chloro-1-methylethyl) benzene is

6 3

Isopropyl) benzene, bis (2-chloro-2-propynole) benzene! / ヽ is also called dicuminochloride, and tris (1-chloro-1- 1-methylethyl) benzene is tris (cyclochloroisopropyl) benzene, tris ( 2—Black mouth 2—Propyl) Benzene! / トリ is also called Tricminolek mouth ride. [0027] When the isobutylene block copolymer is produced by polymerization, a Lewis acid catalyst may be allowed to coexist. Such Lewis acid may be any one that can be used for cationic polymerization. TiCl, TiBr, BC1, BF, BF-OEt, SnCl, SbCl, SbF, WC1, T

4 4 3 3 3 2 4 5 5 6 Metal halides such as aCl, VC1, FeCl, ZnBr, A1C1, AlBr; Et A1C1, EtAlC

5 5 3 2 3 3 2

Organometallic halides such as 1 can be preferably used (Et represents an ethyl group)

2

. Above all, considering the capacity as a catalyst and industrial availability, TiCl, BC1, Sn

4 3

CI is preferred. The amount of Lewis acid used is not particularly limited, but polymerization of the monomer used

Four

It can be set in view of characteristics or polymerization concentration. Usually, 0.1 to L00 molar equivalent can be used with respect to the compound represented by the general formula (1), preferably in the range of 1 to 50 molar equivalent.

[0028] In the polymerization of the isobutylene block copolymer, an electron donor component may be allowed to coexist if necessary. This electron donor component is believed to have the effect of stabilizing the growing carbon cation during cation polymerization, and the addition of an electron donor produces a polymer with a controlled molecular weight distribution structure. Can do. The electron donor component that can be used is not particularly limited, and examples thereof include pyridines, amines, amides, sulfoxides, esters, and metal compounds having an oxygen atom bonded to a metal atom. it can.

[0029] The polymerization of the isobutylene block copolymer can be carried out in an organic solvent as necessary, and the organic solvent can be used without any particular limitation as long as it does not substantially inhibit cationic polymerization. Specifically, halogenated hydrocarbons such as methyl chloride, dichloromethane, chloroform, chloro chloride, dichloroethane, _n -propyl chloride, n-butyl chloride, and black benzene; benzene, toluene, xylene, ethylbenzene, propyl Alkylbenzenes such as benzene and butylbenzene; linear aliphatic hydrocarbons such as ethane, propane, butane, pentane, hexane, heptane, octane, nonane, and decane; 2-methylpropane, 2-methylbutane, 2, Branched aliphatic hydrocarbons such as 3,3-trimethylpentane and 2,2,5-trimethylhexane; Cyclic aliphatic hydrocarbons such as cyclohexane, methylcyclohexane and ethylcyclohexane; Petroleum Examples thereof include paraffin oil obtained by hydrotreating the fraction. [0030] These solvents are used singly or in combination of two or more in consideration of the balance of the polymerization characteristics of the monomers constituting the block copolymer and the solubility of the resulting polymer.

[0031] The amount of the solvent used is preferably 1 to 50% by weight, more preferably 5 to 35% by weight in consideration of the viscosity of the polymer solution obtained and ease of heat removal. Can be determined.

[0032] In carrying out the actual polymerization, it is preferable to mix the components under cooling, for example, at a temperature of 100 ° C or higher and lower than 0 ° C. In order to balance the energy cost and the stability of the polymerization, it is particularly preferred that the temperature range is 80 ° C to 30 ° C.

[0033] As the (b) thermoplastic polyurethane-based resin of the present invention, various thermoplastic polyurethane-based resins such as ester-based, ether-based, and carbonate-based resins are used.

[0034] Examples of the thermoplastic polyurethane-based resin (b) include (i) an organic diisocyanate, (mouth) a chain extender, and (c) a thermoplastic polyurethane-based resin having a polymer polyol power. Any manufacturing method can be used. For example, the (i) component, the (mouth) component and the (c) component, which are uniformly mixed in advance, are cast on a vat that has been subjected to mold release treatment by high-speed stirring and mixing. Depending on the reaction force at a temperature of 200 ° C or less, or (i) component and (mouth) component are added to form a terminal isocyanate group prepolymer, and then (c) component is added and mixed at high speed. Conventionally known techniques such as casting on a release-treated bat and reacting at a temperature of 200 ° C. or lower as necessary can be used.

[0035] As the organic diisocyanate (i), any conventionally known ones can be used. For example, hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, xylene diisocyanate, Cyclohexane diisocyanate, toluidine diisocyanate, 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, 4, 4, — diphenylmethane diisocyanate, p-phenol Range isocyanate, m-phenolic isocyanate, 1,5 naphthalenediocyanate alone or a mixture thereof can be used.

[0036] As the chain extender (mouth), dihydroxy compounds having a molecular weight of less than 500 can be used. For example, ethylene glycol, 1, 2 propylene glycol, 1, 3 propylene glycol 2, 3, butylene glycol, 1,4 butanediol, 2,2,1-dimethyl-1,3-propanediol, diethylene glycol, 1,5 pentanediol, 1,6 hexanediol, cyclohexane 1,4 -Diol, cyclohexane-1,4-dimethanol, etc., alone or as a mixture.

[0037] The polymer polyol (c) is a force capable of using a dihydroxy compound having an average molecular weight of 500 to 4000. Examples thereof include polyester diol, polyether diol, and polycarbonate diol.

[0038] Polyester diols include ethylene glycol, propylene glycol, 1,4 butanediol, 1,5 pentanediol, 1,6 hexanediol, neopentyl glycol, 3-methyl-1,5 pentanediol, cyclohexanedimethanol Or one or more of the other low molecular diol components and one or more of the low molecular dicarboxylic acids such as dartaric acid, suberic acid, sebacic acid, terephthalic acid, and isophthalic acid. Examples thereof include polylataton diols obtained by condensation polymerization products and ring-opening polymerization of latatones such as polyproviolatatone diols, polyprolatatone diols, polyvalerolataton diols, and the like.

[0039] Examples of the polyether diol include polypropylene ether glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol, and other copolymerized polyether glycols.

[0040] Examples of the polycarbonate diol include polyhexamethylene carbonate diol, diol obtained by ring-opening addition polymerization of ratatone to polyhexamethylene carbonate diol, polyhexamethylene carbonate diol and other polyester diols, polyether diol, Examples include co-condensates with polyether ester diols.

[0041] One or more of the above thermoplastic polyurethane-based resins can be used.

[0042] In order to increase the transparency of the thermoplastic resin composition of the present invention, it can be realized by combining the components (a) and (b) having similar refractive indexes. As the refractive index, a value measured by a method using sodium D-line such as Abbe refractometer NAR-3T (manufactured by Atago Co., Ltd.) can be used.

[0043] Ingredient (b) Thermoplastic polyurethane resin is blended as follows: Component (a) Isobutylene block It is 5 to 95% by weight with respect to 5 to 95% by weight of the copolymer, preferably (a) 25 to 75% by weight with respect to 25 to 75% by weight of the isobutylene block copolymer. If it is less than 5% by weight, the oil resistance of the resulting thermoplastic resin composition is reduced, and if it exceeds 95% by weight, the hardness of the resulting thermoplastic resin composition is increased and the soft feel is reduced. End up.

[0044] The functional group in the olefin-based polymer or styrenic polymer containing a functional group used for the component (c) of the present invention is a functional group having polarity, and is an epoxy group, an amino group, a water group. It is at least one functional group selected from the group consisting of acid groups, acid anhydride groups, carboxyl groups and salts thereof, and carboxylic acid esters. The term “polymer” as used herein includes a copolymer, and the copolymerization mode of the copolymer is not particularly limited. Random copolymers, graft copolymers, block copolymers, etc. The style may be good.

[0045] Examples of olefin polymers and styrene polymers include ethylene propylene copolymers, ethylene-butene copolymers, ethylene octene copolymers, ethylene monohexene copolymers, and other ethylene. Copolymer: polyethylene, polypropylene, polystyrene, polybutene, ethylene propylene copolymer, styrene butadiene copolymer, styrene butadiene styrene block copolymer (SBS), styrene isoprene styrene block copolymer (SIS), Examples thereof include polybutadiene, butadiene-acrylonitrile copolymer, polyisoprene, butene-isoprene copolymer, styrene ethylene butylene styrene block copolymer (SEBS), and styrene ethylene propylene / styrene block copolymer (SEPS).

[0046] Specific examples of the olefin-based polymer having a functional group and the styrene-based polymer used in the component (c) of the present invention include polyolefin-based polymers such as ethylene'-olefin-based copolymers, Copolymers of acid anhydrides such as maleic anhydride, succinic anhydride, and fumaric anhydride, carboxylic acids such as acrylic acid, methacrylic acid, and butyl acetate and their Na, Zn, K, Ca, Mg, etc. Salts, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, olefin methacrylate copolymerized carboxylic acid ester, etc. Is mentioned.

[0047] More specifically, ethylene methyl acrylate copolymer, ethylene ethyl acrylate Copolymer, Ethylene acrylate n-propyl copolymer, Ethylene acrylate propyl copolymer, Ethylene acrylate n-butyl copolymer, Ethylene acrylate t-butyl copolymer, Ethylene acrylate isobutyl copolymer, Ethylene -Methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-n-propyl methacrylate copolymer, ethylene-isopropyl methacrylate copolymer, ethylene-methacrylic acid n-butyl copolymer, ethylene-methacrylic acid t Butyl copolymer, ethylene-isobutyl methacrylate copolymer, ethylene (meth) acrylic acid copolymer and its metal salts such as Na, Zn, K, Ca, Mg, ethylene maleic anhydride copolymer, Ethylene butylene maleic anhydride copolymer, ethylene propylene monomer Inic anhydride copolymer, ethylene monohexene maleic anhydride copolymer, ethylene octene-maleic anhydride copolymer, propylene maleic anhydride copolymer, maleic anhydride modified SBS, maleic anhydride Examples include modified SIS, maleic anhydride modified SEBS, hydrous maleic acid modified SEPS, and maleic anhydride modified ethylene acrylate copolymer. As the component (c), one or a combination of two or more can be used.

[0048] As the component (c), from the viewpoint of transparency, a styrene-ethylene-butylene-styrene copolymer (MAH-SEBS) having an acid anhydride group is preferred! /.

[0049] The thermoplastic resin composition of the present invention comprises (f) the olefin-based polymer or styrene-based polymer as component (c) with respect to 100 parts by weight of the total amount of component (a) and component (b). It contains 1 to 50 parts by weight. The preferred lower limit is 0.5 parts by weight, and the preferred upper limit is 20 parts by weight.

[0050] When the olefin polymer or styrene polymer as component (c) is less than 0.1 part by weight, the compatibility is not sufficiently exhibited, and when it exceeds 50 parts by weight, (a ) It is preferable because the proportion of the component is reduced.

[0051] The component (c) may be added during the melt-kneading of the components (a) and (b)! /, And may be added to the component (a) or the component (b) in advance. Yo ... The addition to the component (a) or the component (b) in advance is preferable immediately because the effect of improving the compatibility is exhibited.

[0052] In the composition of the present invention, polyolefin resin is also used if necessary. Poliophy As a resin, a homopolymer of a 1-year-old refin, a random copolymer, a block copolymer and a mixture thereof, or a random copolymer of an α-olefin and another unsaturated monomer, a block Copolymers, graft copolymers, and those obtained by oxidation, halogenation or sulfonation of these polymers can be used alone or in combination. Specifically, polyethylene, ethylene-propylene copolymer, ethylene-propylene non-conjugated diene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene otaten copolymer, ethylene acetate butyl copolymer, ethylene butyl Polyethylene resin such as alcohol copolymer, ethylene ethyl acrylate copolymer, chlorinated polyethylene; polypropylene such as polypropylene, propylene monoethylene random copolymer, propylene monoethylene block copolymer, chlorinated polypropylene Examples thereof include polybutene, polyisobutylene, polymethylpentene, (co) polymers of cyclic olefins, and the like. Among these, polyethylene-based resin, polypropylene-based resin, or a mixture thereof can be preferably used from the viewpoint of balance of physical properties of thermoplastic resin.

[0053] The amount of the polyolefin-based rosin blended is 0 to: L 00 parts by weight, preferably 0 to 50 parts by weight, and more preferably 0 to 100 parts by weight of the total amount of the components (a) and (b). ~ 30 parts by weight. If it exceeds 100 parts by weight, the hardness increases, such being undesirable.

[0054] A softener is also used in the composition of the present invention as needed. Although not particularly limited, usually a liquid or liquid material is preferably used at room temperature. Both hydrophilic and hydrophobic softeners can be used. Examples of such softeners include various rubber or rosin softeners such as mineral oil, vegetable oil, and synthetic oil. As mineral oils, process oils such as naphthenes and norafins, etc. As vegetable oils, castor oil, cottonseed oil, linseed oil, rapeseed oil, soybean oil, palm oil, palm oil, peanut oil, peanut oil, pine Examples of the synthetic system include oil and olive oil, and polybutene and low molecular weight polybutadiene. Among these, paraffinic process oil and polybutene are preferably used from the viewpoint of compatibility with component (a) or balance of physical properties of the thermoplastic resin composition. These softening agents may be used alone or in combination of two or more kinds in order to obtain the desired viscosity and physical properties.

[0055] The blending amount of the softening agent is 0 to L00 weight with respect to 100 parts by weight of the total amount of the component (a) and the component (b). Parts, preferably 0 to 50 parts by weight, more preferably 0 to 30 parts by weight. If the amount exceeds 100 parts by weight, the softener bleeds out, which is not preferable.

[0056] Furthermore, a filler can be blended in the resin composition of the present invention for improving physical properties or economic merit. Suitable fillers include flaky inorganic fillers such as clay, diatomaceous earth, silica, talc, norlium sulfate, calcium carbonate, magnesium carbonate, metal oxide, my strength, graphite, aluminum hydroxide; various metal powders Examples thereof include granular or powdered solid fillers such as wood chips, glass powder, ceramic powder, carbon black, granular or powdered polymer; and other various natural or artificial short fibers and long fibers. In addition, by blending hollow fillers, such as inorganic hollow fillers such as glass balloons and silica balloons, polyvinylidene fluoride, organic hollow fillers that also have polyvinylidene fluoride copolymer power, etc., weight reduction is achieved. be able to. Furthermore, in order to improve various physical properties such as weight reduction and shock absorption, various foaming agents can be mixed, and gas can be mixed mechanically during mixing. These can be used alone or in combination of two or more.

[0057] The blending amount of the filler is 0 to: LOO parts by weight, preferably 0 to 50 parts by weight, more preferably 100 parts by weight of the total amount of the components (a) and (b). 0 to 30 parts by weight. When the amount exceeds 100 parts by weight, the mechanical strength of the resulting thermoplastic resin composition is lowered, and the flexibility is also impaired.

[0058] In addition, the thermoplastic rosin composition of the present invention can be blended with an antioxidant and Z or an ultraviolet absorber as necessary, and the blending amounts of the components (a) and (b) The total amount is from 0.01 to 10 parts by weight, preferably from 0.01 to 5 parts by weight, based on 100 parts by weight.

[0059] In addition, flame retardants, antibacterial agents, light stabilizers, colorants, fluidity improvers, lubricants, antiblocking agents, antistatic agents, crosslinking agents, crosslinking aids, and the like can be added as other additives. These can be used alone or in combination of two or more.

[0060] Among the above-mentioned additives, a lubricant can be blended in the thermoplastic resin composition of the present invention for the purpose of adjusting moldability and imparting releasability. Preferred lubricants include fatty acid metal salt lubricants, fatty acid amide lubricants, fatty acid sterol lubricants, fatty acid lubricants, aliphatic alcohol lubricants, partial esters of fatty acids and polyhydric alcohols, and norafine lubricants. You can select and use two or more of these. [0061] Examples of the fatty acid metal salt lubricant include calcium stearate, magnesium stearate, aluminum stearate, zinc stearate, barium stearate, and metal montanate.

[0062] Fatty acid amide-based lubricants include ethylene bis stearic acid amide, L force acid amide, oleic acid amide, stearic acid amide, behenic acid amide, ethylene bisoleic acid amide, and ethylene bisenolic acid. Examples thereof include amides, ethylenebislauric acid amides, m-xylylene bisstearic acid amides, and p-phenolene bisstearic acid amides. Fatty acid ester lubricants include methyl laurate, methyl myristate, methyl palmitate, methyl stearate, methyl oleate, methyl erucate, methyl behenate, butyl laurate, butyl stearate, isopropyl myristate, Isopropyl palmitate, octyl palmitate, octyl palm fatty acid, octyl stearate, special beef tallow fatty acid octyl, lauryl laurate, stearyl stearate, behenyl behenate, cetyl myristate, beef tallow oil, hydrogenated castor oil And montanic acid ester.

[0063] Examples of fatty acid lubricants include stearic acid, palmitic acid, oleic acid, linoleic acid, linoleic acid, and montanic acid.

[0064] Examples of the aliphatic alcohol include stearyl alcohol, cetyl alcohol, myristyl alcohol, lauryl alcohol, and the like.

[0065] Examples of partial esters of fatty acids and polyhydric alcohols include stearic acid monodalideside, stearic acid diglycerides, olein-based monodalyrides, and montanic acid partial quinic esters.

[0066] Examples of the paraffinic lubricant include paraffin wax, liquid paraffin, polyethylene wax, oxidized polyethylene wax, and polypropylene wax.

Of these, fatty acid amides and fatty acid esters and paraffinic lubricants are preferred from the standpoint of moldability improvement effect and cost balance.

[0067] The blending amount of the lubricant is preferably 0 to: LO parts by weight, more preferably 100 parts by weight based on the total amount of (a) isobutylene block copolymer and (b) thermoplastic polyurethane resin. 0 to 5 parts by weight, more preferably 0 to 3 parts by weight. If it exceeds 10 parts by weight, it is not sufficiently mixed, and the lubricant tends to bleed out. There is also a tendency for the mechanical strength of the object to decrease, which is not preferable. The lubricant may be added during melt kneading of the component (a) and the component (b), or may be added in advance to the component (a) or the component (b). For component (a), a relatively low polarity paraffin lubricant is preferred. For component (b), a relatively polar high fatty acid amide lubricant or fatty acid ester lubricant is preferred. In order to efficiently obtain the effect of improving moldability, it is preferable to add a paraffinic lubricant to component (a) and a fatty acid amide lubricant or a fatty acid ester lubricant to component (b) in advance. ,.

[0068] Further, various thermoplastic resins, thermosetting resins, other thermoplastic elastomers and the like may be blended as long as the performance of the thermoplastic resin composition of the present invention is not impaired.

[0069] A known method without particular limitation can be applied to the method for producing the thermoplastic rosin composition of the present invention. For example, the above-mentioned components and optionally the additive components are melt-kneaded using a heat-kneader such as a single screw extruder, twin screw extruder, roll, Banbury mixer, brabender, kneader, high shear mixer, etc. By doing so, it can be manufactured. Further, the kneading order of each component is not particularly limited, and can be determined according to the apparatus used, workability, or physical properties of the obtained thermoplastic resin composition.

Example

[0070] The present invention will be described more specifically with reference to the following examples. It should be noted that the present invention is not limited in any way by these examples, and various modifications can be made without departing from the scope of the present invention.

[0071] The molecular weight of the block copolymer shown in this example and the physical properties of the composition were measured by the following methods.

(1) Hardness

In accordance with JIS K 6352, three 2 mm thick press sheets were stacked and measured.

(2) Oil resistance

A 2 mm thick press sheet was prepared, immersed in paraffinic oil and IRM # 3 oil at room temperature for 72 hours, taken out, observed for changes in surface properties, and oil absorption was measured.

Y: No change

X: Changed (deformation or swelling) (3) Mechanical strength

The composition was compression molded at 170 ° C. to prepare a JIS No. 3 dumbbell test piece. According to JIS K6251, tensile strength and elongation were measured at a tensile speed of 500 mmZsec.

(4) Transparency

The composition was compression molded at 170 ° C. to prepare a JIS No. 3 dumbbell test piece. The transparency of the obtained press sheet was judged visually.

○: Transparency

Somewhat transparent

X: No transparency

In addition, a turbidimeter (model: NDH 300A, manufactured by Nippon Denshoku Industries Co., Ltd.) was used for the purpose of quantitatively measuring the transparency, and the turbidity of the sheet obtained from the press sheet was measured.

(5) Molecular weight

A gel permeation chromatography (GPC) system manufactured by Waters (column: Shodex K-804 (polystyrene gel) manufactured by Showa Denshi Co., Ltd., mobile phase: black mouth form) was used. The number average molecular weight is expressed in terms of polystyrene.

Production Example 1 Production of isobutylene block copolymer

In a 2L reaction vessel equipped with a stirrer, 45 ml of 1-chlorobutane (dried with molecular sieves), 319 ml of hexane (dried with molecular sieves), 0.55 g of 1,4 bis (1-chloro-1-methylethyl) benzene added. After the reaction vessel was cooled to -75 ° C, 0.42 g of dimethylacetamide and 182 mL of isobutylene were added. Furthermore, 6.53 mL of tetrachloride-titanium was added to initiate polymerization, and the reaction was allowed to react for 1.5 hours while stirring the solution at 75 ° C. Next, 5 lg of styrene was added to the reaction solution, and the reaction was continued for another 60 minutes, and then the reaction solution was poured into a large amount of water to stop the reaction.

[0073] When the separation state of the organic layer and the aqueous layer was visually confirmed, the separability was good and separation was easy with a separatory funnel. After washing twice with water, after confirming that the aqueous layer is neutral, the organic layer is poured into a large amount of methanol to precipitate the polymer, and the resulting polymer is heated to 60 ° C. And isobutylene block copolymer (SIBS) was obtained by vacuum drying for 24 hours. GPC analysis of the isoprene-based block copolymer (SIBS) revealed that the number average molecule [0074] Examples 1 to 4, Comparative Examples 1 to 4

The following components (a), (b), and (c) were melt-kneaded at a ratio shown in Table 1 using Laboplast Mill (manufactured by Toyo Seiki Co., Ltd.) set at 190 ° C. The obtained composition was compression molded to prepare test pieces, and various physical properties were evaluated. The evaluation results are shown in Table 1.

Component (a): Styrene-isobutylene-styrene block copolymer (SIBS): obtained in Production Example 1.

Component (b): Thermoplastic polyurethane l (TPU): Ester type, manufactured by Dick Bayer Polymer (trade name: Pandettas T-1375), hardness 75.

Component (c): Styrene having an acid anhydride group Ethylene butylene Styrene copolymer (MAH-SEBS): Shell (trade name: Kraton FG1901X), hardness 65.

[0075] [Table 1]

Example 14 The power of the composition of 4 is excellent in all of flexibility (low hardness), oil resistance, and transparency. The composition of Comparative Example 1 4 is flexible (low hardness), oil resistance As a result, it was proved that the difference between the property and transparency was insufficient. Industrial applicability

The thermoplastic resin composition of the present invention is excellent in low hardness, oil resistance and transparency, and also in heat resistance stability and mechanical strength. It can be used for moving equipment use, stationery use, automobile interior / exterior use, civil engineering, construction use, home appliance use, clothing, footwear use, medical use, sanitary goods, packaging transportation materials, electric wire use, etc. In particular, it is suitable for daily goods that require oil resistance and low hardness.

Claims

The scope of the claims

[1] (a) 5 to 95% by weight of an isobutylene block copolymer composed of a polymer block containing isobutylene as a main component and a polymer block containing no isobutylene as a main component and having a monomer component;

(b) Thermoplastic polyurethane 5 to 95% by weight

For a total of 100 parts by weight

(c) An olefin polymer or styrene containing an epoxy group, amino group, hydroxyl group, acid anhydride group, carboxyl group and salt thereof, and at least one functional group selected from the group consisting of carboxylic acid ester forces 0.1 to 50 parts by weight of a polymer

A thermoplastic rosin composition comprising:

[2] The heat according to claim 1, wherein the monomer component is a monomer component mainly composed of an aromatic butyl monomer, wherein the component (a) is not primarily composed of isobutylene. Plastic rosin composition.

[3] The thermoplastic resin according to claim 2, wherein the aromatic bur monomer is at least one selected from the group force of styrene, p-methylstyrene, α-methylstyrene and indene force. A rosin composition.

[4] (a) An isobutylene-based block copolymer is a polymer block containing an aromatic vinyl monomer as a main component. A polymer block containing an isobutylene as a main component is an aromatic vinyl monomer as a main component. Polymer block strength, triblock copolymer, polymer block mainly composed of aromatic vinyl monomer Monoblock polymer, main block composed of isobutylene, and diblock copolymer based on aromatic vinyl monomer A polymer block consisting mainly of a monomer and a polymer block consisting mainly of isobutylene. The thermoplastic resin composition according to claim 2 or 3.

[5] The olefin polymer or the styrene polymer power of component (c) is a styrene, ethylene butylene, or styrene copolymer having an acid anhydride group. The thermoplastic rosin composition as described.