WO2006137134A1 - Thermoplastic resin composition - Google Patents
Thermoplastic resin composition Download PDFInfo
- Publication number
- WO2006137134A1 WO2006137134A1 PCT/JP2005/011454 JP2005011454W WO2006137134A1 WO 2006137134 A1 WO2006137134 A1 WO 2006137134A1 JP 2005011454 W JP2005011454 W JP 2005011454W WO 2006137134 A1 WO2006137134 A1 WO 2006137134A1
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- WIPO (PCT)
- Prior art keywords
- isobutylene
- polymer
- component
- group
- styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/005—Modified block copolymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
Definitions
- 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.
- 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.
- various polymers such as polyolefins, polyurethanes, polyesters, and polystyrenes have been developed and are commercially available.
- 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
- An object of the present invention is to provide a thermoplastic resin composition excellent in low hardness, oil resistance, transparency and the like.
- thermoplastic resin composition containing a styrene polymer or a styrene polymer solves the above problems, and has led to the present invention.
- 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.
- thermoplastic polyurethane 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
- 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.
- 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.
- 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.
- 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.
- 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.
- MAH-SEBS styrene ethylene butylene styrene copolymer
- the present invention relates to a thermoplastic rosin composition.
- 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.
- 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.
- 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.
- block copolymers, diblock copolymers, triblock copolymers, multiblock copolymers, etc. having a linear, branched, or star structure can be selected. is there.
- a polymer block having a monomer component that does not contain isobutylene as the main component is composed 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.
- 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.
- 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.
- Aromatic bulle monomers include styrene, o-methylstyrene, m-methylstyrene. , P-methylstyrene, ⁇ -methylstyrene, ⁇ -methylenostyrene, 2,6 dimethylstyrene, 2,4 dimethylstyrene, ⁇ -methyl- ⁇ -methylstyrene, ⁇ -methyl-m-methylstyrene, ⁇ -methyl- ⁇ — Methyl styrene, j8-methyl-o-methyl styrene, ⁇ -methyl-m-methyl styrene, 13-methyl-p-methyl styrene, 2, 4, 6 trimethyl styrene, ⁇ -methyl-2, 6 dimethyl styrene, ⁇ -methyl-2, 4 dimethyl styrene , 13-methyl-2,6 dimethylstyrene, 13-methyl-2,4 dimethylstyrene, ⁇
- Examples of the gen-based monomer include butadiene, isoprene, hexagen, cyclopentagen, cyclohexagen, dicyclopentagen, divinylbenzene, ethylidene norbornene, and the like.
- butyl ether monomer examples 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.
- silane compound examples include butyltrichlorosilane, butylmethyldichlorosilane, butyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyltrimethylsilane, dibutyldichlorosilane, divininoresimethoxymethoxy, divininoresimethinolessilane, 1,3 dibi- Nore -1, 1, 3, 3-tetramethyldisiloxane, trivinylmethylsilane, ⁇ -methacryloyloxypropyltrimethoxysilane, ⁇ -methacryloyloxypropylmethyldimethoxysilane, and the like.
- 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.
- the aromatic bur monomer it is preferable to use one or more monomers selected from styrene, ⁇ -methyl styrene, ⁇ -methyl styrene, and indene group power. From the viewpoint of cost, styrene, ⁇ —It is particularly preferable to use methylstyrene or a mixture thereof.
- 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.
- 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.
- 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! /.
- 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). .
- GPC gel permeation chromatography
- 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.
- 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. ].
- 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.
- Isopropyl) benzene, bis (2-chloro-2-propynole) benzene! / ⁇ is also called dicuminochloride, and tris (1-chloro-1- 1-methylethyl) benzene is tris (cyclochloroisopropyl) benzene, tris ( 2—Black mouth 2—Propyl) Benzene! / ⁇ ⁇ is also called Tricminolek mouth ride.
- a Lewis acid catalyst may be allowed to coexist.
- Such Lewis acid may be any one that can be used for cationic polymerization.
- Metal halides such as aCl, VC1, FeCl, ZnBr, A1C1, AlBr; Et A1C1, EtAlC
- Organometallic halides such as 1 can be preferably used (Et represents an ethyl group)
- the amount of Lewis acid used is not particularly limited, but polymerization of the monomer used
- 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.
- 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.
- 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.
- 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.
- 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-trimethyl
- 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.
- the components under cooling for example, at a temperature of 100 ° C or higher and lower than 0 ° C.
- the temperature range is 80 ° C to 30 ° C.
- 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.
- thermoplastic polyurethane-based resin (b) examples 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.
- 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.
- 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.
- organic diisocyanate (i) any conventionally known ones can be used.
- dihydroxy compounds having a molecular weight of less than 500 can be used.
- 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.
- 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.
- polyether diol examples include polypropylene ether glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol, and other copolymerized polyether glycols.
- polycarbonate diol examples 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.
- thermoplastic polyurethane-based resins can be used.
- thermoplastic resin composition of the present invention 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.
- 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.
- 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.
- 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.
- 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).
- SBS styrene butadiene copolymer
- SIS styrene isoprene styrene block copolymer
- SEBS styrene ethylene
- 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.
- styrene-ethylene-butylene-styrene copolymer (MAH-SEBS) having an acid anhydride group is preferred! /.
- 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.
- component (c) 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.
- 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.
- 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 ⁇ -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.
- 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.
- 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.
- 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.
- 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.
- softening agents may be used alone or in combination of two or more kinds in order to obtain the desired viscosity and physical properties.
- 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.
- 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.
- 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.
- 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.
- 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.
- the amount exceeds 100 parts by weight, the mechanical strength of the resulting thermoplastic resin composition is lowered, and the flexibility is also impaired.
- 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.
- 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.
- 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.
- Examples of the fatty acid metal salt lubricant include calcium stearate, magnesium stearate, aluminum stearate, zinc stearate, barium stearate, and metal montanate.
- 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.
- fatty acid lubricants include stearic acid, palmitic acid, oleic acid, linoleic acid, linoleic acid, and montanic acid.
- Examples of the aliphatic alcohol include stearyl alcohol, cetyl alcohol, myristyl alcohol, lauryl alcohol, and the like.
- partial esters of fatty acids and polyhydric alcohols include stearic acid monodalideside, stearic acid diglycerides, olein-based monodalyrides, and montanic acid partial quinic esters.
- paraffinic lubricant examples include paraffin wax, liquid paraffin, polyethylene wax, oxidized polyethylene wax, and polypropylene wax.
- fatty acid amides and fatty acid esters and paraffinic lubricants are preferred from the standpoint of moldability improvement effect and cost balance.
- 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).
- component (a) a relatively low polarity paraffin lubricant is preferred.
- component (b) a relatively polar high fatty acid amide lubricant or fatty acid ester lubricant is preferred.
- a paraffinic lubricant to component (a) and a fatty acid amide lubricant or a fatty acid ester lubricant to component (b) in advance.
- 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.
- thermoplastic rosin composition of the present invention A known method without particular limitation can be applied to the method for producing the thermoplastic rosin composition of the present invention.
- 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.
- a heat-kneader such as a single screw extruder, twin screw extruder, roll, Banbury mixer, brabender, kneader, high shear mixer, etc.
- 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.
- 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.
- 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.
- 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.
- 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.
- GPC gel permeation chromatography
- Component (a) Styrene-isobutylene-styrene block copolymer (SIBS): obtained in Production Example 1.
- SIBS Styrene-isobutylene-styrene block copolymer
- TPU Thermoplastic polyurethane l
- MAH-SEBS Ethylene butylene Styrene copolymer
- Shell Shell (trade name: Kraton FG1901X), hardness 65.
- 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
- 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.
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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
明 細 書 Specification
熱可塑性樹脂組成物 Thermoplastic resin composition
技術分野 Technical field
[0001] 本発明は、特定のイソブチレン系ブロック共重合体、熱可塑性ポリウレタン系榭脂、 及び、特定の官能基を含有するォレフイン系重合体又はスチレン系重合体を含有し てなる熱可塑性榭脂組成物に関する。 [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.
背景技術 Background art
[0002] 近年ゴム的な軟質材料であって、加硫工程を要せず、熱可塑性榭脂と同様な成形 加工性を有する熱可塑性エラストマ一が注目されている。このような熱可塑性エラスト マーには現在、ポリオレフイン系、ポリウレタン系、ポリエステル系、ポリスチレン系等 の種々のポリマーが開発され、市販されている。これら熱可塑性エラストマ一のなか でも、ポリスチレン系熱可塑性エラストマ一(特許文献 1参照)は加工性、コスト面より 広く利用されているが、低硬度、耐油性、透明性等をすベて満足するものはな力つた 特許文献 1:特開平 11― 293083号公報 [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
発明の開示 Disclosure of the invention
発明が解決しょうとする課題 Problems to be solved by the invention
[0003] 本発明の目的は、低硬度、耐油性、透明性等に優れた熱可塑性榭脂組成物を提 供することにある。 [0003] An object of the present invention is to provide a thermoplastic resin composition excellent in low hardness, oil resistance, transparency and the like.
課題を解決するための手段 Means for solving the problem
[0004] 本発明者らは、上記課題を解決するために鋭意研究を積み重ねた結果、特定のィ ソブチレン系ブロック共重合体、熱可塑性ポリウレタン系榭脂、及び、特定の官能基 を含有するォレフイン系重合体又はスチレン系重合体を含有してなる熱可塑性榭脂 組成物が前記課題を解決することを見出し、本発明に至ったものである。 [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] 即ち本発明は、(a)イソブチレンを主成分とする重合体ブロックと、イソブチレンを主 成分としない単量体成分力もなる重合体ブロックとから構成されるイソブチレン系ブロ ック共重合体 5〜95重量%、(b)熱可塑性ポリウレタン 5〜95重量%力もなる組成物
の総量 100重量部に対し、(c)エポキシ基、アミノ基、水酸基、酸無水物基、カルボキ シル基及びその塩、並びに、カルボン酸エステルカゝらなる群より選ばれる少なくとも 1 種の官能基を含有するォレフイン系重合体又はスチレン系重合体 0. 1〜50重量部 、を含有することを特徴とする熱可塑性榭脂組成物に関する。 [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] 好ましい実施態様としては、(a)成分のイソブチレンを主成分としない単量体成分 力 芳香族ビュル系単量体を主成分とする単量体成分であることを特徴とする熱可 塑性榭脂組成物に関する。 [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] 好ましい実施態様としては、芳香族ビニル系単量体がスチレン、 p—メチルスチレン 、 a—メチルスチレン及びインデン力 なる群力 選ばれる少なくとも 1種以上である 熱可塑性榭脂組成物に関する。 [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] 好ましい実施態様としては、(a)イソブチレン系ブロック共重合体力 芳香族ビュル 系単量体を主成分とする重合体ブロック イソブチレンを主成分とする重合体ブロッ クー芳香族ビュル系単量体を主成分とする重合体ブロック力 なるトリブロック共重合 体、芳香族ビュル系単量体を主成分とする重合体ブロック イソブチレンを主成分と する重合体ブロック力 なるジブロック共重合体、及び、芳香族ビニル系単量体を主 成分とする重合体ブロックとイソブチレンを主成分とする重合体ブロック力 なるァー ムを 3つ以上有する星型ブロック共重合体力 なる群力 選ばれる少なくとも 1種以上 であることを特徴とする熱可塑性榭脂組成物に関する。 [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] 好ましい実施態様としては、(c)成分のォレフィン系重合体又はスチレン系重合体 が、酸無水物基を有するスチレン エチレンブチレン スチレン共重合体(MAH— SEBS)であることを特徴とする熱可塑性榭脂組成物に関する。 [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.
発明の効果 The invention's effect
[0010] 本発明の熱可塑性榭脂組成物は低硬度、耐油性、透明性に優れており、さらに、 耐熱安定性、機械強度にも優れていることから、食品用途、日用雑貨用途、玩具 ·運 動用具用途、文具用途、自動車内外装用途、土木,建築用途、家電機器用途、衣料 ,履き物用途、医療用途、衛生用品、包装輸送資材、電線用途等に利用可能である 。特に、耐油性と低硬度を要求される日用雑貨用途に好適である。 [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.
発明を実施するための最良の形態
[0011] 以下に本発明を詳細に説明する。 BEST MODE FOR CARRYING OUT THE INVENTION [0011] The present invention is described in detail below.
[0012] 本発明の(a)イソブチレン系ブロック共重合体は、イソブチレンを主成分とする重合 体ブロック及びイソブチレンを主成分としない単量体成分からなる重合体ブロックを 有しているものであれば特に制限はなぐ例えば、直鎖状、分岐状、星状等の構造を 有するブロック共重合体、ジブロック共重合体、トリブロック共重合体、マルチブロック 共重合体等のいずれも選択可能である。好ましいブロック共重合体としては、物性バ ランス及び必要に応じて使用される後述の軟化剤の吸収能の点から、イソブチレンを 主成分としない単量体成分力 なる重合体ブロック イソブチレンを主成分とする重 合体ブロック イソブチレンを主成分としない単量体成分力 なる重合体ブロックから なるトリブロック共重合体、イソブチレンを主成分としな 、単量体成分からなる重合体 ブロック イソブチレンを主成分とする重合体ブロック力 なるジブロック共重合体、ィ ソブチレンを主成分としない単量体成分からなる重合体ブロックとイソブチレンを主成 分とする重合体ブロック力 なるアームを 3本以上有する星型ブロック共重合体等が 挙げられる。これらは所望の物性'成形加工性を得る為に 1種又は 2種以上を組み合 わせて使用可能である。 [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.
[0013] 本発明のイソブチレンを主成分としない単量体成分は、イソブチレンの含有量が 30 重量%以下である単量体成分を示す。イソブチレンを主成分としな!ヽ単量体成分中 のイソブチレンの含有量は 10重量%以下であることが好ましぐ 3重量%以下である ことがさらに好ましい。 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] 本発明のイソブチレンを主成分としない単量体成分中の、イソブチレン以外の単量 体は、カチオン重合可能な単量体成分であれば特に限定されないが、脂肪族ォレフ イン系、芳香族ビュル系、ジェン系、ビニルエーテル系、シラン化合物、ビニルカル バゾール、 13—ビネン、ァセナフチレン等の単量体が例示できる。これらは 1種又は 2 種以上組み合わせて使用される。 [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] 脂肪族ォレフイン系単量体としては、エチレン、プロピレン、 1ーブテン、 2 メチル [0015] Aliphatic olefin monomers include ethylene, propylene, 1-butene, and 2-methyl.
1ーブテン、 3—メチルー 1ーブテン、ペンテン、へキセン、シクロへキセン、 4ーメチ ルー 1 ペンテン、ビュルシクロへキサン、オタテン、ノルボルネン等が挙げられる。 Examples include 1-butene, 3-methyl-1-butene, pentene, hexene, cyclohexene, 4-methyl pentene, butylcyclohexane, otaten, norbornene, and the like.
[0016] 芳香族ビュル系単量体としては、スチレン、 o—メチルスチレン、 m—メチルスチレン
、 p—メチルスチレン、 α—メチルスチレン、 βーメチノレスチレン、 2, 6 ジメチルスチ レン、 2, 4 ジメチルスチレン、 α—メチルー ο—メチルスチレン、 α—メチルー m— メチルスチレン、 α—メチルー ρ—メチルスチレン、 j8—メチルー ο—メチルスチレン、 βーメチルー m—メチルスチレン、 13ーメチルー p—メチルスチレン、 2, 4, 6 トリメ チルスチレン、 α—メチルー 2, 6 ジメチルスチレン、 α—メチルー 2, 4 ジメチル スチレン、 13ーメチルー 2, 6 ジメチルスチレン、 13ーメチルー 2, 4 ジメチルスチ レン、 ο クロロスチレン、 m—クロロスチレン、 p クロロスチレン、 2, 6 ジクロロスチ レン、 2, 4 ジクロロスチレン、 α クロ口一 o クロロスチレン、 α—クロ口一 m クロ ロスチレン、 ひ一クロロー p—クロロスチレン、 ;8—クロロー o クロロスチレン、 β —ク ロロ m—クロロスチレン、 β クロロー ρ—クロロスチレン、 2, 4, 6 トリクロロスチレ ン、 α クロロー 2, 6 ジクロロスチレン、 α クロロー 2, 4 ジクロロスチレン、 /3— クロ口一 2, 6 ジクロロスチレン、 /3—クロ口一 2, 4 ジクロロスチレン、 o— t—ブチ ノレスチレン、 m—t ブチルスチレン、 p—t—ブチルスチレン、 o—メトキシスチレン、 m—メトキシスチレン、 ρ—メトキシスチレン、 o クロロメチルスチレン、 m—クロロメチ ノレスチレン、 p クロロメチノレスチレン、 o ブロモメチノレスチレン、 m—ブロモメチノレス チレン、 p ブロモメチルスチレン、シリル基で置換されたスチレン誘導体、インデン、 ビュルナフタレン等が挙げられる。 [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] ジェン系単量体としては、ブタジエン、イソプレン、へキサジェン、シクロペンタジェ ン、シクロへキサジェン、ジシクロペンタジェン、ジビニルベンゼン、ェチリデンノルボ ルネン等が挙げられる。 [0017] Examples of the gen-based monomer include butadiene, isoprene, hexagen, cyclopentagen, cyclohexagen, dicyclopentagen, divinylbenzene, ethylidene norbornene, and the like.
[0018] ビュルエーテル系単量体としては、メチルビ-ルエーテル、ェチルビ-ルエーテル 、 n—プロピルビニルエーテル、イソプロピルビニルエーテル、 n—ブチルビニルエー テル、 sec ブチルビニルエーテル、 tert ブチルビニルエーテル、イソブチルビ二 ノレエーテノレ、メチノレプロぺニノレエーテノレ、ェチノレプロぺニノレエーテノレ等が挙げられ る。 [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] シラン化合物としては、ビュルトリクロロシラン、ビュルメチルジクロロシラン、ビュル ジメチルクロロシラン、ビニルジメチルメトキシシラン、ビニルトリメチルシラン、ジビュル ジクロロシラン、ジビニノレジメトキシシラン、ジビニノレジメチノレシラン、 1, 3 ジビ-ノレ
- 1, 1, 3, 3—テトラメチルジシロキサン、トリビニルメチルシラン、 γ—メタクリロイル ォキシプロピルトリメトキシシラン、 Ίーメタクリロイルォキシプロピルメチルジメトキシシ ラン等が挙げられる。 [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] 本発明のイソブチレンを主成分としない単量体成分は、物性及び重合特性等のバ ランスから、芳香族ビニル系単量体を主成分とする単量体成分であることが好まし 、 。本発明の芳香族ビュル系単量体を主成分とする単量体成分は、芳香族ビニル系 単量体の含有量が 60重量%以上、好ましくは 80重量%以上である単量体成分を示 す。芳香族ビュル系単量体としては、スチレン、 α—メチルスチレン、 ρ—メチルスチ レン及びインデン力 なる群力 選ばれる 1種以上の単量体を使用することが好ましく 、コストの面からスチレン、 α—メチルスチレン、あるいはこれらの混合物を用いること が特に好ましい。 [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] また本発明のイソブチレンを主成分とする単量体成分は、イソプチレン以外の単量 体を含んでいてもよいし、含んでいなくても良ぐ通常、イソブチレンを 60重量%以上 、好ましくは 80重量%以上含有する単量体成分である。イソプチレン以外の単量体 としてはカチオン重合可能な単量体であれば特に制限はな!/、が、例えば上記の単量 体等が挙げられる。 [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] イソブチレンを主成分とする重合体ブロックとイソブチレンを主成分としな!/、単量体 成分力もなる重合体ブロックの割合に関しては、特に制限はないが、各種物性の面 から、イソブチレンを主成分とする重合体ブロック力 0から 95重量%、イソブチレンを 主成分としない単量体成分力もなる重合体ブロックが 5から 60重量%であることが好 ましぐイソブチレンを主成分とする重合体ブロックが 50から 85重量%、イソブチレン を主成分としない単量体成分力もなる重合体ブロックが 15から 50重量%であること が特に好ましい。 [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] またイソブチレン系ブロック共重合体の数平均分子量にも特に制限はないが、流動 '性、カロ工'性、物'性等の面力ら、 30000〜500000であること力 S好ましく、 50000〜40 0000であることが特に好まし!/、。イソブチレン系ブロック共重合体の数平均分子量が 30000よりも低い場合には、必要に応じて使用される軟化剤のブリードアウトが起こ る傾向にあり機械的な物性が十分に発現されず、一方 500000を超える場合には流
動性、加工性の面で不利である。上記数平均分子量は、 Waters社製ゲルパーミエ ーシヨンクロマトグラフィー(GPC)システム(カラム:昭和電工株式会社製 Shodex K - 804 (ポリスチレンゲル)、移動相:クロ口ホルム)を用いて測定した値である。 [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] イソブチレン系ブロック共重合体の製造方法につ!、ては特に制限はな!/、が、例え ば、下記一般式(1)で表される化合物の存在下に、イソブチレンを主成分とする単量 体成分及びイソブチレンを主成分としない単量体成分を重合させることにより得られ る。 [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) R3 (1) (CR'R'X) R 3 (1)
[式中 Xはハロゲン原子、炭素数 1〜6のアルコキシ基又は炭素数 1〜6のァシロキシ 基を示す。
R2はそれぞれ水素原子または炭素数 1〜6の 1価の炭化水素基を示 し、 R2は同一であっても異なっていても良い。 R3は多価芳香族炭化水素基また は多価脂肪族炭化水素基であり、 nは 1〜6の自然数を示す。 ]。 [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] 上記一般式(1)で表される化合物は開始剤となるもので、ルイス酸等の存在下炭素 陽イオンを生成し、カチオン重合の開始点になると考えられる。本発明で用いられる 一般式(1)の化合物の例としては、次のような化合物等が挙げられる。 [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—クロル— 1—メチルェチル)ベンゼン〔C H C (CH ) Cl〕、 1, 4 ビス(1—クロ (1-Chloro-1-methylethyl) benzene [C H C (CH) Cl], 1, 4 Bis (1-chloro
6 5 3 2 6 5 3 2
ル— 1—メチルェチル)ベンゼン〔1, 4 Cl (CH ) CC H C (CH ) Cl〕、 1, 3 ビス Ru- 1-methylethyl) benzene [1, 4 Cl (CH) CC H C (CH) Cl], 1, 3 bis
3 2 6 4 3 2 3 2 6 4 3 2
(1—クロル— 1—メチルェチル)ベンゼン〔1, 3— Cl(CH ) CC H C (CH ) Cl〕、 1 (1-Chloro-1-methylethyl) benzene [1, 3-Cl (CH) CC H C (CH) Cl], 1
3 2 6 4 3 2 3 2 6 4 3 2
, 3, 5 トリス(1—クロル— 1—メチルェチル)ベンゼン〔1, 3, 5— (CIC (CH ) ) C , 3, 5 Tris (1-chloro-1-methylethyl) benzene [1, 3, 5— (CIC (CH)) C
3 2 3 6 3 2 3 6
H〕、 1, 3 ビス(1—クロル— 1—メチルェチル)— 5— (tert—ブチル)ベンゼン〔1,H], 1, 3 bis (1-chloro-1-methylethyl) -5- (tert-butyl) benzene [1,
3 Three
3—(C (CH ) C1) - 5 -(C (CH ) ) C H〕。 3— (C (CH) C1) -5-(C (CH)) C H].
3 2 2 3 3 6 3 3 2 2 3 3 6 3
[0026] これらの中でも特に好まし!/、のはビス(1 クロル一 1—メチルェチル)ベンゼン [C [0026] Particularly preferred among these! / Is bis (1-chloro-1-methylethyl) benzene [C
6 6
H (C (CH ) C1) ]、トリス(1 クロルー1ーメチルェチル)ベンゼン [ (C1C (CH ) )H (C (CH) C1)], tris (1 chloro 1-methylethyl) benzene [(C1C (CH))
4 3 2 2 3 2 34 3 2 2 3 2 3
C H ]である。なおビス(1—クロル一 1—メチルェチル)ベンゼンは、ビス(ひ一クロ口C H]. Note that bis (1-chloro-1-methylethyl) benzene is
6 3 6 3
イソプロピル)ベンゼン、ビス(2—クロ口 2—プロピノレ)ベンゼンある!/ヽはジクミノレクロ ライドとも呼ばれ、トリス(1—クロル一 1—メチルェチル)ベンゼンは、トリス(ひ クロ口 イソプロピル)ベンゼン、トリス(2—クロ口一 2—プロピル)ベンゼンある!/ヽはトリクミノレク 口ライドとも呼ばれる。
[0027] イソブチレン系ブロック共重合体を重合により製造する際に、さらにルイス酸触媒を 共存させることもできる。このようなルイス酸としてはカチオン重合に使用できるもので あれば良く、 TiCl、 TiBr、 BC1 , BF , BF -OEt、 SnCl、 SbCl、 SbF、 WC1、 T 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 aCl、 VC1、 FeCl、 ZnBr、 A1C1、 AlBr等の金属ハロゲン化物; Et A1C1、 EtAlC 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 25 5 3 2 3 3 2
1等の有機金属ハロゲンィ匕物を好適に使用することができる(Etはェチル基を表す)Organometallic halides such as 1 can be preferably used (Et represents an ethyl group)
2 2
。中でも触媒としての能力、工業的な入手の容易さを考えた場合、 TiCl、 BC1、 Sn . Above all, considering the capacity as a catalyst and industrial availability, TiCl, BC1, Sn
4 3 4 3
CIが好ましい。ルイス酸の使用量は、特に限定されないが、使用する単量体の重合CI is preferred. The amount of Lewis acid used is not particularly limited, but polymerization of the monomer used
4 Four
特性あるいは重合濃度等を鑑みて設定することができる。通常は一般式(1)で表さ れる化合物に対して 0. 1〜: L00モル当量使用することができ、好ましくは 1〜50モル 当量の範囲である。 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] イソブチレン系ブロック共重合体の重合に際しては、さらに必要に応じて電子供与 体成分を共存させることもできる。この電子供与体成分は、カチオン重合に際して、 成長炭素カチオンを安定化させる効果があるものと考えられており、電子供与体の添 加によって分子量分布の狭い構造が制御された重合体を生成することができる。使 用可能な電子供与体成分としては特に限定されないが、例えば、ピリジン類、ァミン 類、アミド類、スルホキシド類、エステル類、または金属原子に結合した酸素原子を有 する金属化合物等を挙げることができる。 [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] イソブチレン系ブロック共重合体の重合は必要に応じて有機溶媒中で行うことがで き、有機溶媒としてはカチオン重合を本質的に阻害しなければ特に制約なく使用す ることができる。具体的には、塩化メチル、ジクロロメタン、クロ口ホルム、塩化工チル、 ジクロロエタン、 n—プロピルクロライド、 n—ブチルクロライド、クロ口ベンゼン等のハロ ゲン化炭化水素;ベンゼン、トルエン、キシレン、ェチルベンゼン、プロピルベンゼン、 ブチルベンゼン等のアルキルベンゼン類;ェタン、プロパン、ブタン、ペンタン、へキ サン、ヘプタン、オクタン、ノナン、デカン等の直鎖式脂肪族炭化水素類; 2—メチル プロパン、 2—メチルブタン、 2, 3, 3—トリメチルペンタン、 2, 2, 5—トリメチルへキサ ン等の分岐式脂肪族炭化水素類;シクロへキサン、メチルシクロへキサン、ェチルシ クロへキサン等の環式脂肪族炭化水素類;石油留分を水添精製したパラフィン油等 を挙げることができる。
[0030] これらの溶媒は、ブロック共重合体を構成する単量体の重合特性及び生成する重 合体の溶解性等のバランスを考慮して単独又は 2種以上を組み合わせて使用される [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] 上記溶媒の使用量は、得られる重合体溶液の粘度や除熱の容易さを考慮して、重 合体の濃度が好ましくは 1〜50重量%、より好ましくは 5〜35重量%となるように決定 することができる。 [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] 実際の重合を行うに当たっては、各成分を冷却下例えば 100°C以上 0°C未満の 温度で混合することが好ま 、。エネルギーコストと重合の安定性を釣り合わせるた めに、特に好まし 、温度範囲は 80°C〜一 30°Cである。 [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] 本発明の(b)熱可塑性ポリウレタン系榭脂としては、エステル系、エーテル系、カー ボネート系等、各種の熱可塑性ポリウレタン系榭脂が使用される。 [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] 熱可塑性ポリウレタン系榭脂 (b)としては、例えば、(ィ)有機ジイソシァネート、(口) 鎖伸張剤、(ハ)高分子ポリオール力もなる熱可塑性ポリウレタン系榭脂が挙げられる 。その製造方法はいかなる方法でも良ぐ例えば (ィ)成分と、予め均一に混合した( 口)成分および (ハ)成分とを高速攪拌混合して離型処理したバット上に流延して必要 に応じて 200°C以下の温度で反応して製造する力、或いは、(ィ)成分と(口)成分を 加えて末端イソシァネート基のプレボリマーとした後、(ハ)成分を加えて高速攪拌混 合し離型処理したバット上に流延して、必要に応じて 200°C以下の温度で反応して 製造するなど従来より公知の技術を利用できる。 [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] 有機ジイソシァネート (ィ)としては、従来より公知のものがいずれも使用できるが、 例えばへキサメチレンジイソシァネート、リジンジイソシァネート、イソホロンジイソシァ ネート、キシレンジイソシァネート、シクロへキサンジイソシァネート、トルイジンジイソ シァネート、 2, 4—トリレンジイソシァネート、 2, 6—トリレンジイソシァネート、 4, 4,— ジフエ-ルメタンジイソシァネート、 p フエ-レンジイソシァネート、 m—フエ-レンジ イソシァネート、 1, 5 ナフタレンジイソシァネートなどの単独あるいはこれらの混合 物が使用できる。 [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] 鎖伸張剤(口)としては、分子量が 500より小さいジヒドロキシィ匕合物が使用できるが 、例えば、エチレングリコール、 1, 2 プロピレングリコール、 1, 3 プロピレングリコ
ール、 2, 3 ブチレングリコール、 1, 4 ブタンジオール、 2, 2,一ジメチルー 1, 3— プロパンジオール、ジエチレングリコール、 1, 5 ペンタンジオール、 1, 6 へキサ ンジオール、シクロへキサン一 1, 4ージオール、シクロへキサン一 1, 4ージメタノール などの単独あるいは混合物が挙げられる。 [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] 高分子ポリオール(ハ)としては、平均分子量が 500〜4000のジヒドロキシ化合物 が使用できる力 例えば、ポリエステルジオール、ポリエーテルジオール、ポリカーボ ネートジオール等が挙げられる。 [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] ポリエステルジオールとしては、エチレングリコール、プロピレングリコール、 1, 4 ブタンジオール、 1, 5 ペンタンジオール、 1, 6 へキサンジオール、ネオペンチル グリコール、 3—メチルー 1, 5 ペンタンジオール、シクロへキサンジメタノール、或い はその他の低分子ジオール成分の 1種叉は 2種以上とダルタル酸、スベリン酸、セバ シン酸、テレフタル酸、イソフタル酸等の低分子ジカルボン酸の 1種叉は 2種以上との 縮合重合物やラタトンの開環重合で得たポリラタトンジオール、例えばポリプロビオラ タトンジオール、ポリ力プロラタトンジオール、ポリバレロラタトンジオール等が挙げられ る。 [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] ポリエーテルジオールとしては、ポリプロピレンエーテルグリコール、ポリテトラメチレ ンエーテルグリコール、ポリへキサメチレンエーテルグリコール、その他の共重合ポリ エーテルグリコール等が挙げられる。 [0039] Examples of the polyether diol include polypropylene ether glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol, and other copolymerized polyether glycols.
[0040] ポリカーボネートジオールとしては、ポリへキサメチレンカーボネートジオール、ポリ へキサメチレンカーボネートジオールにラタトンを開環付加重合して得られるジォー ル、ポリへキサメチレンカーボネートジオールと他のポリエステルジオール、ポリエー テルジオール、ポリエーテル ·エステルジオールとの共縮合物等が挙げられる。 [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] 上記熱可塑性ポリウレタン系榭脂は、 1種又は 2種以上を用いることができる。 [0041] One or more of the above thermoplastic polyurethane-based resins can be used.
[0042] 本発明の熱可塑性榭脂組成物の透明性を高めるためには、(a)成分と (b)成分の 屈折率が近いものを組み合わせることで実現できる。屈折率は、アッベ屈折計 NAR - 3T (株式会社ァタゴ製)のような、ナトリウムの D線を用いた方法で測定した値を使 用することができる。 [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] 成分 (b)熱可塑性ポリウレタン系榭脂の配合量は、成分 (a)イソブチレン系ブロック
共重合体 5〜95重量%に対して、 5〜95重量%、好ましくは(a)イソブチレン系ブロ ック共重合体 25〜75重量%に対して、 25〜75重量%である。 5重量%未満の場合 は、得られる熱可塑性榭脂組成物の耐油性が低下し、 95重量%を超えると得られる 熱可塑性榭脂組成物の硬度が上昇し、柔軟な感触が低下してしまう。 [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] 本発明の(c)成分に用いられる、官能基を含有するォレフイン系重合体又はスチレ ン系重合体中の官能基は、極性を有する官能基であり、エポキシ基、アミノ基、水酸 基、酸無水物基、カルボキシル基及びその塩、並びに、カルボン酸エステルからなる 群より選ばれる少なくとも 1種の官能基である。ここでいう重合体とは、共重合体のこと も含み、共重合体の共重合様式には特に制限はなぐランダム共重合体、グラフト共 重合体、ブロック共重合体など 、ずれの共重合体様式であっても良 、。 [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] ォレフィン系重合体、及びスチレン系重合体の例としては、エチレン プロピレン共 重合体、エチレンーブテン共重合体、エチレン オタテン共重合体、エチレン一へキ セン共重合体などのエチレン. (Xーォレフイン系共重合体;ポリエチレン、ポリプロピ レン、ポリスチレン、ポリブテン、エチレン プロピレン ジェン共重合体、スチレン ブタジエン共重合体、スチレン ブタジエン スチレンブロック共重合体(SBS)、ス チレン イソプレン スチレンブロック共重合体(SIS)、ポリブタジエン、ブタジエン —アクリロニトリル共重合体、ポリイソプレン、ブテン—イソプレン共重合体、スチレン エチレンブチレン スチレンブロック共重合体(SEBS)、スチレン エチレンプロ ピレン一スチレンブロック共重合体 (SEPS)などが例示できる。 [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] 本発明の(c)成分に用いられる官能基を有するォレフィン系重合体、及びスチレン 系重合体の具体例としては、エチレン' aーォレフイン系共重合体などのポリオレフィ ン系重合体に、マレイン酸無水物、琥珀酸無水物、フマル酸無水物などの酸無水物 を共重合したもの、アクリル酸、メタクリル酸、酢酸ビュルなどのカルボン酸及びその Na、 Zn、 K、 Ca、 Mgなどの塩、アクリル酸メチル、メタクリル酸メチル、アクリル酸ェ チル、メタクリル酸ェチル、アクリル酸プロピル、メタクリル酸プロピル、アクリル酸ブチ ル、メタクリル酸ブチルなどのカルボン酸エステルが共重合されたォレフイン系重合 体などが挙げられる。 [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] より具体的にはエチレン アクリル酸メチル共重合体、エチレン アクリル酸ェチル
共重合体、エチレン アクリル酸 n プロピル共重合体、エチレン アクリル酸イソプ 口ピル共重合体、エチレン アクリル酸 n ブチル共重合体、エチレン アクリル酸 t ブチル共重合体、エチレン アクリル酸イソブチル共重合体、エチレンーメタクリル 酸メチル共重合体、エチレンーメタクリル酸ェチル共重合体、エチレンーメタクリル酸 n—プロピル共重合体、エチレンーメタクリル酸イソプロピル共重合体、エチレンーメ タクリル酸 n ブチル共重合体、エチレンーメタクリル酸 t ブチル共重合体、ェチレ ンーメタクリル酸イソブチル共重合体、エチレン (メタ)アクリル酸共重合体およびそ の Na、 Zn、 K、 Ca、 Mgなどの金属塩、エチレン マレイン酸無水物共重合体、ェチ レンーブテン マレイン酸無水物共重合体、エチレン プロピレン一マレイン酸無水 物共重合体、エチレン一へキセン マレイン酸無水物共重合体、エチレン ォクテ ンーマレイン酸無水物共重合体、プロピレン マレイン酸無水物共重合体、無水マ レイン酸変性の SBS、無水マレイン酸変性の SIS、無水マレイン酸変性の SEBS、無 水マレイン酸変性の SEPS、無水マレイン酸変性のエチレン アクリル酸ェチル共重 合体などが例示できる。(c)成分としては、 1種又は 2種以上を組み合わせて使用可 能である。 [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] (c)成分としては、透明性の観点から、酸無水物基を有するスチレン エチレンブ チレン スチレン共重合体(MAH— SEBS)が好まし!/、。 [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] 本発明の熱可塑性榭脂組成物は、 (a)成分と (b)成分の総量 100重量部に対して 、 (c)成分であるォレフィン系重合体又はスチレン系重合体を、 0. 1〜50重量部含 有するものである。好ましい下限は、 0. 5重量部、好ましい上限は、 20重量部である [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] (c)成分であるォレフィン系重合体又はスチレン系重合体が 0. 1重量部未満である と、相溶性が十分に発現されず、 50重量部を超えると組成物中の(a)成分の割合が 減少するため好ましくな 、。 [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] (c)成分は、 (a)成分と (b)成分の溶融混練時に添加してもよ!/、し、あらかじめ(a) 成分または (b)成分に添加してぉ 、てもよ 、。あらかじめ(a)成分または (b)成分に 添加しておく方が、相溶性の改良効果が発現しやすぐ好ましい。 [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] 本発明の組成物には、ポリオレフイン系榭脂も必要に応じ使用される。ポリオレフィ
ン系榭脂としては、 a一才レフインの単独重合体、ランダム共重合体、ブロック共重合 体及びそれらの混合物、または α—ォレフインと他の不飽和単量体とのランダム共重 合体、ブロック共重合体、グラフト共重合体及びこれら重合体の酸化、ハロゲン化又 はスルホンィ匕したもの等を 1種又は 2種以上組み合わせて使用できる。具体的には、 ポリエチレン、エチレン プロピレン共重合体、エチレン プロピレン 非共役ジェン 共重合体、エチレンーブテン共重合体、エチレン一へキセン共重合体、エチレン オタテン共重合体、エチレン 酢酸ビュル共重合体、エチレン ビュルアルコール 共重合体、エチレン ェチルアタリレート共重合体、塩素化ポリエチレン等のポリェ チレン系榭脂;ポリプロピレン、プロピレン一エチレンランダム共重合体、プロピレン一 エチレンブロック共重合体、塩素化ポリプロピレン等のポリプロピレン系榭脂;ポリブテ ン、ポリイソプチレン、ポリメチルペンテン、環状ォレフィンの(共)重合体等が例示で きる。これらの中でコスト、熱可塑性榭脂の物性バランスの点からポリエチレン系榭脂 、ポリプロピレン系榭脂、又はこれらの混合物が好ましく使用できる。 [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] ポリオレフイン系榭脂の配合量は、(a)成分と (b)成分の総量 100重量部に対して、 0〜: L 00重量部、好ましくは 0〜 50重量部、さらに好ましくは 0〜 30重量部である。 10 0重量部を超えると硬度が高くなるために好ましくない。 [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] 本発明の組成物には、軟化剤も必要に応じ使用される。特に限定されないが、通 常、室温で液体又は液状の材料が好適に用いられる。また親水性及び疎水性のい ずれの軟化剤も使用できる。このような軟化剤としては鉱物油系、植物油系、合成系 等の各種ゴム用又は榭脂用軟化剤が挙げられる。鉱物油系としては、ナフテン系、 ノ ラフィン系等のプロセスオイル等力 植物油系としては、ひまし油、綿実油、あまみ 油、なたね油、大豆油、パーム油、やし油、落花生油、木ろう、パインオイル、オリー ブ油等が、合成系としてはポリブテン、低分子量ポリブタジエン等が例示できる。これ らの中でも成分 (a)との相溶性あるいは熱可塑性榭脂組成物の物性バランスの点か ら、パラフィン系プロセスオイル、ポリブテンが好ましく用いられる。これら軟化剤は、 単独で用いてもよ!、し、所望の粘度及び物性を得るために 2種以上を適宜組み合わ せて使用することも可能である。 [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] 軟化剤の配合量は、(a)成分と (b)成分の総量 100重量部に対して、 0〜: L00重量
部、好ましくは 0〜50重量部、さらに好ましくは 0〜30重量部である。 100重量部を超 えると軟化剤のブリードアウトが発生するため好ましくない。 [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] さらに本発明の榭脂組成物には、物性改良あるいは経済上のメリットから充填材を 配合することができる。好適な充填材としては、クレー、珪藻土、シリカ、タルク、硫酸 ノリウム、炭酸カルシウム、炭酸マグネシウム、金属酸化物、マイ力、グラフアイト、水 酸化アルミニウム等の麟片状無機充填材;各種の金属粉、木片、ガラス粉、セラミック ス粉、カーボンブラック、粒状又は粉末ポリマー等の粒状又は粉末状固体充填材;そ の他の各種の天然又は人工の短繊維、長繊維等が例示できる。また中空フィラー、 例えば、ガラスバルーン、シリカバルーン等の無機中空フィラー、ポリフッ化ビ -リデ ン、ポリフッ化ビ-リデン共重合体力もなる有機中空フイラ一等を配合することにより、 軽量ィ匕を図ることができる。更に軽量化、衝撃吸収性等の各種物性の改善のために 、各種発泡剤を混入させることも可能であり、また、混合時等に機械的に気体を混ぜ 込むことも可能である。これらは 1種又は 2種以上を組み合わせて使用可能である。 [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] 充填材の配合量は、(a)成分と (b)成分の総量 100重量部に対して、 0〜: LOO重量 部であり、好ましくは 0〜50重量部であり、さらに好ましくは 0〜30重量部である。 10 0重量部を超えると、得られる熱可塑性榭脂組成物の機械強度の低下が起こり、柔 軟性も損なわれるので好ましくな 、。 [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] また本発明の熱可塑性榭脂組成物には、必要に応じて、酸化防止剤及び Z又は 紫外線吸収剤を配合することができ、配合量は (a)成分と (b)成分の総量 100重量 部に対して、 0. 01〜10重量部、好ましくは 0. 01〜5重量部である。 [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] さらに他の添加剤として難燃剤、抗菌剤、光安定剤、着色剤、流動性改良剤、滑剤 、ブロッキング防止剤、帯電防止剤、架橋剤、架橋助剤等を添加することができ、これ らは 1種又は 2種以上を組み合わせて使用可能である。 [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] 上述の添加剤のうち、本発明の熱可塑性榭脂組成物には、成形加工性を整え、離 型性を付与する目的で、滑剤を配合することができる。滑剤としては、脂肪酸金属塩 系滑剤、脂肪酸アミド系滑剤、脂肪酸ヱステル系滑剤、脂肪酸系滑剤、脂肪族アル コール系滑剤、脂肪酸と多価アルコールの部分エステル、ノ ラフィン系滑剤などが好 ましく用いられ、これらの中から 2種以上を選択して用いてもょ 、。
[0061] 脂肪酸金属塩系滑剤としては、ステアリン酸カルシウム、ステアリン酸マグネシウム、 ステアリン酸アルミニウム、ステアリン酸亜鉛、ステアリン酸バリウム、モンタン酸金属 塩などが挙げられる。 [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] 脂肪酸アミド系滑剤としては、エチレンビスステアリン酸アミド、エル力酸アミド、ォレ イン酸アミド、ステアリン酸アミド、ベへニン酸アミド、エチレンビスォレイン酸アミド、ェ チレンビスエノレカ酸アミド、エチレンビスラウリン酸アミド、 m—キシリレンビスステアリン 酸アミド、 p—フエ-レンビスステアリン酸アミドなどが挙げられる。脂肪酸エステル系 滑剤としては、ラウリン酸メチル、ミリスチン酸メチル、パルミチン酸メチル、ステアリン 酸メチル、ォレイン酸メチル、エルカ酸メチル、ベへ-ン酸メチル、ラウリン酸ブチル、 ステアリン酸プチル、ミリスチン酸イソプロピル、パルミチン酸イソプロピル、パルミチン 酸ォクチル、ヤシ脂肪酸ォクチル、ステアリン酸ォクチル、特殊牛脂脂肪酸ォクチル 、ラウリン酸ラウリル、ステアリン酸ステアリル、ベへ-ン酸ベへニル、ミリスチン酸セチ ル、牛脂硬化油、ヒマシ硬化油、モンタン酸エステルなどが挙げられる。 [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] 脂肪酸系滑剤としては、ステアリン酸、パルミチン酸、ォレイン酸、リノール酸、リノレ ン酸、モンタン酸などが挙げられる。 [0063] Examples of fatty acid lubricants include stearic acid, palmitic acid, oleic acid, linoleic acid, linoleic acid, and montanic acid.
[0064] 脂肪族アルコールとしては、ステアリルアルコール、セチルアルコール、ミリスチルァ ルコール、ラウリルアルコールなどが挙げられる。 [0064] Examples of the aliphatic alcohol include stearyl alcohol, cetyl alcohol, myristyl alcohol, lauryl alcohol, and the like.
[0065] 脂肪酸と多価アルコールの部分エステルとしては、ステアリン酸モノダリセライド、ス テアリン酸ジグリセライド、ォレイン系モノダリセライド、モンタン酸部分ケンィ匕エステル などが挙げられる。 [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] パラフィン系滑剤としては、パラフィンワックス、流動パラフィン、ポリエチレンワックス 、酸化ポリエチレンワックス、ポリプロピレンワックスなどが挙げられる。 [0066] Examples of the paraffinic lubricant include paraffin wax, liquid paraffin, polyethylene wax, oxidized polyethylene wax, and polypropylene wax.
これらの中でも、成形性の改良効果とコストのバランスから、脂肪酸アミドゃ脂肪酸ェ ステル、パラフィン系滑剤が好ましい。 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] 滑剤の配合量は、(a)イソブチレン系ブロック共重合体、(b)熱可塑性ポリウレタン 系榭脂の総量 100重量部に対して好ましくは 0〜: LO重量部であり、より好ましくは 0〜 5重量部であり、さらに好ましくは 0〜3重量部である。 10重量部を超えると十分に混 合されず、滑剤がブリードアウトする傾向があり、さらに、得られる熱可塑性榭脂組成
物の機械強度が低下する傾向もあり、好ましくない。滑剤は、(a)成分と (b)成分の溶 融混練時に添加してもよ 、し、あらかじめ(a)成分または (b)成分に添加してお!ヽても よい。(a)成分に対しては、比較的極性の低いパラフィン系滑剤が好ましぐ(b)成分 に対しては、比較的極性の高 ヽ脂肪酸アミド系滑剤や脂肪酸エステル系滑剤が好ま しいため、成形性の改良効果を効率よく得るためには、あらかじめ(a)成分に対して パラフィン系滑剤を、 (b)成分に対して脂肪酸アミド系滑剤や脂肪酸エステル系滑剤 を添加しておくことが好ま 、。 [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] さらに本発明の熱可塑性榭脂組成物の性能を損なわない範囲であれば、各種熱 可塑性榭脂、熱硬化性榭脂、他の熱可塑性エラストマ一等を配合しても良い。 [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] 本発明の熱可塑性榭脂組成物の製造方法には、特に制限はなぐ公知の方法を 適用することができる。例えば、前記の各成分及び所望により添加剤成分を加熱混 練機、例えば、一軸押出機、二軸押出機、ロール、バンバリ一ミキサー、ブラベンダ 一、ニーダー、高剪断型ミキサー等を用いて溶融混練することで製造することができ る。また各成分の混練順序は特に限定されず、使用する装置、作業性あるいは得ら れる熱可塑性榭脂組成物の物性に応じて決定することができる。 [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.
実施例 Example
[0070] 以下実施例により本発明をさらに具体的に説明する。尚、本発明はこれらの実施例 によって何ら限定されるものではなぐその要旨を変更しない範囲において適宜変更 実施可能である。 [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] 本実施例に示すブロック共重合体の分子量及び組成物の物性は以下に示す方法 で測定した。 [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)硬度 (1) Hardness
JIS K 6352に準拠し、 2mm厚のプレスシートを 3枚重ねて測定した。 In accordance with JIS K 6352, three 2 mm thick press sheets were stacked and measured.
(2)耐油性 (2) Oil resistance
2mm厚プレスシートを作製し、パラフィン系オイル、及び、 IRM # 3オイルに室温で 7 2時間浸漬後、取り出して表面性の変化を観察し、オイル吸収量を測定した。 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.
〇:変化なし Y: No change
X:変化有り (変形又は膨潤)
(3)機械強度 X: Changed (deformation or swelling) (3) Mechanical strength
組成物を 170°Cで圧縮成形し、 JIS 3号ダンベル試験片を作成した。 JIS K6251に 従い、引張速度 500mmZsecで引張強度 ·伸びを測定した。 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)透明性 (4) Transparency
組成物を 170°Cで圧縮成形し、 JIS 3号ダンベル試験片を作成した。得られたプレス シートの透明性を目視で判断した。 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.
〇:透明感がある ○: Transparency
若干透明感がある Somewhat transparent
X:透明感がない X: No transparency
また、透明性を定量ィ匕することを目的に濁度計 (モデル: NDH 300A、 日本電色 工業製)を使用し、プレスシートにて得られたシートの濁度を測定した。 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)分子量 (5) Molecular weight
Waters社製ゲルパーミエーシヨンクロマトグラフィー(GPC)システム(カラム:昭和電 ェ株式会社製 Shodex K— 804 (ポリスチレンゲル)、移動相:クロ口ホルム)を用い た。数平均分子量はポリスチレン換算で表記した。 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.
[0072] 製造例 1 イソブチレン系ブロック共重合体の製造 Production Example 1 Production of isobutylene block copolymer
攪拌機付き 2L反応容器に、 1—クロロブタン (モレキュラーシーブスで乾燥したもの ) 452mL、へキサン(モレキュラーシーブスで乾燥したもの) 319mL、 1, 4 ビス(1 —クロル— 1—メチルェチル)ベンゼン 0. 55gを加えた。反応容器を— 75°Cに冷却 した後、ジメチルァセトアミド 0. 42g、イソブチレン 182mLを添カ卩した。さらに四塩ィ匕 チタン 6. 53mLをカ卩えて重合を開始し、 75°Cで溶液を攪拌しながら 1. 5時間反 応させた。次いで反応溶液にスチレン 5 lgを添加し、さらに 60分間反応を続けた後、 反応溶液を大量の水中へあけて反応を停止させた。 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] 有機層と水層の分離状況を目視で確認したところ、分離性は良好であり分液ロート で容易に分別できた。水洗を 2回行った後、水層が中性になっているのを確認してか ら有機層を大量のメタノール中に注 、で重合体を沈殿させ、得られた重合体を 60°C で 24時間真空乾燥することによりイソブチレン系ブロック共重合体 (SIBS)を得た。 該イソプチレン系ブロック共重合体 (SIBS)の GPC分析を行ったところ、数平均分子
[0074] 実施例 1〜4、比較例 1〜4 [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
下記の成分 (a)、(b)、 (c)を表 1に示した割合で、 190°Cに設定したラボプラストミ ル (東洋精機社製)を用いて溶融混練した。得られた組成物を圧縮成形して試験片 を作成し、各種物性を評価した。評価結果を表 1に示した。 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.
成分 (a):スチレン—イソプチレン—スチレンブロック共重合体 (SIBS):製造例 1で得 られたもの。 Component (a): Styrene-isobutylene-styrene block copolymer (SIBS): obtained in Production Example 1.
成分(b):熱可塑性ポリウレタン l (TPU):エステルタイプ、ディックバイエルポリマー 社製 (商品名:パンデッタス T- 1375)、硬度 75。 Component (b): Thermoplastic polyurethane l (TPU): Ester type, manufactured by Dick Bayer Polymer (trade name: Pandettas T-1375), hardness 75.
成分(c):酸無水物基を有するスチレン エチレンブチレン スチレン共重合体(M AH-SEBS): Shell社製(商品名:クレイトン FG1901X)、硬度 65。 Component (c): Styrene having an acid anhydride group Ethylene butylene Styrene copolymer (MAH-SEBS): Shell (trade name: Kraton FG1901X), hardness 65.
[0075] [表 1]
[0075] [Table 1]
実施例 1 4の組成物は、いずれも柔軟性 (低硬度)、耐油性、透明性の全てに優 れたものである力 比較例 1 4の組成物は、柔軟性 (低硬度)、耐油性、透明性の ずれかが不充分であることがわ力つた。
産業上の利用可能性 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
本発明の熱可塑性榭脂組成物は低硬度、耐油性、透明性に優れており、さらに、 耐熱安定性、機械強度にも優れていることから、食品用途、日用雑貨用途、玩具 ·運 動用具用途、文具用途、自動車内外装用途、土木,建築用途、家電機器用途、衣料 ,履き物用途、医療用途、衛生用品、包装輸送資材、電線用途等に利用可能である 。特に、耐油性と低硬度を要求される日用雑貨用途に好適である。
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
[1] (a)イソブチレンを主成分とする重合体ブロックと、イソブチレンを主成分としな 、単 量体成分力 なる重合体ブロックとから構成されるイソブチレン系ブロック共重合体 5 〜95重量%、 [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)熱可塑性ポリウレタン 5〜95重量% (b) Thermoplastic polyurethane 5 to 95% by weight
力もなる組成物の総量 100重量部に対し、 For a total of 100 parts by weight
(c)エポキシ基、アミノ基、水酸基、酸無水物基、カルボキシル基及びその塩、並び に、カルボン酸エステル力 なる群より選ばれる少なくとも 1種の官能基を含有するォ レフイン系重合体又はスチレン系重合体 0. 1〜50重量部、 (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
を含有することを特徴とする熱可塑性榭脂組成物。 A thermoplastic rosin composition comprising:
[2] (a)成分のイソブチレンを主成分としな 、単量体成分が、芳香族ビュル系単量体を 主成分とする単量体成分であることを特徴とする請求項 1記載の熱可塑性榭脂組成 物。 [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] 芳香族ビュル系単量体がスチレン、 p—メチルスチレン、 α—メチルスチレン及びィ ンデン力 なる群力 選ばれる少なくとも 1種以上であることを特徴とする請求項 2記 載の熱可塑性榭脂組成物。 [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)イソブチレン系ブロック共重合体が、芳香族ビニル系単量体を主成分とする重 合体ブロック イソブチレンを主成分とする重合体ブロック 芳香族ビニル系単量体 を主成分とする重合体ブロック力 なるトリブロック共重合体、芳香族ビニル系単量体 を主成分とする重合体ブロック イソブチレンを主成分とする重合体ブロック力 なる ジブロック共重合体、及び、芳香族ビニル系単量体を主成分とする重合体ブロックと イソブチレンを主成分とする重合体ブロック力 なるアームを 3つ以上有する星型ブロ ック共重合体力 なる群力 選ばれる少なくとも 1種以上であることを特徴とする請求 項 2または 3に記載の熱可塑性榭脂組成物。 [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] (c)成分のォレフィン系重合体又はスチレン系重合体力 酸無水物基を有するスチ レン エチレンブチレン スチレン共重合体であることを特徴とする請求項 1〜4のい ずれか 1項に記載の熱可塑性榭脂組成物。
[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.
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000086859A (en) * | 1998-07-13 | 2000-03-28 | Kanegafuchi Chem Ind Co Ltd | Thermoplastic resin composition |
JP2000086884A (en) * | 1998-09-10 | 2000-03-28 | Kuraray Co Ltd | Thermoplastic polymer composition |
JP2000160023A (en) * | 1998-11-24 | 2000-06-13 | Yokohama Rubber Co Ltd:The | Thermoplastic elastomer composition |
WO2001074764A1 (en) * | 2000-03-30 | 2001-10-11 | Teijin Limited | Intermediates for vitamin d and processes for the preparation thereof |
JP2005187721A (en) * | 2003-12-26 | 2005-07-14 | Kaneka Corp | Thermoplastic resin composition |
-
2005
- 2005-06-22 WO PCT/JP2005/011454 patent/WO2006137134A1/en active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000086859A (en) * | 1998-07-13 | 2000-03-28 | Kanegafuchi Chem Ind Co Ltd | Thermoplastic resin composition |
JP2000086884A (en) * | 1998-09-10 | 2000-03-28 | Kuraray Co Ltd | Thermoplastic polymer composition |
JP2000160023A (en) * | 1998-11-24 | 2000-06-13 | Yokohama Rubber Co Ltd:The | Thermoplastic elastomer composition |
WO2001074764A1 (en) * | 2000-03-30 | 2001-10-11 | Teijin Limited | Intermediates for vitamin d and processes for the preparation thereof |
JP2005187721A (en) * | 2003-12-26 | 2005-07-14 | Kaneka Corp | Thermoplastic resin composition |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008247972A (en) * | 2007-03-29 | 2008-10-16 | Kaneka Corp | Thermoplastic resin composition |
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