WO2006070624A1 - Composition d'elastomere a base de styrene ne pouvant pas generer de styrene - Google Patents

Composition d'elastomere a base de styrene ne pouvant pas generer de styrene Download PDF

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Publication number
WO2006070624A1
WO2006070624A1 PCT/JP2005/023227 JP2005023227W WO2006070624A1 WO 2006070624 A1 WO2006070624 A1 WO 2006070624A1 JP 2005023227 W JP2005023227 W JP 2005023227W WO 2006070624 A1 WO2006070624 A1 WO 2006070624A1
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styrene
weight
elastomer
phosphorus
parts
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PCT/JP2005/023227
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English (en)
Japanese (ja)
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Koichiro Ohara
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Kaneka Corporation
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds

Definitions

  • the present invention relates to a styrene-based elastomer composition in which the formation of styrene-based monomers during high-temperature treatment such as kneading is suppressed.
  • General elastomers including styrene elastomers are rubber-like materials that can be melt-molded, and can be molded by commonly used molding methods such as injection molding, extrusion molding, and calendar molding. . As specific applications, it can be used as an elastomer material, a sealant, a modifier, a vibration damper, a base polymer of an adhesive, and a component of a resin modifier.
  • Patent Document 1 discloses an elastomer composition in which a phenol compound and a weathering agent (ultraviolet absorber or light stabilizer) are added to an elastomer to improve the weather resistance.
  • a weathering agent ultraviolet absorber or light stabilizer
  • Patent Document 2 discloses a cyanobule-based monomer, an aromatic vinyl-based monomer, and other copolymerizable monomers such as methyl methacrylate.
  • a phenol-reinforced antioxidant and a phosphite-based antioxidant together with a rubber-reinforced thermoplastic resin composed of the strength of the body, transparency, chemical resistance, color stability, and heat stability during processing
  • a method of making a balanced oil composition is disclosed.
  • a stabilizer When a stabilizer is added to an elastomer composition, the composition is mixed under a detailed polymer ratio and a stabilizer blend ratio for each composition so as to obtain a quality suitable for each application.
  • these elastomer compositions and resin compositions are often used in industrial applications such as industrial products. In this case, the final industrial product ensures specifications of physical properties such as weather resistance and heat resistance. As long as it was, it was almost impossible for the deterioration of the base resin itself to be a problem.
  • Patent Document 1 Japanese Patent Laid-Open No. 2001-98163
  • Patent Document 2 JP 2002-317093 A
  • An object of the present invention is to provide a styrene-based elastomer composition that can suppress the formation of styrene during high-temperature treatment such as kneading and can be suitably used for food-related applications.
  • the present invention relates to the following invention.
  • a styrene-based elastomer and a phosphorus-based antioxidant or a styrene-based elastomer composition containing a phosphorus-based antioxidant and a phenol-based antioxidant.
  • styrene elastomer wherein the styrene elastomer is a block copolymer comprising a block having a styrene monomer unit force and a block having an aliphatic olefinic compound monomer unit force. Len-based elastomer and yarn.
  • styrene-based elastomer 100 parts by weight of styrene-based elastomer, containing 0.1 part by weight or more of phosphorus-based anti-oxidation agent, and containing phosphorus-based anti-acid agent and phenol-based anti-acid agent.
  • styrene-based elastomer yarn and composition of the present invention By using the styrene-based elastomer yarn and composition of the present invention, styrene formation during high-temperature treatment such as kneading can be suppressed, and the residual styrene concentration in the styrene-based elastomer yarn and composition can be reduced. .
  • the present invention is described in detail below.
  • the “styrene elastomer” in the present invention is a block copolymer containing, as a structural unit, a polymer block obtained by polymerizing monomers of styrene and its derivatives (hereinafter referred to as “styrene monomers”). .
  • the styrenic monomer used as a raw material for the streamer is not particularly limited, but styrene, o-, m- or p-methylstyrene, ⁇ -methylstyrene, ⁇ -methylstyrene, 2, 6 dimethylstyrene, 2 , 4 Dimethylstyrene, ⁇ -methyl- ⁇ -methylstyrene, ⁇ -methyl-m-methylstyrene, ⁇ -methyl- ⁇ -methylstyrene, ⁇ -methyl- ⁇ -methylstyrene, j8-methyl-m-methylstyrene, j8-methyl-p —Methylstyrene, 2, 4, 6 Trimethylstyrene, ⁇ -Methyl-2,6 Dimethylstyrene, ⁇ -Methyl-2,4 Dimethylstyrene, 13-Methyl-2,6 Dimethylstyrene,
  • More preferable styrenic monomers include styrene, a-methylstyrene, p-methylstyrene, and the use of one or more monomers selected from the group power of styrene, and styrene, a-methylstyrene. Or a mixture of these is particularly preferred.
  • the styrene elastomer in the present invention is obtained by block copolymerization of a styrene monomer and a monomer other than the styrene monomer.
  • a monomer other than the styrene monomer is not particularly limited, but preferred examples of the monomer component that can be cationically polymerized include aliphatic olefins and gens. And monomers such as butyl ethers, silanes, burcarbazole, 13 vinylene, and acenaphthylene. These are used alone or in combination.
  • Examples of the aliphatic olefin-based monomers include ethylene, propylene, 1-butene, 2-methyl-1-butene, 3-methyl-1-butene, isobutylene, pentene, hexene, hexene, 4-methyl-1 pentene. , Bullcyclohexene, otaten, norbornene Or the like.
  • Examples of the above-mentioned gen-based monomers include butadiene, isoprene, cyclopentagen, cyclohexane, dicyclopentagen, dibutenebenzene, ethylidene norbornene, and the like.
  • butyl ether monomers include methyl butyl ether, ethyl butyl ether, (n-, iso) propyl butyl ether, (n-, sec-, tert-, iso) butyl vinyl enothere, methinole prope
  • examples include Ninore Etenore and Echinore Propeninore Etenore.
  • silane compound examples include butyltrichlorosilane, butylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyltrimethylsilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3 divinyl Examples include 1,1,3,3 tetramethyldisiloxane, tributylmethylsilane, ⁇ -methacryloylpropylpropyltrimethoxysilane, and ⁇ -methacryloyloxypropylmethyldimethoxysilane.
  • the styrene elastomer in the present invention is a block copolymer obtained by copolymerizing a styrene monomer and an aliphatic olefin monomer, but is preferably a styrene monomer. More preferred is a block copolymer comprising a block having a unit strength and an aliphatic olefin compound monomer unit.
  • the block composed of the aliphatic olefin monomer unit is a block mainly composed of an isobutylene monomer unit.
  • styrene elastomers composed of blocks composed mainly of styrene monomers and blocks mainly composed of isobutylene monomer units, for example, ⁇ -chloroisopropylbenzene, 1,4 bis-chloro-isopropyl).
  • FERFAR that performs living cationic polymerization using benzene as an initiator and chain transfer agent and a Lewis acid such as BC1 or TiCl as a catalyst
  • the polymer block obtained by polymerizing the styrene monomer is a styrene It may or may not contain a monomer other than the monomer. Usually, it is composed of a monomer component containing 60% by weight or more, preferably 80% by weight or more of a styrene monomer. .
  • the monomer other than the styrene monomer is not particularly limited as long as it is a monomer capable of cationic polymerization. For example, the above aliphatic olefins, gens, butyl ethers, silans, butyl And monomers such as carbazole, 13 binene, and acenaphthylene.
  • the ratio of the polymer block mainly composed of styrene monomer and the polymer block mainly composed of monomer other than styrene monomer is not particularly limited, and various physical properties In view of the above, 5 to 60% by weight of polymer block mainly composed of styrene monomer, and 95 to 40% polymer block mainly composed of monomer other than styrene monomer 15% to 50% by weight of a polymer block composed mainly of styrene monomers, and a polymer block composed mainly of monomers other than styrene monomers. Particularly preferred is 85 to 50% by weight.
  • the molecular weight of the styrene-based elastomer is not particularly limited, but the surface strength such as fluidity, workability, physical properties, etc., and the number average molecular weight is preferably 30000-500000 S, preferably 50000-4 U, especially preferred to be 00000.
  • the number average molecular weight of the styrenic elastomer is lower than the above range, mechanical properties tend not to be sufficiently exhibited.
  • the number exceeds the above range, it is disadvantageous in terms of fluidity and workability. There is a risk.
  • the number average molecular weight is a molecular weight in terms of polystyrene by GPC measurement using a polystyrene gel column with black mouth form as a mobile phase.
  • GPC measurement can be performed using, for example, a Waters GPC system (column: Shodex K-804 (polystyrene gel) manufactured by Showa Denko KK).
  • Polymerization of the styrene-based elastomer is usually performed by cationic polymerization in a solvent.
  • the polymerization solvent to be used is not particularly limited, but a mixed solvent of primary and Z or secondary monohalogenated hydrocarbons having 3 to 8 carbon atoms and aliphatic and Z or aromatic hydrocarbons is preferable.
  • Halogenated hydrocarbons are methyl chloride, methylene chloride, 1 chlorobutane, black benzene, and aliphatic hydrocarbons are hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane, aromatic As the hydrocarbon, toluene, xylene and the like can be used.
  • the initiator used in the cationic polymerization is not particularly limited, but the following compounds are preferable. (1-Chloro-1-methylethyl) benzene [CHC (CH) Cl], 1, 4—
  • a Lewis acid catalyst Any Lewis acid can be used for living cationic polymerization.
  • BC1 and TiCl which are also used in the above-mentioned Fifer method, TiBr, BF, BF -OEt
  • Gold such as SnCl, SbCl, SbF, WC1, TaCl, VC1, FeCl, ZnBr, A1C1, AlBr
  • the amount of Lewis acid used is not particularly limited, but the single amount 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 60 molar equivalent.
  • an electron donor component can be allowed to coexist if necessary.
  • This electron donor component is believed to have the effect of stabilizing the growth carbon catalyst during cationic 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. be able to.
  • the respective components are mixed under cooling, for example, at a temperature of 100 ° C or more and less than 0 ° C.
  • the temperature range is particularly preferably from 30 ° C to 80 ° C.
  • the reaction solution obtained by polymerization deactivates the Lewis acid catalyst by a method using an inorganic basic aqueous solution or water, and further, impurities such as catalyst residues are removed by washing with water or filtration. Thereby, a styrene elastomer solution can be obtained.
  • the polymerization solvent and unreacted monomer are subsequently removed by an evaporation operation to isolate the styrene-based elastomer.
  • a thin film evaporation method a flash evaporation method, a crumbization method, a horizontal evaporation method with an extrusion screw, and the like can be used. Since styrene elastomers are sticky, among the above evaporation methods, a crumbization method obtained by taking out styrene elastomers in a slurry state with water, a horizontal evaporation method with an extrusion screw, etc. are used. Thus, particularly efficient evaporation is possible.
  • the polymer from which the solvent has been removed by the evaporation operation is subsequently supplied to an extruder and pelletized.
  • Extruder outlet is 2mn in diameter!
  • the styrenic elastomer which is composed of dies with single or multiple holes of ⁇ 8mm and extruded, is cooled in a strand form and then cut into cylindrical pellets. Cylindrical pellets can be obtained as spherical pellets by further removal of solvent and styrenic monomer using an extruder with a devolatilization mechanism and an underwater cutting system.
  • the styrene-based elastomer composition of the present invention is prepared by adding a phosphorus-based antioxidant, a phosphorus-based acid / antioxidant and a phenol-based acid / anti-oxidant, a phosphorus-phenol composite-based acid / anti-oxidant to the pellet, or Further, it can be obtained by adding a phosphorus-phenol composite system and a phenol-based anti-oxidation agent and mixing them by kneading. Such kneading can be performed, for example, by mixing for 10 minutes using a mill kneader (manufactured by Toyo Seisakusho) at a set temperature of 250 ° C.
  • a mill kneader manufactured by Toyo Seisakusho
  • Examples of the phosphorus-based anti-oxidation agent used in the present invention include a phosphite-based anti-oxidation agent, a phosphaphenanthrene-based anti-oxidation agent, and the like.
  • An example of a phosphite-based anti-oxidation agent For example, triphenylphosphite, diphenylisodecyl phosphite, ferrodiisodecyl phosphite, 4,4, -butylidene-bis (3-methyl-6-tert-butylphenylditridecyl) phosphite, cyclic neopentanetetraylbis (Octadecyl phosphite), tris (norphenol) phosphite, tris (mono and Z or dinoferule) phosphite, diisodecyl pentaerythritol diphosphite, tri
  • Cyclic neopentanetetraylbis (octadecyl phosphite) for which phosphite-based anti-oxidants are preferred (for example, Adeka Stub PEP-8 manufactured by Asahi Denki) )
  • distearyl pentaerythritol diphosphite and bis (2,6-di-tert-butyl 4-methyl-phenol) pentaerythritol rosy phosphite are particularly preferred.
  • phenolic antioxidant examples include a monophenolic antioxidant, a bisphenolic antioxidant, and a polymer type phenolic acid antioxidant.
  • Monophenol-based antioxidants include n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenol) propionate, 2,6-di-tert-butyl-cresole, butylated hydroxy-anol, 2,6 di- — T-butyl-4-ethylphenol, stearyl-13- (3,5-di-tert-butyl-4-hydroxyphenol) propionate, and the like.
  • Bisphenol-based antioxidants include 2,2, -methylenebis (4-methyl-6t-butylphenol), 2,2, -methylenebis (4-ethyl-6t-butylphenol), 4,4'-thiopis (3-methyl-). 6-t butylphenol), 4, 4, -butylidenebis (3-methyl) — 6— t-butylphenol), 3, 9 bis [1, 1-dimethyl-2- [j8— (3-tert-butyl-4-hydroxy-5-methylphenol) propio-loxy] ethyl] —2, 4, 8, 10-tetraoxaspiro [5,5 '] undecane.
  • Polymeric phenols include (1, 1, 3 tris (2-methyl-4-hydroxy-5-tert-butylphenol) butane, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenol).
  • the anti-wrinkle agent is preferred in terms of its good handleability and reactivity, such as (1, 1, 3 tris (2-methyl-4-hydroxy-5t-butylphenol) butane, n-octadecyl 3- (3,5-Di-tert-butyl 4-hydroxyphenol) propionate, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl)] propionate
  • the products sold by Sumitomo Chemical are Sumitomo Chemical's GM and GS, Chinoku 'Specialty'Chemicals' Irganox 1010, Asahi Denka's Adeka Stub AO-30.
  • the content of the anti-oxidation agent is preferably 0.1-5 parts by weight with respect to 100 parts by weight of the styrene-based elastomer.
  • a force of 2 to 1.0 part by weight is preferred.
  • a part of 0.2 to 0.5 part by weight is particularly preferred.
  • Less than 1 part by weight Styrenic monomers may be formed.
  • mechanical properties such as strength may decrease.
  • a phosphorus-based anti-oxidation agent and a phenol-based anti-oxidation agent are used in combination, 0.1 parts by weight of the phosphorus-based anti-oxidation agent is added to 100 parts by weight of the styrene-based elastomer.
  • a phosphorus-based antioxidant that preferably contains a phosphorus-based acid inhibitor and a phenol-based carboxylic acid inhibitor in a total amount of 5 parts by weight or less. More preferably, the total content of the phosphorus-based antioxidant and the phenol-based antioxidant is 0.5 parts by weight or less. If the content of the phosphoric acid antioxidant is less than 0.1 part by weight, a styrene monomer may be formed. If the total number of parts exceeds 5 parts by weight, mechanical properties such as strength may decrease.
  • the content of the antioxidant is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the styrene elastomer. 2 to 1.0 part by weight is more preferred 0.2 to 0.5 part by weight is particularly preferred. If the amount is less than 0.1 part by weight, a styrenic monomer may be formed. On the other hand, if it exceeds 5 parts by weight, mechanical properties such as strength may be deteriorated.
  • the phosphorus phenol complex acid inhibitor when used in combination with 100 parts by weight of the styrene elastomer, the phosphorus phenol complex acid inhibitor is used. It is preferable to contain 0.1 part by weight or more of a phosphorus-phenol composite acid / antioxidant and a phenolic acid / anti-oxidant in a total amount of 5 parts by weight or less. Containing 0.1 part by weight or more of an acid-based anti-oxidant, and containing a phosphorus phenol complex antioxidant and a phenolic antioxidant in a total amount of 0.5 parts by weight or less. More preferred.
  • the addition amount of the phosphorus phenol complex type antioxidant is less than 0.1 part by weight, a styrene monomer may be formed, and the phosphorus phenol complex type antioxidant and phenolic acid may be formed. If the total number of parts with the ricin inhibitor exceeds 5 parts by weight, mechanical properties such as strength may be reduced.
  • styrene generation literally means not only styrene itself but also styrene monomers other than styrene. When is used as a monomer for polymerization, it means that the styrene monomer is formed.
  • styrene concentration in the present invention does not strictly mean the concentration of only a styrene monomer, and a styrene monomer other than styrene is used as a polymerization monomer. In this case, it means the concentration of the entire styrenic monomer used in the composition.
  • a styrene elastomer composition having a low styrene concentration in the styrene elastomer composition can be obtained.
  • the styrene concentration in the composition was several ppm to several tens of ppm, whereas in the present invention, it is 1 ppm or less, more preferably 0.5 ppm or less, and
  • a styrene elastomer composition having a low styrene concentration of 0.25 ppm or less can be obtained.
  • the styrene-based elastomer composition of the present invention is preferably produced by kneading at a temperature of 150 ° C or higher and 300 ° C or lower, and is preferably kneaded at 200 ° C or higher and 280 ° C or lower. More preferably, kneading at 250 ° C. or higher and 270 ° C. is particularly preferable. If the temperature is lower than 150 ° C, the styrene elastomer may be difficult to dissolve, and it becomes difficult to uniformly mix the oxidizer with the styrene elastomer.
  • the styrene elastomer may decompose.
  • the kneading time is preferably 5 minutes or more and 30 minutes or less, more preferably 5 minutes or more and 15 minutes or less, and more preferably about 10 minutes. If the kneading time is shorter than 5 minutes, it may be difficult to stir uniformly. On the other hand, it is usually sufficient to mix for 30 minutes. Is preferred, in many cases.
  • the styrenic elastomer composition that is useful in the present invention includes additives such as fillers, other thermoplastic resins, thermoplastic elastomers, and lyo mouth pick liquid according to the required physical properties. Crystalline resin, liquid resin, thermosetting resin, crosslinked rubber and the like can be blended. Suitable fillers include flaky inorganic fillers such as clay, diatomaceous earth, silica, talc, barium sulfate, calcium carbonate, magnesium carbonate, metal oxides, my strength, graphite, and hydroxyaluminum hydroxide. Various metal powders, wood chips, glass powders, ceramic powders, carbon black, etc. are listed. [0044] Examples of other thermoplastic resin include (i) general-purpose thermoplastic resin, (ii) general-purpose engineering plastic, and (iii) special engineering plastic.
  • thermoplastic resins include polyolefin resin, aromatic vinyl compound resin, polysalt vinyl resin, polyacrylic resin, polyether resin, etc. Can be raised.
  • the polyolefin resin includes a-olefin homopolymers, random copolymers, block copolymers and mixtures thereof, or random copolymers of ⁇ -olefin and other unsaturated monomers, Examples thereof include block copolymers, graft copolymers, and acids, halogenated or sulfonated polymers of these polymers.
  • polyethylene ethylene-propylene copolymer, ethylene-propylene non-conjugated diene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene otaten copolymer, other ethylene ⁇ -olefin-based copolymers
  • Polymer ethylene acetate butyl copolymer, ethylene vinyl alcohol copolymer, ethylene ethyl acrylate copolymer, polyethylene resin such as chlorinated polyethylene, polypropylene, propylene-ethylene random copolymer, propylene ethylene block copolymer
  • polypropylene-based resins such as chlorinated polypropylene, polybutene, polyisobutylene, polymethylpentene, (co) polymers of cyclic olefins, and the like.
  • aromatic resin-based resin examples include polystyrene, high impact polystyrene, poly ⁇ -methyl styrene, poly ⁇ -methyl styrene, styrene maleic anhydride copolymer and the like.
  • polyvinyl chloride resin examples include polyvinyl chloride, polyvinyl chloride, chlorinated polychlorinated bulls, and the like.
  • polyacrylic resin examples include acrylonitrile monostyrene resin (AS) and acrylonitrile.
  • ABS acrylonitrile monobutadiene resin
  • ABS heat-resistant ABS
  • polymethyl methacrylate and methyl methacrylate monostyrene copolymer polymethyl methacrylate and methyl methacrylate monostyrene copolymer
  • polyether-based resin examples include polyethylene oxide, polypropylene oxide, and polytetrahydrofuran.
  • General-purpose engineering plastics include polyamide-based resins, polyester-based resins, polycarbonate-based resins, polyacetal-based resins, polyphenylene ether-based resins, polymethylpentene, and ultrahigh molecular weight polyethylene. can give.
  • polyamide-based resin examples include nylon 1, 6, nylon 1, 66, nylon 11, 11, nylon 1, 2, nylon 46, nylon 610, nylon 612, and the like.
  • polyester-based resin examples include polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyarylate, amorphous polyethylene terephthalate, and crystalline polyethylene terephthalate.
  • Polycarbonate-based resins include 2,2 bis (4-hydroxyphenol) propane (bisphenol A), a part or all of aromatic hydrogen of bisphenol A substituted with alkyl groups and halogen atoms. And polycarbonate-based resin formed on the basis of hydroquinone, bis (4-hydroxyphenol) sulfone, and the like.
  • Examples of the polyacetal-based resin include polyoxymethylene.
  • Polyphenylene ether-based resins include poly (2,6 dimethyl-1,4 phenylene) ether, poly (2-methyl-6 ethyl 1,4 phenylene) ether, poly (2,6— Dibutyl mono 1,4 phenol) ether, poly (2,6 diphenyl 1,4 phenol) ether, poly (2,6 dimethoxy mono 1,4 phenol) ether, poly (2,6 Dichro Kouichi 1, 4 Fuenylene) Etenore.
  • Special engineering plastics include polysulfone-based resins, polysulfide-based resins, polyimide-based resins, polyamide-imide-based resins, polyetherimide-based resins, fluorine-based resins, and thermoplastic polyurethane-based resins. Examples thereof include fats, polyethersulfone-based resins, polyether ketone-based resins, and thermopick liquid crystal resins.
  • polysulfone-based resin examples include poly (ether sulfone) and poly (4,4 'bisphenol ether sulfone).
  • polysulfide-based resin examples include polyphenylene sulfide and poly (4, 4, di-phenylene sulfide).
  • polyether ketone-based resin examples include polyether ether ketone.
  • Thermopick pick liquid crystal resins include p-hydroxybenzoic acid, biphenol and tetra Examples include copolymers of rephthalic acid, copolymers of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, and copolymers of polyethylene terephthalate (PET) and p-hydroxybenzoic acid.
  • PET polyethylene terephthalate
  • Polyethylene-based resin, polypropylene-based resin, or a mixture thereof can be preferably used.
  • Thermoplastic elastomers include styrene butadiene styrene block copolymer (SBS), styrene isoprene styrene block copolymer (SIS), styrene-ethylene Z-butylene styrene block copolymer (SEBS), styrene-ethylene Z-propylene.
  • SBS styrene butadiene styrene block copolymer
  • SIS styrene isoprene styrene block copolymer
  • SEBS styrene-ethylene Z-butylene styrene block copolymer
  • SEPS Styrene block copolymers
  • hydrogenated elastomers polyolefins, polygens, polychlorinated burs, polyurethanes, polyesters, polyamides, fluorines, silicones, ionomers, etc.
  • Examples of the lyo-mouth pick liquid crystal resin include aramid, poly (p-phenylenebenzobisthiazole), poly (terephthaloyl hydrazide) and the like.
  • liquid resins examples include silicone-based resins, modified silicone (MS) -based resins, polyisobutylene (PIB) -based resins, polysulfide-based resins, modified polysulfide-based resins, polyurethane-based resins, and polyacrylic resins. And the like, and polyacryl urethane urethane.
  • thermosetting resins include unsaturated polyester resins, epoxy resins, hydrosilylation cross-linked resins, phenolic resins, alkyd resins, diallyl phthalate resins, and urea.
  • examples thereof include polyurethane-based resin, polyurethane-based resin, and melamine-based resin.
  • Cross-linked rubbers include natural rubber, polybutadiene rubber (PBD), styrene-butadiene rubber (SBR), hydrogenated styrene-butadiene rubber, acrylonitrile-butadiene rubber, butinore rubber, chlorinated butinole rubber, Examples thereof include black-opened plain rubber, talinole rubber, urethane rubber, isoprene rubber, ethylene propylene rubber, fluorine rubber, and silicone rubber.
  • PBD polybutadiene rubber
  • SBR styrene-butadiene rubber
  • hydrogenated styrene-butadiene rubber acrylonitrile-butadiene rubber
  • butinore rubber chlorinated butinole rubber
  • black-opened plain rubber talinole rubber, urethane rubber, isoprene rubber, ethylene propylene rubber, fluorine rubber, and silicone rubber.
  • the process is the same as in Production Example 1 until the dope is obtained, but the same amount of water and a small amount of demulcent as the dope obtained are added, suspended under stirring and heated with steam to distill off the solvent. did.
  • the composition was obtained as crumbs in water, and after solid-liquid separation by a dehydrator, the crumbs were dried to obtain crumbs.
  • the pellets produced in Production Example 1 were dried by hot air drying so that the styrene concentration in the pellets was 0.2 ppm or less.
  • Phosphorus-phenol composite acid prevention agent (Smallizer GP, manufactured by Sumitomo Chemical Co., Ltd.) 0.2 parts by weight and phenol-based acid prevention against 100 parts by weight of this pellet 0.5 parts by weight of an agent (Irganoxl010, manufactured by Chinoku 'Specialty' Chemicals) was added and kneaded at 250 ° C for 10 minutes using a mill kneader.
  • an agent Irganoxl010, manufactured by Chinoku 'Specialty' Chemicals
  • the pellets were dried in the same manner as in Example 1, and the phosphite-based antioxidation agent (ADK STAB PEP-8, manufactured by Asahi Denka Co.) was added to 100 parts by weight of the obtained pellets. 0.2 parts by weight and phenolic acid 0.5 parts by weight of an inhibitor (Irganoxl010, manufactured by Chinoku 'Specialty' Chemicals) was added and kneaded at 250 ° C for 10 minutes using a mill kneader. The styrene concentration in the styrene elastomer composition after kneading was measured and found to be 0.2 ppm or less.
  • ADK STAB PEP-8 phosphite-based antioxidation agent
  • the pellets were dried in the same manner as in Example 1, and only 0.2 parts by weight of a phosphorus-phenol composite antioxidant (Sumilyzer GP, manufactured by Sumitomo Chemical Co., Ltd.) was added to 100 parts by weight of the obtained pellets.
  • a phosphorus-phenol composite antioxidant (Sumilyzer GP, manufactured by Sumitomo Chemical Co., Ltd.) was added to 100 parts by weight of the obtained pellets.
  • phosphonol-complexed anti-oxidation agent (Sumilyzer GP, manufactured by Sumitomo Chemical Co., Ltd.) per 100 parts by weight of crumb resin 0.2 0.5 parts by weight and phenolic antioxidant (Irganoxl010, manufactured by Chinoku “Specialty” Chemicals) were added and kneaded at 250 ° C. for 10 minutes using a mill kneader.
  • the styrene concentration in the styrene elastomer composition after kneading was measured and found to be 0.2 ppm or less.
  • a phosphite-based anti-oxidation agent (ADK STAB PEP-8, manufactured by Asahi Denka) is used in the same manner as in Example 2 except that the crumb resin prepared in Production Example 2 is used.
  • 0.5 parts by weight and phenolic antioxidant (Irganoxl010, manufactured by Chinoku 'Specialty' Chemicals) were added and kneaded at 250 ° C for 10 minutes using a mill kneader.
  • the styrene concentration in the styrene-based elastomer composition after kneading was measured and found to be 0.2 ppm or less.
  • Example 3 As in Example 3, except that the crumb resin prepared in Production Example 2 was used, a phosphorus phenolic complex acid / antioxidant for 100 parts by weight of crumb resin (Sumilyzer GP, manufactured by Sumitomo Chemical Co., Ltd.) 0.2 Only parts by weight were added. When kneaded at 250 ° C. for 10 minutes using a mill kneader, the styrene concentration in the styrene-based elastomer yarn and composition after kneading was 0.2 ppm or less.
  • crumb resin Sudilyzer GP, manufactured by Sumitomo Chemical Co., Ltd.
  • the pellets were dried in the same manner as in Example 1, and only 0.2 parts by weight of a phosphite-based anti-oxidation agent (ADK STAB PEP-8, manufactured by Asahi Denka Co., Ltd.) was added to 100 parts by weight of the obtained pellets.
  • ADK STAB PEP-8 phosphite-based anti-oxidation agent
  • the styrene concentration in the styrene elastomer composition after kneading was 0.2 ppm or less.
  • the pellets were dried in the same manner as in Example 1, and only 0.2 parts by weight of a phenolic acid salt inhibitor (ADK STAB AO-30, manufactured by Asahi Denka Co., Ltd.) was added to 100 parts by weight of the obtained pellets.
  • a phenolic acid salt inhibitor ADK STAB AO-30, manufactured by Asahi Denka Co., Ltd.
  • the styrene concentration in the styrene-based elastomer composition after kneading was 5 ppm.
  • the pellets were dried in the same manner as in Example 1, and only 0.2 parts by weight of a phenolic antioxidant (Sumilyzer GS, manufactured by Sumitomo Chemical Co., Ltd.) was added to 100 parts by weight of the obtained pellets.
  • a phenolic antioxidant Sudilyzer GS, manufactured by Sumitomo Chemical Co., Ltd.
  • the styrene concentration in the styrene elastomer composition after kneading was 5 ppm.
  • a phenolic antioxidant Irganoxl010, manufactured by Chinoku 'Specialty' Chemicals
  • the styrene elastomer composition obtained by the production method of the present invention can be used for various applications.
  • food-related uses such as food containers and food packaging, daily goods, toys' sports equipment use, stationery use, automotive interior and exterior use, civil engineering / architecture use, home appliance use, clothing / footwear use, medical treatment It can be used for applications, sanitary goods, packaging and transport materials, and electric wire applications.
  • food containers and food packaging applications due to low residual styrene concentration

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition d'élastomère à base de styrène comprenant un élastomère à base de styrène, un antioxydant contenant du phosphore ou un antioxydant contenant du phosphore et un antioxydant à base de phénol ; elle concerne également une composition d'élastomère à base de styrène qui comprend un élastomère à base de styrène, un antioxydant composite phosphore-phénol ou un antioxydant composite phosphore-phénol et un antioxydant à base de phénol. Il est possible d'empêcher lesdites compositions de produire du styrène lorsqu'elles sont traitées, par exemple malaxées, à haute température.
PCT/JP2005/023227 2004-12-27 2005-12-19 Composition d'elastomere a base de styrene ne pouvant pas generer de styrene WO2006070624A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013094642A1 (fr) * 2011-12-20 2013-06-27 東洋スチレン株式会社 Composition optique à base de styrène, produit moulé et plaque guide de lumière
JP2018090813A (ja) * 2011-12-20 2018-06-14 東洋スチレン株式会社 光学用スチレン系樹脂組成物
US11054548B2 (en) 2017-08-31 2021-07-06 Asahi Kasei Kabushiki Kaisha Plastic optical fiber, plastic optical fiber cable, connector-attached plastic optical fiber cable, optical communication system, and plastic optical fiber sensor

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JPH04311756A (ja) * 1991-04-11 1992-11-04 Sumitomo Chem Co Ltd 水添ブロック共重合体組成物
JP2000143913A (ja) * 1998-11-10 2000-05-26 Sumitomo Chem Co Ltd 共重合体組成物、その製造方法および共重合体の安定化方法
WO2003091303A1 (fr) * 2002-04-25 2003-11-06 Asahi Kasei Chemicals Corporation Copolymere sequence et sa composition
WO2004033541A1 (fr) * 2002-10-08 2004-04-22 Denki Kagaku Kogyo Kabushiki Kaisha Film thermoretrecissant
JP2005105048A (ja) * 2003-09-29 2005-04-21 Denki Kagaku Kogyo Kk 熱収縮性フィルム

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JP3301694B2 (ja) * 1995-03-08 2002-07-15 株式会社クラレ ブロック共重合体及びその製造方法
JPH10101944A (ja) * 1996-10-02 1998-04-21 Asahi Denka Kogyo Kk 合成樹脂組成物
JP4160378B2 (ja) * 2002-12-26 2008-10-01 株式会社カネカ 熱可塑性エラストマー組成物

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Publication number Priority date Publication date Assignee Title
JPH04311756A (ja) * 1991-04-11 1992-11-04 Sumitomo Chem Co Ltd 水添ブロック共重合体組成物
JP2000143913A (ja) * 1998-11-10 2000-05-26 Sumitomo Chem Co Ltd 共重合体組成物、その製造方法および共重合体の安定化方法
WO2003091303A1 (fr) * 2002-04-25 2003-11-06 Asahi Kasei Chemicals Corporation Copolymere sequence et sa composition
WO2004033541A1 (fr) * 2002-10-08 2004-04-22 Denki Kagaku Kogyo Kabushiki Kaisha Film thermoretrecissant
JP2005105048A (ja) * 2003-09-29 2005-04-21 Denki Kagaku Kogyo Kk 熱収縮性フィルム

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013094642A1 (fr) * 2011-12-20 2013-06-27 東洋スチレン株式会社 Composition optique à base de styrène, produit moulé et plaque guide de lumière
JP2018090813A (ja) * 2011-12-20 2018-06-14 東洋スチレン株式会社 光学用スチレン系樹脂組成物
US11054548B2 (en) 2017-08-31 2021-07-06 Asahi Kasei Kabushiki Kaisha Plastic optical fiber, plastic optical fiber cable, connector-attached plastic optical fiber cable, optical communication system, and plastic optical fiber sensor

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