JP2011080051A - Ethylene-vinyl acetate-based resin composition - Google Patents
Ethylene-vinyl acetate-based resin composition Download PDFInfo
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- JP2011080051A JP2011080051A JP2010201871A JP2010201871A JP2011080051A JP 2011080051 A JP2011080051 A JP 2011080051A JP 2010201871 A JP2010201871 A JP 2010201871A JP 2010201871 A JP2010201871 A JP 2010201871A JP 2011080051 A JP2011080051 A JP 2011080051A
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- ethylene
- vinyl acetate
- graphite
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- acetate resin
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- 239000005038 ethylene vinyl acetate Substances 0.000 title claims abstract description 41
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 title claims abstract description 41
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000011342 resin composition Substances 0.000 title claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 50
- 239000010439 graphite Substances 0.000 claims abstract description 49
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 13
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229920000058 polyacrylate Polymers 0.000 claims description 6
- 230000000704 physical effect Effects 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000006057 Non-nutritive feed additive Substances 0.000 description 8
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920000297 Rayon Polymers 0.000 description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000004609 Impact Modifier Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000005087 graphitization Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 235000011835 quiches Nutrition 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 238000007666 vacuum forming Methods 0.000 description 2
- RVHSTXJKKZWWDQ-UHFFFAOYSA-N 1,1,1,2-tetrabromoethane Chemical compound BrCC(Br)(Br)Br RVHSTXJKKZWWDQ-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- 101000969770 Homo sapiens Myelin protein zero-like protein 2 Proteins 0.000 description 1
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 1
- 102100021272 Myelin protein zero-like protein 2 Human genes 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- PMSNFNRNIGPRQJ-UHFFFAOYSA-N [Cr](=O)(=O)([O-])[O-].[Mo+4].[Cr](=O)(=O)([O-])[O-] Chemical compound [Cr](=O)(=O)([O-])[O-].[Mo+4].[Cr](=O)(=O)([O-])[O-] PMSNFNRNIGPRQJ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- MOVRNJGDXREIBM-UHFFFAOYSA-N aid-1 Chemical compound O=C1NC(=O)C(C)=CN1C1OC(COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C(NC(=O)C(C)=C2)=O)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C(NC(=O)C(C)=C2)=O)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C(NC(=O)C(C)=C2)=O)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)CO)C(O)C1 MOVRNJGDXREIBM-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- QEZIKGQWAWNWIR-UHFFFAOYSA-N antimony(3+) antimony(5+) oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[Sb+3].[Sb+5] QEZIKGQWAWNWIR-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- WWNGFHNQODFIEX-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;styrene Chemical compound C=CC=C.COC(=O)C(C)=C.C=CC1=CC=CC=C1 WWNGFHNQODFIEX-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- NLCKLZIHJQEMCU-UHFFFAOYSA-N cyano prop-2-enoate Chemical class C=CC(=O)OC#N NLCKLZIHJQEMCU-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000003902 salicylic acid esters Chemical class 0.000 description 1
- QYHFIVBSNOWOCQ-UHFFFAOYSA-N selenic acid Chemical compound O[Se](O)(=O)=O QYHFIVBSNOWOCQ-UHFFFAOYSA-N 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、エチレン−酢酸ビニル系樹脂組成物に関する。 The present invention relates to an ethylene-vinyl acetate resin composition.
従来から、熱可塑性樹脂は、耐衝撃性、耐熱性等の物理的性質及び耐溶剤性、耐酸性等の化学的性質に優れた特性を有する材料として、プラント用プレート、パイプ、パイプ継手、シート、フィルム等多くの用途に使用されている。
しかし、燃焼すると有毒ガスや多量の黒煙が発生し、列車などの車両用途では火災の際に乗客の安全性に支障をきたすため、より燃えにくい材料が要求されている。
Conventionally, thermoplastic resin has been used as a plant plate, pipe, pipe joint, sheet as a material having excellent physical properties such as impact resistance and heat resistance and chemical properties such as solvent resistance and acid resistance. It is used for many applications such as film.
However, when it burns, toxic gas and a large amount of black smoke are generated, and in the use of vehicles such as trains, the safety of passengers is impaired in the event of a fire.
熱可塑性樹脂の難燃性を向上させる方法としては、例えば、塩化ビニル系樹脂に水酸化アルミニウムや水酸化マグネシウムなどの難燃剤を添加する方法が提案されている（例えば、特許文献１）。
また、塩化ビニル系樹脂に黒鉛を添加する方法が提案されている（例えば、特許文献２）。
As a method for improving the flame retardancy of a thermoplastic resin, for example, a method of adding a flame retardant such as aluminum hydroxide or magnesium hydroxide to a vinyl chloride resin has been proposed (for example, Patent Document 1).
A method of adding graphite to a vinyl chloride resin has been proposed (for example, Patent Document 2).
しかし、このような熱可塑性樹脂組成物では、「鉄道に関する技術上の基準を定める省令(平成１３年１２月２５日国土交通省令第１５１号)」の第５節車両の火災対策等第８３条に準拠した方法で行った燃焼試験において、燃焼抑制効果を発現するためには、多量の充填量を必要とするため、耐衝撃性等の物性や真空成形性等の二次加工性が著しく低下するという欠点があった。 However, in such a thermoplastic resin composition, Article 83, “Fire Control for Vehicles” in Section 5 of “Ministerial Ordinance Establishing Technical Standards Regarding Railways (Ministry of Land, Infrastructure and Transport Ordinance No. 151 on December 25, 2001)” In a combustion test conducted by a method compliant with the above, a large amount of filling is required to exhibit a combustion suppression effect, so that physical properties such as impact resistance and secondary workability such as vacuum formability are significantly reduced. There was a drawback of doing.
本発明は上記問題点に鑑みなされたものであり、難燃性、二次加工性に優れたエチレン−酢酸ビニル系樹脂組成物を提供することを目的とする。 This invention is made | formed in view of the said problem, and it aims at providing the ethylene-vinyl acetate type-resin composition excellent in the flame retardance and secondary workability.
本発明のエチレン−酢酸ビニル系樹脂組成物は、エチレン−酢酸ビニル共重合体と、膨張後粉砕黒鉛または熱分解黒鉛とを含むエチレン−酢酸ビニル系樹脂組成物であって、
エチレン−酢酸ビニル系樹脂組成物の全重量に対して、前記膨張後粉砕黒鉛または熱分解黒鉛が、１５〜７０重量％で含有されていることを特徴とする。
このエチレン−酢酸ビニル系樹脂組成物は、さらにポリテトラフルオロエチレンと（メタ）アクリル酸アルキル重合体とからなる混合物を含むことが好ましい。
The ethylene-vinyl acetate resin composition of the present invention is an ethylene-vinyl acetate resin composition comprising an ethylene-vinyl acetate copolymer and crushed graphite or pyrolytic graphite after expansion,
The expanded pulverized graphite or pyrolytic graphite is contained at 15 to 70% by weight with respect to the total weight of the ethylene-vinyl acetate resin composition.
The ethylene-vinyl acetate resin composition preferably further contains a mixture of polytetrafluoroethylene and an alkyl (meth) acrylate polymer.
本発明によれば、難燃性及び二次加工性に優れたエチレン−酢酸ビニル系樹脂組成物を提供することができる。 According to the present invention, an ethylene-vinyl acetate resin composition excellent in flame retardancy and secondary processability can be provided.
本発明のエチレン−酢酸ビニル系樹脂組成物は、少なくとも、エチレン−酢酸ビニル共重合体と、膨張後粉砕黒鉛または熱分解黒鉛とを含有してなる。このように、特定の材料を組み合わせることにより、材料自体が有する優れた特性を十分に発揮させることができるとともに、例えば、鉄道車両の内装材として、難燃性、二次加工性を向上させることができる。
なお、内装材用途の場合、通常、表層面に印刷加工が施されるか、加飾層が設けられるが、エチレン−酢酸ビニル系樹脂は、これらの処理が施される場合においても、優れた加工特性を発揮させることができる。
The ethylene-vinyl acetate resin composition of the present invention comprises at least an ethylene-vinyl acetate copolymer, and expanded and pulverized graphite or pyrolytic graphite. In this way, by combining specific materials, it is possible to sufficiently exhibit the excellent characteristics of the materials themselves, and to improve, for example, flame retardancy and secondary workability as interior materials for railway vehicles Can do.
In addition, in the case of interior material use, printing processing is usually performed on the surface layer or a decorative layer is provided, but the ethylene-vinyl acetate resin is excellent even when these treatments are performed. Processing characteristics can be exhibited.
エチレン−酢酸ビニル共重合体は、特に限定されず、公知のもののいずれをも使用することができるが、一般に、全エチレン−酢酸ビニル共重合体重量に対して、酢酸ビニル単位が、３〜４０重量％程度、好ましくは１４〜４０重量％程度含有されているものが適している。 The ethylene-vinyl acetate copolymer is not particularly limited, and any known one can be used, but generally, the vinyl acetate unit is 3 to 40 with respect to the total weight of the ethylene-vinyl acetate copolymer. Those containing about 14% by weight, preferably about 14 to 40% by weight are suitable.
膨張後粉砕黒鉛とは、黒鉛又は膨張黒鉛を膨張させた後粉砕処理した黒鉛を意味する。
膨張黒鉛とは、従来公知のものであり、特に限定されず、いかなるものをも使用することができる。通常、黒鉛を化学処理することにより製造されたものである。例えば、天然鱗状グラファイト、熱分解グラファイト、キッシュグラファイト等の粉末を濃硫酸、硝酸、セレン酸等の無機酸と濃硝酸、過塩素酸、過塩素酸塩、過マンガン酸塩、重クロム酸塩、過酸化水素等の強酸化剤とを利用して、黒鉛の層間に無機酸を挿入し、酸処理をして得られる炭素の層状構造を維持した結晶化合物等が挙げられる。
The expanded and pulverized graphite means graphite which has been expanded after being expanded or expanded.
The expanded graphite is a conventionally known one and is not particularly limited, and any one can be used. Usually, it is produced by chemically treating graphite. For example, natural scale-like graphite, pyrolytic graphite, quiche graphite and other powders such as concentrated sulfuric acid, nitric acid, selenic acid and other inorganic acids and concentrated nitric acid, perchloric acid, perchlorate, permanganate, dichromate, Examples include crystalline compounds that maintain a carbon layer structure obtained by inserting an inorganic acid between graphite layers using a strong oxidizing agent such as hydrogen peroxide and performing acid treatment.
黒鉛又は膨張黒鉛を膨張させる方法としては、特に限定されない。例えば、炉の中で数百度〜千度程度の温度にて数分〜数時間、加熱処理を施して膨張させる方法等が挙げられる。
このように膨張させた膨張化黒鉛は、黒鉛の層間が開くことにより、黒鉛の表面積が大きくなり、エチレン−酢酸ビニル系樹脂組成物中又はその成形後において、黒鉛同士がより近接する確率が高まると考えられる。
The method for expanding graphite or expanded graphite is not particularly limited. For example, a method of performing a heat treatment at a temperature of about several hundred degrees to several thousand degrees for several minutes to several hours in a furnace and the like can be mentioned.
In the expanded graphite thus expanded, the surface area of the graphite is increased by opening the interlayer of the graphite, and the probability that the graphites are closer to each other in or after the ethylene-vinyl acetate resin composition is increased. it is conceivable that.
粉砕処理は、特に限定されず、例えば、ロッドミル、ボールミル、ジェットミル等の従来公知の装置を用いて行うことができる。 The pulverization process is not particularly limited, and can be performed using a conventionally known apparatus such as a rod mill, a ball mill, or a jet mill.
熱分解黒鉛とは従来公知のものであり、特に限定されずいかなるものをも使用することができる。通常、熱分解黒鉛は、黒鉛の基材を炭化水素雰囲気中で高温（２０００〜３０００℃程度)で加熱することにより、炭化水素の分解重合等で基材表面に炭素が沈積することによって得られたものであるが、コークスを高温で処理した黒鉛であってもよい。
黒鉛の基材は、特に限定されず、天然に存在するもの、人工的に作られたもの等、例えば、天然グラファイト、キッシュグラファイト等のいずれであってもよい。黒鉛基材及びコークスの形状は、固体状、粉末状等のいずれであってもよい。
The pyrolytic graphite is conventionally known and is not particularly limited, and any pyrolytic graphite can be used. Usually, pyrolytic graphite is obtained by heating the graphite substrate at a high temperature (about 2000 to 3000 ° C.) in a hydrocarbon atmosphere, and depositing carbon on the surface of the substrate by hydrocarbon decomposition polymerization or the like. However, graphite obtained by treating coke at a high temperature may be used.
The graphite substrate is not particularly limited, and may be any of naturally occurring materials, artificially produced materials such as natural graphite and quiche graphite. The shapes of the graphite base material and the coke may be either solid or powder.
エチレン−酢酸ビニル系樹脂組成物中の黒鉛の平均粒径は、エチレン−酢酸ビニル共重合体との分散性及び／又は物性発現性を考慮すると、５００μｍ程度以下とすることが好ましく、さらに３００μｍ程度以下とすることが好ましい。ここで、粒径は、黒鉛をＴＨＦ溶液中に充分分散させ、レーザー回折式粒度分布計ＳＡＬＤ−２２００（島津製作所社製）を用いて測定した値である。
黒鉛を適当な粒径にするために、上述した粉砕処理と同様の処理を行うことができる。
The average particle size of the graphite in the ethylene-vinyl acetate resin composition is preferably about 500 μm or less, more preferably about 300 μm, considering the dispersibility and / or physical properties of the ethylene-vinyl acetate copolymer. The following is preferable. Here, the particle diameter is a value measured by using a laser diffraction particle size distribution analyzer SALD-2200 (manufactured by Shimadzu Corporation) after sufficiently dispersing graphite in a THF solution.
In order to make graphite an appropriate particle size, the same process as the above-mentioned grinding process can be performed.
このように、特定の黒鉛をエチレン−酢酸ビニル共重合体に添加することにより、耐燃焼性シートにおいて、著しく耐燃焼性を向上させることができる。このため、「鉄道に関する技術上の基準を定める省令(平成１３年１２月２５日国土交通省令第１５１号)」の第５節車両の火災対策等第８３条に準拠した方法で行った燃焼試験において、試験体への着火を抑制する効果を発現させることができる。 Thus, by adding specific graphite to the ethylene-vinyl acetate copolymer, the combustion resistance can be remarkably improved in the flame resistance sheet. For this reason, the combustion test conducted by the method in accordance with Article 83 of Section 5 of Vehicle Fire Countermeasures of "Ministerial Ordinance for Establishing Technical Standards on Railways (December 25, 2001, Ministry of Land, Infrastructure, Transport and Tourism Ordinance No. 151)" The effect of suppressing the ignition of the test body can be expressed.
耐燃焼性を上げる効果は、添加する黒鉛の黒鉛化度及び／又はアスペクト比が高い方が有利であり、薄い形状と高温(２０００〜３０００℃)処理による高黒鉛化度により、耐燃焼性が高まるため、特に好ましい。 The effect of increasing the flame resistance is advantageous when the graphite to be added has a higher degree of graphitization and / or aspect ratio, and the flame resistance is reduced due to the thin shape and the high degree of graphitization by high-temperature (2000 to 3000 ° C.) treatment. This is particularly preferable because it increases.
黒鉛は、エチレン−酢酸ビニル系樹脂組成物の全重量に対して、１５〜７０重量％で含有されることが適しており、好ましくは３０〜７０重量％であり、さらに好ましくは４０〜６５重量％である。この範囲とすることにより、適切な難燃効果を得ることができるとともに、成形性の低下を防止することができる。 Graphite is suitably contained in an amount of 15 to 70% by weight, preferably 30 to 70% by weight, more preferably 40 to 65% by weight, based on the total weight of the ethylene-vinyl acetate resin composition. %. By setting it as this range, while being able to acquire a suitable flame-retardant effect, the fall of a moldability can be prevented.
本発明のエチレン−酢酸ビニル系樹脂組成物は、さらに、二次加工性を改善する加工助剤が含有されていることが好ましい。このような加工助剤としては、ポリテトラフルオロエチレン（ＰＴＦＥ）系モノマー、（メタ）アクリレート系モノマー又はこれらの混合物、さらに、これらモノマーの単独重合体又は共重合体等が挙げられる。これらモノマーは単独で用いてもよく、２種類以上を併用してもよい。なかでも、真空成形性等の二次加工性にはポリテトラフルオロエチレン（ＰＴＦＥ）と（メタ）アクリル酸アルキル重合体とからなる混合物が好ましい。
ポリテトラフルオロエチレンと（メタ）アクリル酸アルキル重合体とからなる混合物は、せん断力によりポリテトラフルオロエチレンがフィブリル化されるものが好ましい。このような混合物として、メタブレンＡ−３０００（三菱レイヨン（株）社製）等が挙げられる。
The ethylene-vinyl acetate resin composition of the present invention preferably further contains a processing aid for improving secondary processability. Examples of such processing aids include polytetrafluoroethylene (PTFE) monomers, (meth) acrylate monomers or mixtures thereof, and homopolymers or copolymers of these monomers. These monomers may be used independently and may use 2 or more types together. Of these, a mixture of polytetrafluoroethylene (PTFE) and an alkyl (meth) acrylate polymer is preferable for secondary processability such as vacuum formability.
The mixture of polytetrafluoroethylene and the alkyl (meth) acrylate polymer is preferably one in which polytetrafluoroethylene is fibrillated by shearing force. Examples of such a mixture include methabrene A-3000 (manufactured by Mitsubishi Rayon Co., Ltd.).
エチレン−酢酸ビニル系樹脂組成物における上述した加工助剤は、エチレン−酢酸ビニル共重合体を含む全樹脂成分、言い換えると、エチレン−酢酸ビニル系樹脂組成物において黒鉛以外の成分の０重量％〜５０重量％程度で添加されていることが適しており、１重量％〜３０重量％程度が好ましく、３重量％〜２５重量％程度がより好ましい。例えば、耐燃焼性シートの表層に加飾層を追加する等の場合には、より不燃性を確保するために黒鉛が増量されるが、黒鉛を増量すると、高温伸び性が低下する。これに対して、エチレン−酢酸ビニル系樹脂組成物において加工助剤、特に、上述したＰＴＦＥと（メタ）アクリル酸アルキル重合体とからなる混合物を添加する場合には、黒鉛成分が比較的多く添加された場合においても、それに起因する高温伸び性を良好に保つことができる。 The above-mentioned processing aids in the ethylene-vinyl acetate resin composition include all resin components including an ethylene-vinyl acetate copolymer, in other words, 0% by weight to components other than graphite in the ethylene-vinyl acetate resin composition. It is suitable that it is added at about 50% by weight, preferably about 1% to 30% by weight, more preferably about 3% to 25% by weight. For example, when a decorative layer is added to the surface layer of the flame resistant sheet, the graphite is increased in order to ensure more nonflammability, but when the graphite is increased, the high temperature extensibility decreases. On the other hand, in the case of adding a processing aid in an ethylene-vinyl acetate resin composition, particularly a mixture of PTFE and an alkyl (meth) acrylate polymer described above, a relatively large amount of graphite component is added. Even in such a case, it is possible to maintain good high-temperature elongation due to it.
エチレン−酢酸ビニル系樹脂組成物には、上述した加工助剤の有無にかかわらず、その意図する機能に影響を与えない限り、以下に示した種々の添加剤を添加してもよい。
本発明のエチレン−酢酸ビニル系樹脂組成物には、燃焼抑制効果を補助する目的で、さらに難燃剤が添加されていてもよい。また、必要に応じて、衝撃改質剤、酸化防止剤、光安定剤、顔料等の各種添加剤の１種又は２種以上が添加されていてもよい。また、エチレン−酢酸ビニル共重合体以外の樹脂成分を含有してもよい。これらの各添加剤は単独で用いてもよく、２種以上を併用してもよい。
Various additives shown below may be added to the ethylene-vinyl acetate resin composition as long as the intended function is not affected, regardless of the presence or absence of the processing aid described above.
A flame retardant may be further added to the ethylene-vinyl acetate resin composition of the present invention for the purpose of assisting the combustion suppressing effect. Moreover, 1 type, or 2 or more types of various additives, such as an impact modifier, antioxidant, a light stabilizer, and a pigment, may be added as needed. Moreover, you may contain resin components other than an ethylene-vinyl acetate copolymer. Each of these additives may be used alone or in combination of two or more.
上記難燃剤としては、例えば、二酸化アンチモン、三酸化アンチモン、五酸化アンチモン等の酸化アンチモン、三酸化モリブデン、二硫化モリブデン、アンモニウムモリブデート等のモリブデン化合物、テトラブロモビスフェノールＡ、テトラブロムエタン等の臭素系化合物、トリフェニルフォスフェート、アンモニウムポリフォスフェート等のリン系化合物などが挙げられる。 Examples of the flame retardant include antimony oxide such as antimony dioxide, antimony trioxide, and antimony pentoxide, molybdenum compounds such as molybdenum trioxide, molybdenum disulfide, and ammonium molybdate, and bromine such as tetrabromobisphenol A and tetrabromoethane. And phosphorus compounds such as triphenyl phosphate and ammonium polyphosphate.
衝撃改質剤としては、特に限定されず、例えば、メタクリル酸メチル−ブタジエン−スチレングラフト共重合体（ＭＢＳ樹脂）、アクリロニトリル−ブタジエン−スチレン共重合体（ＡＢＳ樹脂）、アクリル系改質剤等が挙げられる。これらは、単独で用いてもよく、２種類以上を併用してもよい。 The impact modifier is not particularly limited, and examples thereof include methyl methacrylate-butadiene-styrene graft copolymer (MBS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylic modifier, and the like. Can be mentioned. These may be used alone or in combination of two or more.
光安定剤としては、特に限定されず、例えば、サリチル酸エステル系、ベンゾフェノン系、ベンゾトリアゾール系、シアノアクリレート系等の紫外線吸収剤、あるいはヒンダードアミン系の光安定剤等が挙げられる。 The light stabilizer is not particularly limited, and examples thereof include ultraviolet absorbers such as salicylic acid esters, benzophenones, benzotriazoles, and cyanoacrylates, or hindered amine light stabilizers.
顔料としては、特に限定されず、例えば、アゾ系、フタロシアニン系、スレン系、染料レーキ系等の有機顔料、酸化物系、クロム酸モリブデン系、硫化物・セレン化物系、フェロシアン化物系等の無機顔料等が挙げられる。 The pigment is not particularly limited, and examples thereof include organic pigments such as azo, phthalocyanine, selenium, and dye lakes, oxides, molybdenum chromate, sulfide / selenide, ferrocyanide, and the like. An inorganic pigment etc. are mentioned.
エチレン−酢酸ビニル共重合体以外の樹脂成分としては、特に限定されず、種々のものを用いることができる。例えば、ポリプロピレン系樹脂、ポリエチレン系樹脂等のポリオレフィン系樹脂；ポリ（１−）ブテン系樹脂、ポリペンテン系樹脂、ポリスチレン系樹脂、アクリロニトリル−ブタジエン−スチレン系樹脂、ポリカーボネート系樹脂、ポリフェニレンエーテル系樹脂、アクリル系樹脂、ポリアミド系樹脂、塩素化ポリエチレン、塩化ビニル系樹脂、塩素化塩化ビニル系樹脂等が挙げられる。 It does not specifically limit as resin components other than an ethylene-vinyl acetate copolymer, A various thing can be used. For example, polyolefin resins such as polypropylene resins and polyethylene resins; poly (1-) butene resins, polypentene resins, polystyrene resins, acrylonitrile-butadiene-styrene resins, polycarbonate resins, polyphenylene ether resins, acrylics Resin, polyamide resin, chlorinated polyethylene, vinyl chloride resin, chlorinated vinyl chloride resin and the like.
以下、本発明のエチレン−酢酸ビニル重合体系樹脂組成物の実施例について説明するが、下記の例に限定されるものではない。 Examples of the ethylene-vinyl acetate polymer resin composition of the present invention will be described below, but are not limited to the following examples.
実施例１〜１７及び比較例１〜４
表１〜表３に示した所定量のエチレン−酢酸ビニル重合体、黒鉛およびポリテトラフルオロエチレンと（メタ）アクリル酸アルキル重合体とからなる混合物（以下、「ＰＴＦＥ系加工助剤」と記載する）を、８インチミキシングロール混練機（安田精機社製）に供給し、温度１７０℃で溶融混練して、厚さ１ｍｍのシートを得た。
次いで、熱プレス成形機(東邦マシナリー社製)に供給し、温度１８０℃、２００ｋｇｆで加圧し、３ｍｍのＢ５プレス板を得た。
なお、表１〜表３において、各成分の単位は重量％である。
Examples 1-17 and Comparative Examples 1-4
A mixture of a predetermined amount of ethylene-vinyl acetate polymer, graphite and polytetrafluoroethylene and an alkyl (meth) acrylate polymer shown in Tables 1 to 3 (hereinafter referred to as “PTFE processing aid”). ) Was supplied to an 8-inch mixing roll kneader (manufactured by Yasuda Seiki Co., Ltd.) and melt-kneaded at a temperature of 170 ° C. to obtain a sheet having a thickness of 1 mm.
Subsequently, it was supplied to a hot press molding machine (manufactured by Toho Machinery Co., Ltd.) and pressurized at a temperature of 180 ° C. and 200 kgf to obtain a 3 mm B5 press plate.
In Tables 1 to 3, the unit of each component is% by weight.
使用した材料は以下の通りである。
（１）ＥＶＡ１：エチレン−酢酸ビニル（商品名「エバフレックスＥＶ５６０」、三井・デュポンポリケミカル社製）
ＥＶＡ２：エチレン−酢酸ビニル（商品名「エバフレックスＥＶ２６０」、三井・デュポンポリケミカル社製）
（２）ＰＴＦＥ系加工助剤１：三菱レイヨン社製、商品名「メタブレンＡ−３０００」、
ＰＴＦＥ系加工助剤２：三菱レイヨン社製、商品名「メタブレンＡ−３８００」
（３）膨張後粉砕黒鉛：（商品名「ＣＳ−Ｆ４００」、丸豊鋳材社製）
熱分解黒鉛：（商品名「ＰＣ−３０」、伊藤黒鉛社製）
The materials used are as follows.
(1) EVA1: Ethylene-vinyl acetate (trade name “Evaflex EV560”, manufactured by Mitsui DuPont Polychemical Co., Ltd.)
EVA2: Ethylene-vinyl acetate (trade name “Evaflex EV260”, manufactured by Mitsui DuPont Polychemical Co., Ltd.)
(2) PTFE-based processing aid 1: manufactured by Mitsubishi Rayon Co., Ltd., trade name “Metablene A-3000”,
PTFE processing aid 2: manufactured by Mitsubishi Rayon Co., Ltd., trade name “METABBRENE A-3800”
(3) Post-expanded pulverized graphite: (trade name “CS-F400”, manufactured by Maruhyo Casting Co., Ltd.)
Pyrolytic graphite: (trade name “PC-30”, manufactured by Ito Graphite Co., Ltd.)
＜車両燃焼試験＞
着火：「鉄道に関する技術上の基準を定める省令(平成１３年１２月２５日国土交通省令第１５１号)」の第５節車両の火災対策等第８３条に準拠して評価
判定基準：
◎：着火無し(不燃相当)
○：着火時間が７０秒以上であり、着火後の火勢も弱い(極難燃相当)
△：３０秒を超え、７０秒未満に着火(難燃相当)
×：３０秒以内に着火
<Vehicle combustion test>
Ignition: Evaluation in accordance with Article 83 of Section 5 of Vehicle Fire Countermeasures of "Ministerial Ordinance Establishing Technical Standards on Railways (December 25, 2001, Ministry of Land, Infrastructure and Transport Ordinance No. 151)
A: No ignition (equivalent to nonflammability)
○: Ignition time is 70 seconds or more and the fire after ignition is weak (equivalent to extremely flame retardant)
Δ: Ignition over 30 seconds and less than 70 seconds (equivalent to flame retardant)
X: Ignition within 30 seconds
＜引張破壊伸び率＞
（ダンベル作製）
得られた厚さ３ｍｍのＢ５プレス板を切断し、ＪＩＳ Ｋ６７４１(２００４)の図１に記載されている呼び径２５以下の管から切り出される引張ダンベル形状と同サイズのダンベルを作製した。
（測定）
ＪＩＳ Ｋ７１１３に準拠して、１３０℃で引張試験を行った。
試験機は島津製作所社製オートグラフＡＧＳ−Ｊを使用し、
試験速度は５００ｍｍ／ｍｉｎ、状態調節は２ｈとした。
<Tensile fracture elongation>
(Dumbell production)
The obtained B5 press plate having a thickness of 3 mm was cut to produce a dumbbell having the same size as a tensile dumbbell cut out from a tube having a nominal diameter of 25 or less described in FIG. 1 of JIS K6741 (2004).
(Measurement)
A tensile test was performed at 130 ° C. in accordance with JIS K7113.
The test machine uses Shimadzu Autograph AGS-J,
The test speed was 500 mm / min, and the state adjustment was 2 h.
（引張破壊伸び率の算定）
標線間距離ａ(ｍｍ)を２３℃にて測定した。ダンベルが破壊するまで引張試験を行い、引張試験前後のチャック移動距離をｂ(ｍｍ)とし、
ａ÷(ｂ-ａ)×１００(％)を引張破壊伸び率とした。
高温での引張破壊伸び率は真空成形などの二次加工性を反映することから真空成形性の代用評価法として本評価を用いた。
なお、引張破壊伸び率における判定基準は、以下のとおりとした。
◎○：１３０℃引張破壊伸び率が４００％以上
◎：１３０℃引張破壊伸び率が２００％以上４００％未満
○：１３０℃引張破壊伸び率が１００％以上２００％未満
△：１３０℃引張破壊伸び率が３０％以上１００％未満
×：１３０℃引張破壊伸び率が３０％未満
(Calculation of tensile fracture elongation)
The distance a (mm) between the marked lines was measured at 23 ° C. A tensile test is performed until the dumbbell breaks, and the chuck moving distance before and after the tensile test is b (mm).
a ÷ (b−a) × 100 (%) was defined as tensile elongation at break.
Since the tensile fracture elongation at high temperature reflects secondary workability such as vacuum forming, this evaluation was used as a substitute evaluation method for vacuum forming.
The criteria for the tensile elongation at break were as follows.
◎: 130 ° C. tensile elongation at break of 400% or more ◎: 130 ° C. tensile elongation at break of 200% or more and less than 400% ○: 130 ° C. tensile elongation at break of 100% or more but less than 200% Δ: 130 ° C. tensile elongation at break 30% or more and less than 100% ×: 130 ° C. tensile fracture elongation is less than 30%
本発明は、エチレン−酢酸ビニル系樹脂組成物を使用することを期待するあらゆる分野、例えば、車両内装材として、特に、鉄道車両の内装材として好適に用いることができる。 INDUSTRIAL APPLICABILITY The present invention can be suitably used in all fields where the ethylene-vinyl acetate resin composition is expected to be used, for example, as a vehicle interior material, particularly as an interior material for a railway vehicle.
Claims (2)
膨張後粉砕黒鉛又は熱分解黒鉛とを含むエチレン−酢酸ビニル系樹脂組成物であって、
エチレン−酢酸ビニル系樹脂組成物の全重量に対して、前記膨張後粉砕黒鉛または熱分解黒鉛が、１５〜７０重量％で含有されていることを特徴とするエチレン−酢酸ビニル系樹脂組成物。 An ethylene-vinyl acetate copolymer;
An ethylene-vinyl acetate resin composition comprising expanded graphite and pyrolytic graphite after expansion,
An ethylene-vinyl acetate resin composition comprising 15 to 70% by weight of the expanded graphite or pyrolytic graphite with respect to the total weight of the ethylene-vinyl acetate resin composition.
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| JP2012067204A (en) * | 2010-09-24 | 2012-04-05 | Sekisui Chem Co Ltd | Vinyl resin composition molding and flame-retardant sheet |
| JP2017089306A (en) * | 2015-11-13 | 2017-05-25 | 積水化学工業株式会社 | Multi-layered heat expansion packing for building material |
| JP2019002273A (en) * | 2018-06-18 | 2019-01-10 | 積水化学工業株式会社 | Thermally-expansible multilayer packing for building materials |
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