JP4878455B2 - Thermoplastic soft composition - Google Patents
Thermoplastic soft composition Download PDFInfo
- Publication number
- JP4878455B2 JP4878455B2 JP2005238507A JP2005238507A JP4878455B2 JP 4878455 B2 JP4878455 B2 JP 4878455B2 JP 2005238507 A JP2005238507 A JP 2005238507A JP 2005238507 A JP2005238507 A JP 2005238507A JP 4878455 B2 JP4878455 B2 JP 4878455B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- acid
- thermoplastic
- styrene
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000203 mixture Substances 0.000 title claims description 30
- 229920001169 thermoplastic Polymers 0.000 title claims description 23
- 239000004416 thermosoftening plastic Substances 0.000 title claims description 23
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 42
- 229920001971 elastomer Polymers 0.000 claims description 22
- 239000000806 elastomer Substances 0.000 claims description 21
- 229920000728 polyester Polymers 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 229920001400 block copolymer Polymers 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 9
- 239000004925 Acrylic resin Substances 0.000 claims description 8
- 229920000178 Acrylic resin Polymers 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 5
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical group CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002834 transmittance Methods 0.000 claims description 4
- 229920001519 homopolymer Polymers 0.000 claims description 3
- 238000010030 laminating Methods 0.000 claims description 2
- 239000000178 monomer Substances 0.000 description 19
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 9
- -1 methacryloyl group Chemical group 0.000 description 9
- 229920002554 vinyl polymer Polymers 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 8
- 239000011342 resin composition Substances 0.000 description 8
- 229920005992 thermoplastic resin Polymers 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000002009 diols Chemical class 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
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- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000004566 building material Substances 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920001890 Novodur Polymers 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229920003232 aliphatic polyester Polymers 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 150000002596 lactones Chemical class 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007779 soft material Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- RCJMVGJKROQDCB-UHFFFAOYSA-N 2-methylpenta-1,3-diene Chemical compound CC=CC(C)=C RCJMVGJKROQDCB-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 229930182556 Polyacetal Natural products 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000007646 gravure printing Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 230000002522 swelling effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- OCTVDLUSQOJZEK-UHFFFAOYSA-N 4,5-diethylocta-1,3-diene Chemical compound CCCC(CC)C(CC)=CC=C OCTVDLUSQOJZEK-UHFFFAOYSA-N 0.000 description 1
- UGWOAPBVIGCNOV-UHFFFAOYSA-N 5-ethenyldec-5-ene Chemical compound CCCCC=C(C=C)CCCC UGWOAPBVIGCNOV-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
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- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229920002633 Kraton (polymer) Polymers 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
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Description
本発明は、建材、家具、家電製品、日用雑貨等の用途に幅広く用いられ、スチレン系樹脂との２色成形性、柔軟性、グリップ性、着色性に優れた熱可塑性軟質組成物に関する。 The present invention relates to a thermoplastic flexible composition that is widely used in applications such as building materials, furniture, home appliances, and household goods, and that is excellent in two-color moldability, flexibility, grip properties, and colorability with a styrene resin.
従来より、種々のエラストマーにエステル系エラストマーを添加することによって得られる熱可塑性樹脂組成物（例えば、特許文献１および２参照。）や、スチレン系エラストマー、アクリル系樹脂、スチレン系樹脂からなる熱融着性に優れた樹脂（例えば、特許文献３参照）が報告されている。また、スチレン系樹脂特にスチレン−アクリロニトリル共重合体（ＡＳ）、スチレン−アクリロニトリル−ブタジエン共重合体（ＡＢＳ）に熱融着するエラストマーとしてウレタン系エラストマーが知られているが、ウレタン系エラストマーは耐候性が悪い事も知られている。
しかし、ＡＢＳ、ＡＳに充分に熱融着しかつ着色性、耐候性に優れた軟質素材は知られていなかった。
However, a soft material that is sufficiently heat-fused to ABS and AS and excellent in colorability and weather resistance has not been known.
本発明は、家具、家電製品、日用品等の各種工業用部材の用途に有用な、耐熱性、柔軟性、熱融着性、耐候性、着色性に優れたスチレン系樹脂組成物を提供することを目的とする。 The present invention provides a styrenic resin composition excellent in heat resistance, flexibility, heat-fusibility, weather resistance, and colorability, which is useful for various industrial members such as furniture, household appliances, and daily necessities. With the goal.
本発明者らは上記課題を解決するため検討を重ね本発明に到った。
即ち、本発明は、
１．スチレン系エラストマ−（Ａ）３０〜８０重量部、アクリル系樹脂（Ｂ）１８〜４０重量部および融点３０〜２００℃の結晶性ポリエステル（Ｃ）２〜３０重量部から構成され、前記アクリル系樹脂（Ｂ）がメタクリル酸メチル単独重合体、または１５重量％以下のアクリル酸メチル単位またはアクリル酸エチル単位を含有するメタクリル酸メチル共重合体であることを特徴とする熱可塑性軟質組成物、
２．スチレン系エラストマ−（Ａ）が、スチレン系水素添加ブロック共重合体であることを特徴とする上記１に記載の熱可塑性軟質組成物、
３．上記１または２に記載の熱可塑性軟質組成物と硬質材を積層してなる複層成形品、
４．透過率６０％以上の上記３に記載の複層成形品、
に関する。
The inventors of the present invention have repeatedly studied to solve the above problems and have arrived at the present invention.
That is, the present invention
1. Styrene elastomers - (A) 30 to 80 parts by weight, it is composed of an acrylic resin (B) 18 to 40 parts by weight of a melting point 30 to 200 ° C. of the crystalline polyester (C) 2 to 30 parts by weight, the acrylic resin A thermoplastic soft composition characterized in that (B) is a methyl methacrylate homopolymer or a methyl methacrylate copolymer containing 15 wt% or less of a methyl acrylate unit or an ethyl acrylate unit,
2. 2. The thermoplastic soft composition as described in 1 above, wherein the styrenic elastomer (A) is a styrenic hydrogenated block copolymer,
3. A multilayer molded article obtained by laminating the thermoplastic soft composition according to 1 or 2 and a hard material,
4). The multilayer molded article according to the above 3, having a transmittance of 60% or more,
About.
本発明は、建材、家具、家電製品、日用雑貨等の用途に幅広く用いられ、スチレン系樹脂との２色成形性、柔軟性、グリップ性、着色性に優れた熱可塑性軟質組成物に関する。 The present invention relates to a thermoplastic flexible composition that is widely used in applications such as building materials, furniture, home appliances, and household goods, and that is excellent in two-color moldability, flexibility, grip properties, and colorability with a styrene resin.
必須成分であるスチレン系エラストマー（Ａ）とは、具体的には共役ジエン系単量体と芳香族ビニル単量体からなるブロック共重合体あるいはその水素添加物が好ましい。
スチレン系エラストマー（Ａ）の含有量は３０〜８０重量部である。より好ましくは、４０〜６５重量部である。スチレン系エラストマー（Ａ）が３０重量部未満になると、熱可塑性軟質組成物の柔軟性が不足する。また、８０重量部以上になると、２色成形品の硬質材との密着性が足りなくなる。
該スチレン系エラストマー（Ａ）は、具体的には共役ジエン系単量体と芳香族ビニル単量体からなるブロック共重合体あるいはその水素添加物が好ましい。好ましくは芳香族ビニル単量体単位を５重量％以上、４０重量％未満含むスチレン系エラストマーである。
Specifically, the essential component styrene elastomer (A) is preferably a block copolymer comprising a conjugated diene monomer and an aromatic vinyl monomer, or a hydrogenated product thereof.
The content of the styrenic elastomer (A) is 30 to 80 parts by weight. More preferably, it is 40 to 65 parts by weight. When the amount of the styrene elastomer (A) is less than 30 parts by weight, the flexibility of the thermoplastic flexible composition is insufficient. Moreover, when it becomes 80 weight part or more, adhesiveness with the hard material of a 2 color molded product will run short.
Specifically, the styrene elastomer (A) is preferably a block copolymer comprising a conjugated diene monomer and an aromatic vinyl monomer, or a hydrogenated product thereof. Styrenic elastomers containing an aromatic vinyl monomer unit in an amount of 5% by weight or more and less than 40% by weight are preferred.
共役ジエン系単量体としては、例えば１，３−ブタジエン、イソプレン、２，３−ジメチル−１，３−ブタジエン、１，３−ペンタジエン、２−メチル−１，３−ペンタジエン、１，３−ヘキサジエン、４，５−ジエチル−１，３−オクタジエン、３−ブチル−１，３−オクタジエン、クロロプレン等が挙げられ、これら単量体から選ばれる１種あるいはこれら２種以上の混合物で使用できる。その中でも、物性の優れたエラストマーを得るには１，３−ブタジエン、イソプレンが好ましい。
芳香族ビニル単量体としては、スチレン、α−メチルスチレン、ｐ−メチルスチレン、ビニルトルエン、クロルスチレン等が好ましく、より好ましくはスチレンである。
Examples of the conjugated diene monomer include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3- Hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene and the like can be mentioned, and one kind selected from these monomers or a mixture of two or more kinds thereof can be used. Among these, 1,3-butadiene and isoprene are preferable for obtaining an elastomer having excellent physical properties.
As the aromatic vinyl monomer, styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, chlorostyrene and the like are preferable, and styrene is more preferable.
また、スチレン系エラストマ−（Ａ）のメルトフローレイト（ＭＦＲ）は、成形性、機械的強度から１〜３０ｇ／１０分（ＩＳＯ１１３３、条件；２３０℃、２．１６ｋｇｆ）が好ましい、また、２〜２０ｇ／１０分がより好ましい。
熱可塑性軟質組成物としての柔軟性を保持するためにはスチレン系エラストマ−（Ａ）は、その硬度がＪＩＳ Ａ硬度で８０以下のものであることが好ましい。また、ＪＩＳ Ａ硬度で７０以下のものであることがさらに好ましい。
本発明において好ましいスチレン系エラストマー（Ａ）は、芳香族ビニル単量体と共役ジエン単量体のブロック共重合体あるいは該ブロック共重合体の水素添加物である。本発明においては、水素添加されているブロック共重合体の方が水素添加されていないブロック共重合体に比べて耐熱性に優れ、経時的な物性変化が少なく、望ましい。この水素添加物は、スチレン系エラストマー中のオレフィン性二重結合の５０％以上が水素添加されていることが好ましく、より好ましくは８０％以上が水素添加されていることである。
Further, the melt flow rate (MFR) of the styrene elastomer (A) is preferably 1 to 30 g / 10 minutes (ISO 1133, conditions: 230 ° C., 2.16 kgf) in view of moldability and mechanical strength. 20 g / 10 min is more preferable.
In order to maintain flexibility as the thermoplastic soft composition, the styrene elastomer (A) preferably has a JIS A hardness of 80 or less. Further, it is more preferable that the JIS A hardness is 70 or less.
The styrene elastomer (A) preferred in the present invention is a block copolymer of an aromatic vinyl monomer and a conjugated diene monomer or a hydrogenated product of the block copolymer. In the present invention, a hydrogenated block copolymer is more preferable than a non-hydrogenated block copolymer because it is superior in heat resistance and has little change in physical properties over time. In this hydrogenated product, 50% or more of the olefinic double bonds in the styrene-based elastomer are preferably hydrogenated, and more preferably 80% or more are hydrogenated.
ブロック共重合体の分子構造は、直鎖状、分岐状、放射状あるいはこれらの組み合わせのいずれであってもよい。このスチレン系エラストマーは、どの様な製造方法によって製造したものでもよい。例えば、特公昭４０−２３７９８号公報に記載された方法により、リチウム触媒等を用いて不活性溶媒中でブロック共重合させて得ることができる。また、こうしたブロック共重合体の水素添加処理は、例えば特公昭４２−８７０４号公報、特公昭４３−６６３６号公報、あるいは特開昭５９−１３３２０３号公報および特開昭６０−７９００５号公報に記載された方法により、不活性溶媒中で水素添加触媒の存在下に行うことができる。
このようなスチレン系水素添加ブロック共重合体の市販品としては「ＫＲＡＴＯＮ（登録商標）−Ｇ」（シェル化学）、「セプトン（登録商標）」（クラレ）、「タフテック（登録商標）」（旭化成ケミカルズ（株）製）等がある。
The molecular structure of the block copolymer may be linear, branched, radial, or a combination thereof. This styrenic elastomer may be produced by any production method. For example, it can be obtained by block copolymerization in an inert solvent using a lithium catalyst or the like by the method described in Japanese Patent Publication No. 40-23798. In addition, the hydrogenation treatment of such a block copolymer is described in, for example, JP-B-42-8704, JP-B-43-6636, JP-A-59-133203, and JP-A-60-79005. Can be carried out in an inert solvent in the presence of a hydrogenation catalyst.
Commercial products of such styrenic hydrogenated block copolymers include “KRATON (registered trademark) -G” (Shell Chemical), “Septon (registered trademark)” (Kuraray), “Tuftec (registered trademark)” (Asahi Kasei). Chemicals Co., Ltd.).
また、上記スチレン系エラストマー（Ａ）に反応性基を導入しても良い。反応性基としては、エポキシ基、グリシジル基、カルボキシル基、メタクリロイル基、ヒドロキシル基等がある。反応性基を導入する方法には、エポキシ基、グリシジル基、カルボキシル基、メタクリロイル基、ヒドロキシル基等を有する単量体を共重合させる方法や、反応性基をもつ単量体をラジカル反応でグラフトさせる方法がある。カルボキシル基を持つビニル単量体としては、例えば、アクリル酸、クロトン酸、ケイ皮酸、イタコン酸、マレイン酸等の遊離カルボキル基を含有する不飽和化合物、無水マレイン酸、無水イタコン酸、クロロ無水マレイン酸、無水シトラコン酸などの酸無水物型カルボキシル基を含有する不飽和化合物等があげられるが、これらの中で、アクリル酸、メタクリル酸、無水マレイン酸が反応性、安価な事から好適である。また、グリシジル基を含有するビニル単量体としては、例えば、メタクリル酸グリシジル、アクリル酸グリシジル、アリルグリシジルエーテル、メチルグリシジルエーテル、メチルグリシジルメタクリレート等が挙げられるが、これらの中でもメタクリル酸グリシジルが好適である。
反応性基の含有量としては、０．１〜５重量％が望ましい。さらに好ましくは０．１〜２重量％が望ましい。
Moreover, you may introduce | transduce a reactive group into the said styrene-type elastomer (A). Examples of the reactive group include an epoxy group, a glycidyl group, a carboxyl group, a methacryloyl group, and a hydroxyl group. The reactive group can be introduced by copolymerizing a monomer having an epoxy group, glycidyl group, carboxyl group, methacryloyl group, hydroxyl group or the like, or by grafting a monomer having a reactive group by radical reaction. There is a way to make it. Examples of the vinyl monomer having a carboxyl group include unsaturated compounds containing a free carboxyl group such as acrylic acid, crotonic acid, cinnamic acid, itaconic acid, maleic acid, maleic anhydride, itaconic anhydride, and chloroanhydride. Examples include unsaturated compounds containing an acid anhydride-type carboxyl group such as maleic acid and citraconic anhydride. Among these, acrylic acid, methacrylic acid, and maleic anhydride are preferred because they are reactive and inexpensive. is there. Examples of the vinyl monomer containing a glycidyl group include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, methyl glycidyl ether, and methyl glycidyl methacrylate. Among these, glycidyl methacrylate is preferred. is there.
The content of reactive groups is preferably 0.1 to 5% by weight. More preferably, the content is 0.1 to 2% by weight.
本発明におけるアクリル系樹脂（Ｂ）は、通常はメタクリル酸メチル重合体（ＰＭＭＡ）、アクリル酸メチル重合体（ＰＭＡ）を使用でき、好ましくは、メタクリル酸メチル単独重合体、１５重量％以下のアクリル酸メチル単位またはアクリル酸エチル単位を含有するメタクリル酸メチル共重合体が好ましく、より好ましくは、メタクリル酸メチル単位８５〜９９重量％とアクリル酸メチル単位またはアクリル酸エチル単位１〜１５重量％とを含有するメタクリル酸メチル共重合体である。また、本発明の効果を損なわない範囲で、アクリル酸エステル、メタクリル酸エステル、無水マレイン酸、アクリル酸、メタクリル酸、ｐ−メチルスチレン、ｐ−ｔ−ブチルスチレン、ブチルアクリレート、アクリロニトリル、メタクリロニトリル、Ｎ−フェニルマレイミド等の共重合可能なビニル系単量体を併用することも可能である。アクリル酸エステル、メタクリル酸エステルの具体的な例としては、アクリル酸プロピル、アクリル酸ブチル、アクリル酸ステアリル、アクリル酸グリシジル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ブチル、メタクリル酸ステアリル、メタクリル酸グリシジル等がある。アクリル系樹脂（Ｂ）の製造方法としては、特に限定はされず、乳化重合、懸濁重合、塊状重合、溶液重合、およびこれらの重合法の組み合わせ等の方法がある。 As the acrylic resin (B) in the present invention, a methyl methacrylate polymer (PMMA) or a methyl acrylate polymer (PMA) can be usually used, preferably a methyl methacrylate homopolymer, 15% by weight or less of acrylic. A methyl methacrylate copolymer containing a methyl acid unit or an ethyl acrylate unit is preferred, and more preferably 85 to 99% by weight of a methyl methacrylate unit and 1 to 15% by weight of a methyl acrylate unit or an ethyl acrylate unit. It is a methyl methacrylate copolymer containing. In addition, acrylic acid ester, methacrylic acid ester, maleic anhydride, acrylic acid, methacrylic acid, p-methylstyrene, pt-butylstyrene, butyl acrylate, acrylonitrile, methacrylonitrile as long as the effects of the present invention are not impaired. It is also possible to use a copolymerizable vinyl monomer such as N-phenylmaleimide. Specific examples of acrylic esters and methacrylic esters include propyl acrylate, butyl acrylate, stearyl acrylate, glycidyl acrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, stearyl methacrylate, glycidyl methacrylate Etc. The method for producing the acrylic resin (B) is not particularly limited, and examples thereof include emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization, and combinations of these polymerization methods.
本発明の結晶性ポリエステル（Ｃ）とは、ジカルボン酸とジオールからなるポリエステル、ラクトン類を開環して得られる脂肪族ポリエステルの中で、結晶性でかつ融点が３０〜２００℃である事を特徴とする結晶性ポリエステルである。
上記融点とは、ＪＩＳ Ｋ７１２１に準拠し、示差熱分析（ＤＴＡ）又は示差走査熱量測定（ＤＳＣ）から求められる。示差走査熱量測定（ＤＳＣ）で、サンプル約１０ｍｇ、昇温速度２０℃／ｍｉｎ、冷却速度１０℃／ｍｉｎおよび窒素ガス流量１０ｍｌ／ｍｉｎの条件より求められることが好ましい。
上記ジカルボン酸とジオールからなる結晶性ポリエステルのジカルボン酸としては、具体的には、炭素数４〜２０のものが好ましく、その例として、テレフタル酸、イソフタル酸、フタル酸、ナフタレン−２，７−ジカルボン酸、ジフェニル−４，４−ジカルボン酸、ジフェノキシエタンジカルボン酸、３−スルホイソフタル酸ナトリウムのような芳香族ジカルボン酸、１，４−シクロヘキサンジカルボン酸、１，２−シクロヘキサンジカルボン酸、ジシクロヘキシル−４，４−ジカルボン酸のような脂環族ジカルボン酸、コハク酸、シュウ酸、アジピン酸、セバシン酸、１，１０−デカンジカルボン酸が挙げられる。
The crystalline polyester (C) of the present invention is a polyester composed of a dicarboxylic acid and a diol, an aliphatic polyester obtained by ring-opening a lactone, and is crystalline and has a melting point of 30 to 200 ° C. It is a crystalline polyester characterized.
The melting point is determined from differential thermal analysis (DTA) or differential scanning calorimetry (DSC) in accordance with JIS K7121. It is preferably determined by differential scanning calorimetry (DSC) from the conditions of about 10 mg of sample, temperature rising rate 20 ° C./min, cooling rate 10 ° C./min, and nitrogen gas flow rate 10 ml / min.
Specifically, as the dicarboxylic acid of the crystalline polyester composed of the dicarboxylic acid and the diol, those having 4 to 20 carbon atoms are preferable, and examples thereof include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,7- Dicarboxylic acid, diphenyl-4,4-dicarboxylic acid, diphenoxyethanedicarboxylic acid, aromatic dicarboxylic acid such as sodium 3-sulfoisophthalate, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, dicyclohexyl- Examples include alicyclic dicarboxylic acids such as 4,4-dicarboxylic acid, succinic acid, oxalic acid, adipic acid, sebacic acid, and 1,10-decanedicarboxylic acid.
上記ジカルボン酸とジオールからなる結晶性ポリエステル樹脂のジオールとしては、炭素数２〜１２の脂肪族及び／又は脂環族のジオールの事で、エチレングリコール、１，４−ブタンジオール、１，６−ヘキサンジオール、ポリエチレングリコール、ポリプロピレングリコール、１，４−シクロヘキサンジオール等が上げられる。また、ポリエステル系熱可塑性樹脂の融点が３０〜２００℃なら、これらのジオールと、芳香族系のジオール、例えばビスフェノールＡ、ヒドロキノン等を併用しても良い。これらのジオール成分は、１種単独で、又は２種以上組合わせて用いることが出来る。
本発明の結晶性ポリエステルとしては、テレフタル酸、フタル酸、１，４−ブタンジオールを用いた結晶性ポリエステル樹脂である。このような市販のポリマーは、「バイロン（結晶性ポリエステル）」東洋紡株式会社等を上げる事ができる。
The diol of the crystalline polyester resin comprising the dicarboxylic acid and the diol is an aliphatic and / or alicyclic diol having 2 to 12 carbon atoms, such as ethylene glycol, 1,4-butanediol, 1,6- Hexanediol, polyethylene glycol, polypropylene glycol, 1,4-cyclohexanediol and the like can be mentioned. If the melting point of the polyester thermoplastic resin is 30 to 200 ° C., these diols and aromatic diols such as bisphenol A and hydroquinone may be used in combination. These diol components can be used alone or in combination of two or more.
The crystalline polyester of the present invention is a crystalline polyester resin using terephthalic acid, phthalic acid, or 1,4-butanediol. Examples of such commercially available polymers include “Byron (crystalline polyester)” Toyobo Co., Ltd.
ラクトン類を開環して得られる脂肪族ポリエステルとは、炭素数５〜１２のラクトン類とは、具体的にはε−カプロラクトン、ω−オキシカプロン酸等が挙げられる。このような市販のポリマーは、「プラクセル」ダイセル化学工業株式会社等を上げる事ができる。
本発明の熱可塑性軟質組成物の特に好ましい組み合わせの例としては、スチレン−ブタジエン共重合体水素添加物、ＰＭＭＡ樹脂および結晶性ポリエステルの三成分からなる樹脂組成物があげられる。
本発明の熱可塑性軟質組成物中のポリエステル系熱可塑性樹脂は２〜３０重量部であるが、５〜２０重量部がより好ましい。添加量が２重量部未満だと、２色成形品の硬質材との熱融着性が足りなくなし、３０重量部以上だと熱可塑性樹脂軟質組成物が硬くなる。
Specific examples of the aliphatic polyester obtained by ring-opening lactones include lactones having 5 to 12 carbon atoms such as ε-caprolactone and ω-oxycaproic acid. Such commercially available polymers can include “Placcel” Daicel Chemical Industries, Ltd.
Examples of particularly preferred combinations of the thermoplastic soft composition of the present invention include a resin composition comprising three components of a styrene-butadiene copolymer hydrogenated product, a PMMA resin and a crystalline polyester.
The polyester-based thermoplastic resin in the thermoplastic soft composition of the present invention is 2 to 30 parts by weight, more preferably 5 to 20 parts by weight. If the addition amount is less than 2 parts by weight, the heat fusion property with the hard material of the two-color molded product is insufficient, and if it is 30 parts by weight or more, the thermoplastic resin soft composition becomes hard.
本発明の熱可塑性軟質組成物の成分（Ａ）、（Ｂ）および（Ｃ）の各成分を溶融混合する方法については特に制限はなく、単軸押出機、ニ軸押出機、バンバリーミキサー、加圧ニーダー、ミキシングロール等通常公知の方法を用いることができる。
また、本発明のスチレン系樹脂組成物は、発泡させて使用することもできる。発泡させる方法は特に制限されないが、例えば熱分解型発泡剤を配合する方法、加圧下で水を配合し発泡剤として利用する方法、溶融成形時に高圧ガスを注入する方法など、従来公知の方法が利用可能である。
There is no particular limitation on the method of melt-mixing the components (A), (B) and (C) of the thermoplastic soft composition of the present invention, and there is no particular limitation, and a single screw extruder, a twin screw extruder, a Banbury mixer, an additive A generally known method such as a pressure kneader or a mixing roll can be used.
Moreover, the styrenic resin composition of the present invention can be used after being foamed. The method for foaming is not particularly limited. For example, conventionally known methods such as a method of blending a pyrolytic foaming agent, a method of blending water under pressure and using it as a foaming agent, and a method of injecting a high-pressure gas during melt molding are available. Is available.
本発明の熱可塑性軟質組成物には、必要に応じて、酸化防止剤、耐候剤、金属不活性剤、紫外線吸収剤、光安定剤、ブリード・ブルーム剤、シール性改良剤、結晶核剤、難燃化剤、架橋剤、共架橋剤、加硫剤、防菌、防カビ剤、分散剤、軟化剤、可塑剤、粘土調整剤、着色防止剤、発泡剤、発泡助剤、酸化チタン、カーボンブラックなどの着色剤、フェライトなどの金属粉末、ガラス繊維、金属繊維などの無機繊維、炭素繊維、アラミド繊維などの有機繊維、複合繊維、チタン酸カリウムウィスカーなどの無機ウィスカー、ガラスビーズ、ガラスバルーン、ガラスフレーク、アスベスト、マイカ、炭酸カルシウム、タルク、シリカ、ケイ酸カルシウム、ハイドロタルサイト、カオリン、ケイソウ土、グラファイト、軽石、エボ粉、コットンフロック、コルク粉、硫酸バリウム、フッ素樹脂、ポリマービーズなどの充填剤、またはこれらの混合物、あるいは他のゴム質重合体、例えばＳＢＲ、ＮＢＲ、ＢＲ、ＮＲ、ＩＲ、ＡＲ，ＣＲ、ＩＩＲ、ＥＰＤＭ、ＴＰＯ、ＴＰＶまた、その他必要に応じて上記成分以外の熱可塑性樹脂、例えばポリカーボネート系樹脂、ポリアセタール系樹脂、ポリアミド系樹脂、ポリエステル系樹脂、ポリエーテル系樹脂、ポリスルホン、ポリフェニレンサルファイド、ポリアセタール樹脂など、適宜、配合することができる。 In the thermoplastic soft composition of the present invention, an antioxidant, a weathering agent, a metal deactivator, an ultraviolet absorber, a light stabilizer, a bleed / bloom agent, a sealability improving agent, a crystal nucleating agent, Flame retardant, crosslinking agent, co-crosslinking agent, vulcanizing agent, antibacterial, antifungal agent, dispersant, softener, plasticizer, clay adjuster, anti-coloring agent, foaming agent, foaming aid, titanium oxide, Colorant such as carbon black, metal powder such as ferrite, inorganic fiber such as glass fiber and metal fiber, organic fiber such as carbon fiber and aramid fiber, composite fiber, inorganic whisker such as potassium titanate whisker, glass beads, glass balloon , Glass flakes, asbestos, mica, calcium carbonate, talc, silica, calcium silicate, hydrotalcite, kaolin, diatomaceous earth, graphite, pumice, evo flour, cotton flour Filler, cork powder, barium sulfate, fluororesin, polymer beads, etc., or mixtures thereof, or other rubbery polymers such as SBR, NBR, BR, NR, IR, AR, CR, IIR, EPDM , TPO, TPV, and other thermoplastic resins other than the above components as necessary, such as polycarbonate resins, polyacetal resins, polyamide resins, polyester resins, polyether resins, polysulfones, polyphenylene sulfide, polyacetal resins, etc. It can mix | blend suitably.
本発明の熱可塑性軟質組成物は、押出、射出、ブロー、プレス成形等の各種成形法により成形することができる。中でも押出成形が好ましく、異型押出、シート押出、複層押出等の押出成形法が幅広く適用できる。
本発明における硬質材とは、本発明の熱可塑性軟質組成物と共押出または、射出成形により成形可能な熱可塑性樹脂のことをいう。例えば、不飽和ニトリル単量体単位を含有したスチレン系熱可塑性樹脂、メタクリル酸メチル重合体（ＰＭＭＡ）、ポリカーボネート、メタクリル酸メチル−スチレン共重合体（ＭＳ）、メタクリル酸メチル−スチレン−ブタジエン共重合体（ＭＢＳ）等が挙げられる。中でも不飽和ニトリル単量体単位を含有したスチレン系熱可塑性樹脂が好ましく、その中でもＡＢＳ樹脂、ＡＳ樹脂が特に好ましい。
The thermoplastic soft composition of the present invention can be molded by various molding methods such as extrusion, injection, blow, and press molding. Of these, extrusion molding is preferable, and extrusion molding methods such as profile extrusion, sheet extrusion, and multilayer extrusion can be widely applied.
The hard material in the present invention refers to a thermoplastic resin that can be formed by coextrusion or injection molding with the thermoplastic soft composition of the present invention. For example, styrene thermoplastic resin containing unsaturated nitrile monomer units, methyl methacrylate polymer (PMMA), polycarbonate, methyl methacrylate-styrene copolymer (MS), methyl methacrylate-styrene-butadiene copolymer Examples include coalescence (MBS). Of these, styrene-based thermoplastic resins containing unsaturated nitrile monomer units are preferable, and among these, ABS resins and AS resins are particularly preferable.
本発明の熱可塑性軟質組成物からなる成形品には表面に印刷や塗装を施すこと、接着剤を用いて他の素材と接着することが可能である。各種成形法で成形された成形品に対して、表面を塗装したり、グラビア印刷等で表面に種々の意匠、図柄を印刷して外観を見栄えの良いものにすることができる。また、他の素材と接着剤を用いて接着することにより製品の一部に本熱可塑性軟質組成物の成形品を組み合わせて用いることができる。
本発明の熱可塑性軟質組成物は、溶剤に対して適度の膨潤性を示すため、塗料、印刷用インク、接着剤に含まれる溶剤により膨潤することで塗料、インク、接着剤の樹脂素材と密着することが可能となる。
The molded article made of the thermoplastic flexible composition of the present invention can be printed or painted on the surface, and can be bonded to other materials using an adhesive. The surface of a molded product molded by various molding methods can be painted or various designs and designs can be printed on the surface by gravure printing or the like to improve the appearance. Moreover, the molded article of this thermoplastic soft composition can be combined and used for a part of product by adhere | attaching with another raw material and an adhesive agent.
Since the thermoplastic soft composition of the present invention exhibits an appropriate swelling property with respect to a solvent, it is in close contact with a resin material of the paint, ink, or adhesive by swelling with a solvent contained in the paint, printing ink, or adhesive. It becomes possible to do.
ここで、本発明の熱可塑性軟質組成物が膨潤性を示す溶剤としては、メチルエチルケトン（ＭＥＫ）、アセトン、トルエン、シクロヘキサン、ノルマルヘキサン、酢酸エチル、酢酸ブチル、酢酸イソプロピル、塩化メチレンあるいはこれらの混合物が挙げられる。このような溶剤を含む塗料や印刷用インク、接着剤に対して密着することが可能である。例えば、グラビア印刷インキは、樹脂成分が、ＥＶＡ、変性塩ビ等であり、溶剤がＭＥＫ、トルエン、シクロヘキサン、酢酸ブチル等の混合物であり、本発明のスチレン系樹脂組成物成形品の印刷用に好適に使用することができる。
また、例えば、接着剤としては、アセトン、ノルマルヘキサン、酢酸ブチル等の混合溶剤を用いたウレタン系接着剤、合成ゴム系接着剤により他の素材と良好に接着することができる。
本発明の熱可塑性軟質組成物成形品の用途としては、屋内外の家具・建材の一部材として、例えば、木口材、戸あたり、敷居板、サッシ、グレーチング、テーブルエッジ、滑り止め、等があげられる。また２色成形品として、例えば、家電、筆記具等の各種グリップや、パッキン、衝撃吸収材、滑り止め、手すり、目地、風呂蓋等が挙げられる。
Here, as a solvent in which the thermoplastic soft composition of the present invention exhibits swelling properties, methyl ethyl ketone (MEK), acetone, toluene, cyclohexane, normal hexane, ethyl acetate, butyl acetate, isopropyl acetate, methylene chloride or a mixture thereof can be used. Can be mentioned. It is possible to adhere to a paint, printing ink, or adhesive containing such a solvent. For example, gravure printing ink has a resin component of EVA, modified vinyl chloride, etc., and a solvent is a mixture of MEK, toluene, cyclohexane, butyl acetate, etc., and is suitable for printing the styrene resin composition molded product of the present invention. Can be used for
Further, for example, as an adhesive, it can be satisfactorily bonded to other materials by a urethane adhesive or a synthetic rubber adhesive using a mixed solvent such as acetone, normal hexane, and butyl acetate.
Applications of the thermoplastic flexible composition molded article of the present invention include, for example, interior and exterior furniture and building materials, such as wood ends, doors, sill boards, sashes, gratings, table edges, anti-slip, etc. It is done. Examples of the two-color molded product include various grips such as home appliances and writing instruments, packing, shock absorbers, anti-slip, handrails, joints, bath lids, and the like.
以下、実施例を挙げ、本発明をさらに詳細に説明する。下記の実施例において、部および％は、特に断らない限り重量基準である。
（１）実施例および比較例に用いた原材料
＜スチレン系エラストマ−（Ａ）＞
（Ａ−１）：水素添加スチレンブタジエンブロック共重合体
（旭化成ケミカルズ（株）製、タフテックＨ１２２１（商品名））ＪＩＳ Ａ硬度４２
（成分）芳香族ビニル単量体単位含有量 １２重量％
＜アクリル系樹脂（Ｂ）＞
（Ｂ−１）：旭化成ケミカルズ（株）製、デルペット ７２０Ｖ（ＰＭＭＡ樹脂）
＜エステル系樹脂組成物＞
（Ｃ−１）：東洋紡株式会社 バイロン ２４５（非晶性ポリエステル）
（Ｃ−２）：東洋紡株式会社 バイロン ＧＭ９２０（結晶性ポリエステル）融点 １０７℃
（Ｃ−３）：ダイセル化学工業株式会社 プラクセル Ｈ７（脂肪族ポリエステル）融点 ６０℃
（Ｃ−４）：ウィンテックポリマー（株） ＤＵＲＡＮＥＸ ２００２（ＰＢＴ）融点 ２２８℃
＜ＡＢＳ樹脂＞
（Ｄ−１）：旭化成ケミカルズ（株）製、スタイラックＡＢＳ ３２１（成分）不飽和ニトリル単量体含有量 ２２重量％
Hereinafter, the present invention will be described in more detail with reference to examples. In the following examples, parts and percentages are by weight unless otherwise specified.
(1) Raw materials used in Examples and Comparative Examples <Styrene Elastomer (A)>
(A-1): Hydrogenated styrene butadiene block copolymer (manufactured by Asahi Kasei Chemicals Corporation, Tuftec H1221 (trade name)) JIS A hardness 42
(Component) Content of aromatic vinyl monomer unit 12% by weight
<Acrylic resin (B)>
(B-1): Delpet 720V (PMMA resin) manufactured by Asahi Kasei Chemicals Corporation
<Ester resin composition>
(C-1): Toyobo Co., Ltd. Byron 245 (amorphous polyester)
(C-2): Toyobo Co., Ltd. Byron GM920 (crystalline polyester) melting point 107 ° C.
(C-3): Daicel Chemical Industries, Ltd. PLACCEL H7 (aliphatic polyester) melting point 60 ° C
(C-4): Wintech Polymer Co., Ltd. DURANEX 2002 (PBT) Melting point 228 ° C
<ABS resin>
(D-1): Asahi Kasei Chemicals Corporation, Stylac ABS 321 (component) Unsaturated nitrile monomer content 22% by weight
（２）評価方法
１．硬度
ＪＩＳ Ｋ−７２１５に準拠し、硬度を測定した。
２．引張試験
ＪＩＳ Ｋ６７６０：引張速度２００ｍｍ／Ｓ 準拠。
１８０℃でプレス成形した２ｍｍ厚シートからＪＩＳ Ａタイプのダンベル試験片を切り出し測定した。
３．ＡＳ樹脂との２色成形品の接着性（図１参照。）
硬質材にＡＳのスタイラック７８３を用い、本発明の熱可塑性軟質組成物を軟質材として用い、あらかじめ成形された９ｃｍ×３ｃｍ×０．１ｃｍの１２１の平板を金型にインサートし、軟質部を２２０℃で成形し硬質材上に約１ｍｍ厚の軟質を被覆してなる複層成形品を用いた。複層成形品を２ｃｍ幅に切り出し、軟質部をチャックにてはさみ直角方向に引っ張って接着強度を確認した。
◎ 軟質部を剥がすのに２ｋｇｆ以上の応力を必要とし、かつ軟質の素材が破壊する。
○ 軟質部を剥がすのに２ｋｇｆ以上の強度を要した。
△ １〜２ｋｇｆで簡単に軟質部が剥がれた。
× 軟質部がほとんど伸びずに剥がれた。
４．全光線透過率
５ｃｍ×９ｃｍ、厚み２．５ｍｍの平板を用いて、全光線透過率を測定した。
測定にはスガ試験機（株）のヘイズメーター（ＳＭ−３型）を用いた。
透過率が、６０％以上の素材が着色性に優れると判断した。
(2) Evaluation method Hardness Hardness was measured according to JIS K-7215.
2. Tensile test JIS K6760: Tensile speed 200 mm / S compliant.
A JIS A type dumbbell test piece was cut out and measured from a 2 mm thick sheet press-molded at 180 ° C.
3. Adhesion of two-color molded product with AS resin (see Fig. 1)
Using AS stylac 783 as the hard material, using the thermoplastic soft composition of the present invention as the soft material, 121 plates of 9 cm × 3 cm × 0.1 cm, which were previously molded, were inserted into the mold, and the soft part was A multilayer molded product obtained by molding at 220 ° C. and coating a hard material with a softness of about 1 mm thickness was used. The multilayer molded product was cut out to a width of 2 cm, and the soft part was pinched with a chuck and pulled in a direction perpendicular to the adhesive strength.
◎ A stress of 2 kgf or more is required to peel the soft part, and the soft material is destroyed.
○ Strength of 2 kgf or more was required to peel off the soft part.
Δ: The soft part was easily peeled off at 1-2 kgf.
X The soft part was peeled off with little elongation.
4). Total light transmittance was measured using a flat plate having a thickness of 5 cm × 9 cm and a thickness of 2.5 mm.
The haze meter (SM-3 type) of Suga Test Instruments Co., Ltd. was used for the measurement.
A material having a transmittance of 60% or more was judged to be excellent in colorability.
［実施例１〜２および比較例１〜８］
表１に記載の配合比で原材料を用い、２軸押出機を用いて２３０度にて溶融混練し、スチレン系樹脂組成物のペレットを製造した。該ペレットを用い、上記評価方法で評価し、その評価結果を表１に示した。
[Examples 1-2 and Comparative Examples 1-8]
The raw materials were used at the blending ratios shown in Table 1, and melt-kneaded at 230 degrees using a twin-screw extruder to produce styrene resin composition pellets. The pellets were used for evaluation by the above evaluation method, and the evaluation results are shown in Table 1.
本発明は、建材、家具、家電製品等の各種工業用部材の用途に有用な耐熱性、柔軟性、塗装性、印刷性、２色成形性に優れたスチレン系樹脂組成物、その成形体およびその複層成形品を提供することを目的とする。 The present invention relates to a styrenic resin composition excellent in heat resistance, flexibility, paintability, printability, two-color moldability, useful for various industrial members such as building materials, furniture, and home appliances, and molded articles thereof. An object is to provide the multilayer molded product.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005238507A JP4878455B2 (en) | 2005-08-19 | 2005-08-19 | Thermoplastic soft composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005238507A JP4878455B2 (en) | 2005-08-19 | 2005-08-19 | Thermoplastic soft composition |
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| JP2701147B2 (en) * | 1988-02-09 | 1998-01-21 | 旭化成工業株式会社 | Polymer blend composition |
| JPH0324149A (en) * | 1989-06-21 | 1991-02-01 | Japan Synthetic Rubber Co Ltd | Thermoplastic resin composition |
| JP3479167B2 (en) * | 1995-07-19 | 2003-12-15 | 旭化成株式会社 | Method for producing thermoplastic polymer molded article having marble pattern |
| JP2000095925A (en) * | 1998-07-24 | 2000-04-04 | Kureha Elastomer Kk | Elastomer composition and laminate |
| JP4428793B2 (en) * | 2000-03-06 | 2010-03-10 | リケンテクノス株式会社 | Thermally fusible resin composition |
| JP2002105343A (en) * | 2000-10-03 | 2002-04-10 | Mitsubishi Engineering Plastics Corp | Thermoplastic resin composition, method for producing the same and automobile molded product for automobile |
| JP2006249372A (en) * | 2005-03-14 | 2006-09-21 | Asahi Kasei Chemicals Corp | Soft thermoplastic composition |
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