JP4169631B2 - Laminate using thermoplastic polyurethane elastomer composition and method for producing the laminate - Google Patents
Laminate using thermoplastic polyurethane elastomer composition and method for producing the laminate Download PDFInfo
- Publication number
- JP4169631B2 JP4169631B2 JP2003132554A JP2003132554A JP4169631B2 JP 4169631 B2 JP4169631 B2 JP 4169631B2 JP 2003132554 A JP2003132554 A JP 2003132554A JP 2003132554 A JP2003132554 A JP 2003132554A JP 4169631 B2 JP4169631 B2 JP 4169631B2
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- Prior art keywords
- thermoplastic polyurethane
- laminate
- ethylene
- polyurethane elastomer
- vinyl acetate
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- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims description 38
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims description 38
- 229920001971 elastomer Polymers 0.000 title claims description 35
- 239000000806 elastomer Substances 0.000 title claims description 27
- 239000000203 mixture Substances 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229920001897 terpolymer Polymers 0.000 claims description 24
- 229920005989 resin Polymers 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 17
- 239000013538 functional additive Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 6
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- PZWQOGNTADJZGH-SNAWJCMRSA-N (2e)-2-methylpenta-2,4-dienoic acid Chemical compound OC(=O)C(/C)=C/C=C PZWQOGNTADJZGH-SNAWJCMRSA-N 0.000 claims description 2
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims 1
- 239000011342 resin composition Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 15
- 230000006866 deterioration Effects 0.000 description 12
- 238000004898 kneading Methods 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 239000010410 layer Substances 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- 239000011247 coating layer Substances 0.000 description 8
- 238000002845 discoloration Methods 0.000 description 8
- 230000004927 fusion Effects 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 238000000576 coating method Methods 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000004040 coloring Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 239000004611 light stabiliser Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 238000003490 calendering Methods 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- -1 fatty acid ester Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 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
- UWSMKYBKUPAEJQ-UHFFFAOYSA-N 5-Chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O UWSMKYBKUPAEJQ-UHFFFAOYSA-N 0.000 description 1
- SPBDXSGPUHCETR-JFUDTMANSA-N 8883yp2r6d Chemical compound O1[C@@H](C)[C@H](O)[C@@H](OC)C[C@@H]1O[C@@H]1[C@@H](OC)C[C@H](O[C@@H]2C(=C/C[C@@H]3C[C@@H](C[C@@]4(O[C@@H]([C@@H](C)CC4)C(C)C)O3)OC(=O)[C@@H]3C=C(C)[C@@H](O)[C@H]4OC\C([C@@]34O)=C/C=C/[C@@H]2C)/C)O[C@H]1C.C1C[C@H](C)[C@@H]([C@@H](C)CC)O[C@@]21O[C@H](C\C=C(C)\[C@@H](O[C@@H]1O[C@@H](C)[C@H](O[C@@H]3O[C@@H](C)[C@H](O)[C@@H](OC)C3)[C@@H](OC)C1)[C@@H](C)\C=C\C=C/1[C@]3([C@H](C(=O)O4)C=C(C)[C@@H](O)[C@H]3OC\1)O)C[C@H]4C2 SPBDXSGPUHCETR-JFUDTMANSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000181 anti-adherent effect Effects 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene 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
- 229920001778 nylon Polymers 0.000 description 1
- 150000003014 phosphoric acid esters 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
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、熱可塑性ポリウレタンエラストマーの加工性を向上させた積層体に関し、詳しくは、カレンダー成形技術、押出成形技術、注型技術、圧延技術、その他の適宜の成形技術、あるいは塗工技術等により、シート化したり、適宜の基材上に塗工層を形成する際の加工性を向上させ、またこのようにして得られるシートや塗工層の耐久性、外観等の各種の特性を向上させるための組成物を用いた積層体と、該積層体の製造方法に関する。
【０００２】
【技術背景】
熱可塑性ポリウレタンエラストマーは、上記のような各種の成形技術や塗工技術に良好に適応できる加工性を付与するために、あるいは上記のような特性を付与するために、一般に、種々の化合物が配合されている。
【０００３】
例えば、カレンダーロールで圧延成形する際にはロール面との滑性（以下、ロール滑性）を付与するために脂肪酸エステル系ワックスを添加し、また成形品について、難燃性を付与するために難燃剤、外観を良好にするために着色顔料、耐久性を付与するために酸化防止剤や光安定剤等を添加し、あるいは増量のために無機フィラー等を添加する。
【０００４】
これらの化合物を熱可塑性ポリウレタンエラストマーに均一に混合するには、一般には、フェンシェルミキサーを備えた単軸又は多軸押出機や、密閉式混練機（インターナルミキサー）等が使用される。
しかし、熱可塑性ポリウレタンエラストマーは、軟化温度が高く、種々の問題が提起されている。
【０００５】
例えば、上記の密閉式混練機を使用する場合における装置運転上のトラブルがある。
すなわち、このミキサーは、熱可塑性ポリウレタンエラストマーを溶融し、剪断し、この溶融・剪断下で上記の各種化合物を均一に混合させるものであって、ミキサーのジャケットやローターを、熱可塑性ポリウレタンエラストマーの軟化温度まで蒸気で加熱する必要がある。
このジャケットやローターへの加熱と、溶融しているウレタンエラストマーへの剪断とにより、該エラストマーは発熱し、上記のような各種の加工途上において、酸化劣化、ロール滑性の低下、あるいは変色等を生じる懸念がある。
また、添加量の少ない添加剤を均一に混合しようとすると、混合に要する時間が長くなり、熱可塑性ポリウレタンエラストマーの酸化劣化等が起こり易くなる。
【０００６】
上記のフェンシェルミキサーを備えた押出機においても、上記と同様の装置運転上のトラブルの発生を未然に回避することはできない。
【０００７】
【発明の目的】
本発明は、このような点を考慮し、上記のような各種の加工において熱可塑性ポリウレタンエラストマーが酸化劣化、ロール滑性の低下、あるいは変色等を生じさせないよう、該エラストマーの加工性あるいは該エラストマーの製品の特性を向上させるための組成物を用いた積層体と、該積層体の製造方法を提供することを目的とする。
【０００８】
【発明の概要】
本発明者は、上記目的を達成するために検討を重ねた結果、（１）上記のような酸化劣化、ロール滑性の低下、変色等を未然に防ぐための手法として、熱可塑性ポリウレタンエラストマーと上記各種化合物との均一混合を、低温領域で、迅速に行うことが最も好ましいとの結論に達した。
【０００９】
このような結論の下で、更に検討を進めた結果、（２）熱可塑性ポリウレタンエラストマーに、特定の樹脂を配合すれば、熱可塑性ポリウレタンエラストマーのみの場合よりも、低温領域下での剪断が可能となり、各種化合物の均一混合を迅速に行うことができるとの知見を得た。
【００１０】
本発明は、上記の知見に基づいてなされたものであって、その要旨は、
繊維質基材の少なくとも片面に、
（Ａ）熱可塑性ポリウレタンエラストマー（ＴＰＵ）と、
（Ｂ）（Ｂ１）エチレン−酢酸ビニル−一酸化炭素三元共重合体（Ｅ−ＶＡ−ＣＯ）と、酢酸ビニルモノマー部（ＶＡ）が４０重量％以上のエチレン−酢酸ビニル共重合体（Ｅ−ＶＡ）のいずれか一方または双方、
若しくは
（Ｂ２）Ｅ−ＶＡ−ＣＯとエチレン−メタクリル酸エステル−一酸化炭素三元共重合体（Ｅ−ＭＡ−ＣＯ）
を含む熱可塑性ポリウレタンエラストマー組成物層を設けてなり、優れた高周波融着性を有することを特徴とする積層体にある。
上記の（Ａ）成分と、（Ｂ１）成分又は（Ｂ２）成分である（Ｂ）成分（以下、「（Ｂ１）成分又は（Ｂ２）成分」を「（Ｂ）成分」と記すこともある）からなる樹脂成分に、（Ｃ）成分として有機系又は／及び無機系の機能性添加剤を配合してもよい。
この有機系又は／及び無機系の添加剤の含有量は、（Ａ），（Ｂ）からなる樹脂成分１００重量部に対し１重量部未満とすることが好ましい。
【００１１】
また、本発明は、（Ａ），（Ｂ）成分の混合、軟化、溶融と略同時に、あるいは軟化、溶融の直前または直後に、（Ｃ）成分を混合する上記組成物を繊維質基材の少なくとも片面に設けてなる積層体の製造方法をも要旨とする。
【００１２】
上記（Ａ）成分の熱可塑性ポリウレタン（ＴＰＵ）エラストマーは、一般にはゴムの代替樹脂として使用されるものであって、加硫工程が不要であるため成形加工が容易であり、硬度や弾性を任意に設定することができること等に加えて、機械的強度、耐摩耗性、低温特性にも優れており、前記したようなカレンダー成形、押出成形、注型、圧延、その他の適宜の成形技術や塗工技術等により、シート化したり、適宜の基材上に塗工層を形成する際に適した樹脂である。
しかも、ＴＰＵエラストマーによるシートや塗工層は、熱融着あるいは高周波融着特性をも有しており、ゴムに比して、二次加工性にも優れたものである。
本発明の樹脂成分は、この（Ａ）成分である熱可塑性ポリウレタンエラストマーを主体とするものである。
【００１３】
この（Ａ）成分に配合する（Ｂ）成分は、熱可塑性ポリウレタンエラストマーをシート化する際の、あるいは適宜の基材上に塗工する際等の、加工性を向上させるための役割を担い、またこのシートや塗工層の耐久性や外観等の特性を向上させるための役割を担うものである。
すなわち、（Ｂ）成分は、（Ａ）成分と（Ｂ）成分からなる本発明の樹脂組成物をシート化する際や塗工する際等の各種の加工工程において、酸化劣化、ロール滑性の低下、変色等が生じないよう、本発明の樹脂組成物の加工性を向上させるために、またこの結果として製品の品質（外観や耐久性等）を向上させるために配合するものである。
【００１４】
本発明における（Ｂ）成分としては、Ｅ−ＶＡ−ＣＯ三元共重合体、Ｅ−ＭＡ−ＣＯ三元共重合体、ＶＡが４０重量％以上のＥ−ＶＡ共重合体があるが、本発明では（Ａ）成分のＴＰＵと相溶性の高いＥ−ＶＡ−ＣＯ三元共重合体とＶＡが４０重量％以上のＥ−ＶＡ共重合体を各々単独で又は混合して配合するか、Ｅ−ＶＡ−ＣＯ三元共重合体とＥ−ＭＡ−ＣＯ三元共重合体を混合して配合することが、本発明の目的（本発明の樹脂組成物の加工性の向上、本発明の樹脂組成物で得られるシートや積層体の品質やウエルダー特性の向上）を達成する上で好ましい。
【００１５】
なお、上記Ｅ−ＶＡ−ＣＯ三元共重合体、Ｅ−ＭＡ−ＣＯ三元共重合体におけるＶＡ、ＭＡ部の割合や、ＣＯの割合は、特に限定しないが、ＶＡ、ＭＡ部が１０〜４０重量％程度のものであって、ＣＯが１０重量％程度のものを使用することが、上記本発明の目的を達成する上で適している。
【００１６】
（Ｂ）成分の配合量は、本発明の樹脂組成物に適用する加工技術によって異なるため、特に限定されないが、上記したカレンダー成形、押出成形、注型、圧延等の成形技術や、塗工技術等において加工性を向上させるためには、またこれらの成形技術や塗工技術で得られるシートや塗工層の耐久性、外観等の各種の特性を向上させるためには、（Ａ）成分１００重量部に対し、３〜２０重量部程度、好ましくは５〜１０重量部程度とすることが適している。
（Ｂ）成分がこれより少量であると、（Ｂ）成分の配合による上記の効果を得ることができない場合があり、これより多量であっても（Ｂ）成分配合の効果が飽和し不経済となる。
【００１７】
上記のＥ−ＶＡ−ＣＯ三元共重合体とＥ−ＭＡ−ＣＯ三元共重合体の組み合わせ、あるいはＥ−ＶＡ−ＣＯ三元共重合体とＶＡが４０重量％以上のＥ−ＶＡ共重合体の組み合わせとする場合には、Ｅ−ＶＡ−ＣＯ三元共重合体を（Ｂ）成分全量中５０重量％以上とすることが好ましい。
【００１８】
本発明では、上記の（Ａ），（Ｂ）成分からなる樹脂成分に、（Ｃ）成分として有機系又は／及び無機系の機能性添加剤を配合してもよい。
ここで、機能性添加剤とは、その添加剤の添加により、組成物や成形体に、例えば熱安定性や光安定性、紫外線による劣化抑制性、抗菌性、難燃性、ロール滑性、着色性、粘着防止性等の各種の機能を付与する添加剤を言う。
このような機能性添加剤は、組成物や成形体中に部分的に偏在しているのでは意味がなく（例えば、左半分は抗菌性があるが、右半分は抗菌性がない代わりに左半分にはない難燃性がある等）、全体に均一に分散されている必要がある。
【００１９】
上記の有機系の機能性添加剤としては、ヒンダードフェノール系等の酸化防止剤；ベンゾトリアゾール系やベンゾフェノン系等の紫外線吸収剤；ヒンダードフェノール系やヒンダードアミン系等の光安定剤；脂肪酸エステル系ワックス類、モンタン酸系ワックス類等の滑剤；リン酸エステル等の難燃剤；フタロシアニン系顔料やアゾ顔料等の着色剤等が挙げられる。
上記の無機系の機能性添加剤としては、炭酸カルシウム等の粘着防止剤；銀等の抗菌剤；三酸化アンチモン、水酸化アルミニウム、水酸化マグネシウム等の難燃剤；酸化チタンやカーボンブラック等の着色剤等が挙げられる。
これらの有機系、無機系の添加剤はそれぞれ、単独で配合してもよいし、２種以上を適宜組み合わせて配合することもできるし、有機系の機能性添加剤の１種以上と無機系の機能性添加剤の１種以上を組み合わせて配合することもできる。
【００２０】
有機系、無機系の機能性添加剤の配合量は、特に限定せず、本発明の樹脂組成物の用途に応じて、あるいは各添加剤の配合目的に応じて、適宜選定すればよい。
例えば、本発明の樹脂組成物をゴム引布等のような積層体における層構成材料（トッピング剤）として使用する場合には、樹脂成分１００重量部に対し、上記の酸化防止剤、紫外線吸収剤、光安定剤をそれぞれ０．０５〜０．３重量部程度、ロール滑性付与剤（滑剤）を０．２〜０．７重量部程度配合すればよい。
【００２１】
但し、無機系の機能性添加剤は、上記（Ａ），（Ｂ）成分からなる樹脂成分１００重量部に対し、１重量部以下であることが好ましい。
無機系添加剤が１重量部より多いと、製品シートや塗工層の重量が過大となって取扱性を低下させるばかりか、（Ｂ）成分配合による加工性の向上、特に下記するように本発明の樹脂組成物混練時の（Ａ），（Ｂ）両樹脂成分からなる樹脂成分の軟化点あるいは融点降下による酸化劣化、ロール滑性低下、着色等の防止効果を、良好に得難くし、またこの結果として製品シートや塗工層の耐久性、外観等をも低下させる等の不都合を生じる場合がある。
【００２２】
以上の配合からなる本発明の樹脂組成物は、（１）ヘンシェルミキサーを備えた単軸又は多軸押出機、（２）密閉式インテンシブミキサー又は密閉式混練機等を用い、上記各成分（（Ａ），（Ｂ）成分、有機系，無機系添加剤）を混合することによって得ることができる。
【００２３】
例えば、密閉式混練機を用いて本発明の樹脂組成物を得るには、前記したように、密閉式混練機のジャケットやローターをＴＰＵの軟化温度まで蒸気等で加熱し、ここに樹脂成分としての（Ａ），（Ｂ）両成分を投入する。
（Ｂ）成分は、（Ａ）成分のＴＰＵよりも軟化温度が低いため、密閉式混練機のローター等に絡んだＴＰＵが剪断により発熱し軟化、溶融する際には、既に（Ｂ）成分の軟化、溶融が生じている。
従って、ＴＰＵの軟化、溶融と略同時に、あるいは軟化、溶融の直前又は直後に、有機系、無機系の添加剤を投入すれば、これら添加剤の樹脂成分中への分散が迅速かつ均一に行われ、このとき（Ａ）成分と（Ｂ）成分の混合も迅速かつ均一に行われる。
この結果、ＴＰＵは、溶融温度以上の温度に長時間に渡って加熱されることがなくなり、ＴＰＵの酸化劣化、ロール滑性の低下、変色等を良好に防ぐことができる。
【００２４】
また、本発明のゴム引布等の積層体は、繊維質基材の少なくとも片面に上記の樹脂組成物からなる層が設けられたものであって、基材の片面のみに、あるいは両面に上記の樹脂組成物層を設けてもよいし、一方の面にゴム層を設け、他方の面に上記の樹脂組成物層を設けたものであってもよい。
これらのうち、一方の面にゴム層、他方の面に上記の樹脂組成物層を設けたゴム引布は、例えば、次のようにして製造される。
先ず、繊維質基材の一方の面に、カレンダー加工によりゴム組成物を圧延圧着し、加硫する。
次いで、他方の面に、上記した本発明の樹脂組成物をカレンダー加工により、圧延圧着する。この樹脂組成物層は、加硫は不要であり、必要に応じてアニーリング（加熱養生）する。
アニーリングの条件は、特に限定しないが、一般には、１００〜１３０℃程度の温度の常圧下で、０．５〜２時間程度保持すればよい。
【００２５】
実施例１〜２，７〜９、比較例１〜６
〔ＴＰＵ組成物の調製〕
表１及び表２に示す成分を表１及び表２に示す配合で、ジャケット及びローター温度を７０℃に設定したブラベンダーマシンに投入し、混練し、各配合の評価を行った。
なお、このときのマシン容積率は、樹脂成分量で６０％とした。
【００２６】
上記評価は、ローターに樹脂が絡みつきトルクが上昇し始めるまでの時間（混練時間▲１▼）と、発熱しトルクが安定するまでの時間（混練時間▲２▼）とを測定することで行った。これらの結果を、表１及び表２に示した。混練時間▲１▼と混練時間▲２▼のいずれも短時間の配合のものが、加工性が良好と言える。
また、各組成物の混練完了後の状態を目視観察し、変色が有るか否かを観察した。これらの結果も、表１及び表２に合わせて示した。変色なしの混練状態を得ることができれば、迅速に均一な混練が行われたことを意味し、変色がある場合は、かなり高温で混練が行われたことを意味している。
【００２７】
〔フィルムの調製〕
上記のようにして調製したＴＰＵ組成物を用い、カレンダー法により、剥型紙上に厚さ０．３ｍｍのＴＰＵフィルムを成形した。
このフィルムの端部を１ｃｍの幅で折り曲げ、該折り曲げ部を高周波ウエルダーにより融着させ、高周波融着可能な周波数の範囲を下記の基準で評価し、結果を表１及び表２に合わせて示した。
【００２８】
○；かなり広い範囲の周波数において、高周波融着が可能であるもの
×；特定の狭い範囲の周波数でしか高周波融着できないもの
【００２９】
〔積層体の調製〕
カレンダー加工により、ナイロン基布（４２０デニール×４２０デニール／４０本×４０本平織り）の一方の面に、ポリウレタン系接着剤を介して、上記のようにして調製したＴＰＵ組成物による層を厚さ２ｍｍとなるように形成した。
この積層体につき、上記のフィルムの場合と同様に、端部を１ｃｍの幅で折り曲げて高周波融着可能な周波数の範囲を上記の基準で評価し、結果を表１及び表２に合わせて示した。
【００３０】
表１及び表２中、
ＴＰＵ：熱可塑性ポリウレタンエラストマー（ＤＩＣ Ｂｙｅｒ社製商品名“パンデックスＴ８１７５Ｎ”）
ＥＶＡ▲１▼：Ｅ−ＶＡ共重合体（ＶＡ：４０重量％）
ＥＶＡ▲２▼：Ｅ−ＶＡ共重合体（ＶＡ：２６重量％）
ＥＶＡＣＯ：Ｅ−ＶＡ−ＣＯ三元共重合体（デュポンダウエラストマー社製商品名“エルバロイ７４１”）
ＥＭＡＣＯ：Ｅ−ＭＡ−ＣＯ三元共重合体（デュポンダウエラストマー社製商品名“エルバロイ４０５１”）
ＥＡＡＥＣＯ；Ｅ−ＡＡＥ−ＣＯ三元共重合体（デュポンダウエラストマー社製商品名“エルバロイＨＰ４４３”）
ＥＡＥＭＡＨ：Ｅ−ＡＥ−ＭＡＨ三元共重合体（住友化学社製商品名“ボンダイン”）
ＥＧＭＡ：Ｅ−ＧＭＡ共重合体（住友化学工業社製商品名“ボンドファーストＥ”）
ＬＬＤＰＥ：低密度ポリエチレン（密度：０．８９）
ＥＭＭＡ：Ｅ−ＭＭＡ（エチレン−メチルメタクリレート）
酸化防止剤：ヒンダートフェノール系（チバガイギー社製商品名“イルガノックス１０１０”）
紫外線吸収剤：ベンゾトリアゾール系（チバガイギー社製商品名“チヌビン３２７”）
光安定剤：ヒンダードアミン系（三共社製商品名“サノールＬＳ７７０”）
粘着抑制剤：炭酸カルシウム
混練時間▲１▼，▲２▼：秒
高周波融着性▲１▼：フィルムの高周波融着性
高周波融着性▲２▼：積層体の高周波融着性
を意味する。
【００３１】
【表１】
【表２】
【発明の効果】
本発明の樹脂組成物によれば、次のような効果を奏することができる。
（１）樹脂組成物混練時において、比較的低温で、かつ迅速に、樹脂成分物を混練することができるため、混練時における樹脂組成物の酸化劣化、ロール滑性低下、着色等の不都合を回避することができる。
（２）上記の結果として、本発明の樹脂組成物から得られる製品（フィルムや積層体等）は、加工性が非常に良好なものとなる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a laminate having improved processability of a thermoplastic polyurethane elastomer, and more specifically, by a calender molding technique, an extrusion molding technique, a casting technique, a rolling technique, other appropriate molding techniques, or a coating technique. , Improve the workability when forming a sheet or forming a coating layer on an appropriate substrate, and improve various properties such as durability and appearance of the sheet and coating layer thus obtained a laminate composition was used for a method for manufacturing of the laminate.
[0002]
[Technical background]
Thermoplastic polyurethane elastomers are generally blended with various compounds in order to provide processability that can be well adapted to the various molding and coating techniques described above, or to provide the above characteristics. Has been.
[0003]
For example, when roll forming with a calender roll, a fatty acid ester wax is added to impart lubricity to the roll surface (hereinafter referred to as roll lubricity), and to impart flame retardancy to the molded product. A flame retardant, a coloring pigment for improving the appearance, an antioxidant or a light stabilizer for imparting durability, or an inorganic filler for increasing the amount are added.
[0004]
In order to uniformly mix these compounds with the thermoplastic polyurethane elastomer, generally, a single-screw or multi-screw extruder equipped with a fen shell mixer, a closed kneader (internal mixer), or the like is used.
However, thermoplastic polyurethane elastomers have a high softening temperature, and various problems have been raised.
[0005]
For example, there is a trouble in operation of the apparatus when using the above-mentioned closed kneader.
That is, this mixer melts and shears a thermoplastic polyurethane elastomer, and uniformly mixes the above-mentioned various compounds under this melting and shearing. The mixer jacket and rotor are softened by the thermoplastic polyurethane elastomer. It needs to be heated with steam to temperature.
Due to the heating to the jacket and rotor and the shearing to the melted urethane elastomer, the elastomer generates heat, and during the various processing steps as described above, oxidation degradation, roll slippage deterioration, or discoloration occurs. There are concerns that arise.
Further, when an additive with a small addition amount is to be mixed uniformly, the time required for the mixing becomes longer, and the oxidative deterioration of the thermoplastic polyurethane elastomer tends to occur.
[0006]
Even in an extruder equipped with the above-mentioned fen shell mixer, it is impossible to avoid the occurrence of troubles similar to the above in operation of the apparatus.
[0007]
OBJECT OF THE INVENTION
In consideration of these points, the present invention provides the processability of the elastomer or the elastomer so that the thermoplastic polyurethane elastomer does not cause oxidative deterioration, roll slippage deterioration, or discoloration in the various processes as described above. a laminate using the composition to improve the properties of the product, and to provide a manufacturing method of the laminate.
[0008]
SUMMARY OF THE INVENTION
As a result of repeated studies to achieve the above object, the present inventor has (1) a thermoplastic polyurethane elastomer as a technique for preventing the above-described oxidation deterioration, roll slippage deterioration, discoloration and the like. It was concluded that it is most preferable to perform uniform mixing with the above-mentioned various compounds quickly in a low temperature region.
[0009]
As a result of further investigations under these conclusions, (2) If a specific resin is added to the thermoplastic polyurethane elastomer, shearing in a low temperature region is possible compared to the case of using only the thermoplastic polyurethane elastomer. Thus, it was found that uniform mixing of various compounds can be performed quickly.
[0010]
The present invention has been made based on the above findings, and the gist thereof is as follows:
On at least one side of the fibrous base material,
(A) a thermoplastic polyurethane elastomer (TPU);
(B) (B1) Ethylene-vinyl acetate-carbon monoxide terpolymer (E-VA-CO) and ethylene-vinyl acetate copolymer (E) having a vinyl acetate monomer part (VA) of 40% by weight or more One or both of -VA),
Or (B2) E-VA-CO and ethylene-methacrylic acid ester-carbon monoxide terpolymer (E-MA-CO)
The result provided including thermoplastic polyurethane elastomer composition layer, in a laminate characterized by having excellent high-frequency welding properties.
(A) component and (B1) component or (B2) component (B) component (hereinafter, “(B1) component or (B2) component” may be referred to as “(B) component”) You may mix | blend an organic or / and inorganic functional additive as (C) component with the resin component which consists of these.
The content of the organic or / and inorganic additive is preferably less than 1 part by weight with respect to 100 parts by weight of the resin component composed of (A) and (B).
[0011]
Further, the present invention is, (A), (B) mixing of the components, softening, melting and substantially simultaneously, or softening, immediately before or after the melting, the fibrous base on SL composition mixing component (C) The gist is also a method for producing a laminate formed on at least one side of a material .
[0012]
The thermoplastic polyurethane (TPU) elastomer as the component (A) is generally used as an alternative resin for rubber, and since it does not require a vulcanization process, it can be easily molded and can have any hardness and elasticity. In addition to being excellent in mechanical strength, wear resistance, and low-temperature characteristics, it can be set to a calender molding, extrusion molding, casting, rolling, and other appropriate molding techniques and coatings as described above. It is a resin suitable for forming a sheet or forming a coating layer on an appropriate base material by an engineering technique or the like.
Moreover, the sheet or coating layer made of TPU elastomer also has heat fusion or high frequency fusion properties, and is excellent in secondary processability as compared with rubber.
The resin component of the present invention is mainly composed of the thermoplastic polyurethane elastomer as the component (A).
[0013]
(B) component mix | blended with this (A) component bears the role for improving workability, when forming a thermoplastic polyurethane elastomer into a sheet, or when apply | coating on an appropriate base material, Moreover, it plays a role for improving the properties such as durability and appearance of the sheet and the coating layer.
That is, the component (B) is oxidized and deteriorated in various processing steps such as when the resin composition of the present invention comprising the component (A) and the component (B) is formed into a sheet or when it is applied. In order to improve the workability of the resin composition of the present invention and to improve the product quality (appearance, durability, etc.) as a result, it is added so as not to cause deterioration, discoloration and the like.
[0014]
The component (B) in the present invention includes an E-VA-CO terpolymer, an E-MA-CO terpolymer, and an E-VA copolymer having a VA of 40% by weight or more. In the present invention, an E-VA-CO terpolymer having a high compatibility with the TPU of the component (A) and an E-VA copolymer having a VA of 40% by weight or more are blended alone or in combination, E-VA-CO terpolymer and E-MA-CO terpolymer are mixed and blended to improve the processability of the resin composition of the present invention. It is preferable to achieve improvement in quality and welder characteristics of sheets and laminates obtained from the resin composition.
[0015]
Incidentally, the E-VA-CO terpolymer, E-MA-CO that put the terpolymer V A, and the ratio of M A portion, the proportion of CO is not particularly limited, VA, M In order to achieve the object of the present invention, it is suitable to use a part A having about 10 to 40% by weight and CO having about 10% by weight.
[0016]
The blending amount of the component (B) varies depending on the processing technology applied to the resin composition of the present invention, and is not particularly limited. However, the molding technology such as calendar molding, extrusion molding, casting, rolling, etc., and coating technology described above. In order to improve the workability in such as, and in order to improve various properties such as durability and appearance of the sheet and coating layer obtained by these molding techniques and coating techniques, component (A) 100 It is suitable that the amount is about 3 to 20 parts by weight, preferably about 5 to 10 parts by weight with respect to parts by weight.
When the amount of the component (B) is less than this, the above effect due to the blending of the component (B) may not be obtained. Even when the amount is larger than this, the effect of blending the component (B) is saturated and uneconomical. It becomes.
[0017]
Combination of the above E-VA-CO terpolymer and E-MA-CO terpolymer, or E-VA terpolymer with E-VA-CO terpolymer and VA of 40% by weight or more In the case of combining, it is preferable that the E-VA-CO terpolymer is 50% by weight or more based on the total amount of component (B).
[0018]
In the present invention, an organic or / and inorganic functional additive may be added as the component (C) to the resin component composed of the components (A) and (B).
Here, the functional additive is, for example, heat stability and light stability, anti-degradation due to ultraviolet rays, antibacterial properties, flame retardancy, roll lubricity, The additive which provides various functions, such as coloring property and adhesion prevention property.
Such functional additives are meaningless if they are partially unevenly distributed in the composition or molded body (for example, the left half is antibacterial, but the right half is not antibacterial but instead left It has to be evenly distributed throughout.
[0019]
Examples of the above-mentioned organic functional additives include antioxidants such as hindered phenols; UV absorbers such as benzotriazoles and benzophenones; light stabilizers such as hindered phenols and hindered amines; fatty acid esters Examples thereof include lubricants such as waxes and montanic acid waxes; flame retardants such as phosphate esters; colorants such as phthalocyanine pigments and azo pigments.
The above-mentioned inorganic functional additives include: anti-adhesive agents such as calcium carbonate; antibacterial agents such as silver; flame retardants such as antimony trioxide, aluminum hydroxide and magnesium hydroxide; coloring such as titanium oxide and carbon black Agents and the like.
These organic and inorganic additives may be blended singly or in combination of two or more, or one or more of organic functional additives and inorganic One or more of these functional additives may be combined and blended.
[0020]
The blending amount of the organic or inorganic functional additive is not particularly limited, and may be appropriately selected according to the use of the resin composition of the present invention or according to the blending purpose of each additive.
For example, when the resin composition of the present invention is used as a layer constituting material (topping agent) in a laminate such as a rubberized cloth, the above antioxidant and ultraviolet absorber are used with respect to 100 parts by weight of the resin component. The light stabilizer may be added in an amount of about 0.05 to 0.3 parts by weight, and the roll lubricity imparting agent (lubricant) may be added in an amount of about 0.2 to 0.7 parts by weight.
[0021]
However, the inorganic functional additive is preferably 1 part by weight or less with respect to 100 parts by weight of the resin component composed of the components (A) and (B).
If the amount of the inorganic additive is more than 1 part by weight, not only the weight of the product sheet or the coating layer is excessive, but the handleability is lowered, and the workability is improved by blending the component (B). (A), (B) at the time of kneading the resin composition of the invention, it is difficult to satisfactorily obtain the effect of preventing oxidation deterioration, roll slippage deterioration, coloring, etc. due to the softening point or melting point drop of the resin component comprising both resin components, In addition, as a result, there may be inconveniences such as lowering the durability and appearance of the product sheet or coating layer.
[0022]
The resin composition of the present invention having the above composition is obtained by using (1) a single-screw or multi-screw extruder equipped with a Henschel mixer, (2) a closed intensive mixer or a closed kneader, etc. A) and (B) components, organic and inorganic additives) can be mixed.
[0023]
For example, in order to obtain the resin composition of the present invention using a closed kneader, as described above, the jacket or rotor of the closed kneader is heated to the softening temperature of TPU with steam or the like, and this is used as a resin component. (A), (B) both components are thrown in.
Since the softening temperature of the component (B) is lower than the TPU of the component (A), when the TPU entangled with the rotor of the closed kneading machine generates heat due to shearing and softens and melts, the component (B) Softening and melting have occurred.
Therefore, if organic or inorganic additives are added almost simultaneously with softening or melting of TPU, or immediately before or after softening or melting, these additives are dispersed rapidly and uniformly in the resin component. At this time, the mixing of the component (A) and the component (B) is also performed quickly and uniformly.
As a result, the TPU is not heated to a temperature equal to or higher than the melting temperature for a long time, and TPU oxidation deterioration, roll slippage deterioration, discoloration, and the like can be satisfactorily prevented.
[0024]
In addition, the laminate of the present invention, such as a rubberized cloth, is provided with a layer made of the above resin composition on at least one side of a fibrous base material, and the above-mentioned only on one side or both sides of the base material. The resin composition layer may be provided, or a rubber layer may be provided on one side and the resin composition layer described above may be provided on the other side.
Among these, the rubberized cloth provided with the rubber layer on one surface and the resin composition layer on the other surface is produced, for example, as follows.
First, a rubber composition is rolled and pressure-bonded on one surface of a fibrous base material by calendering and vulcanized.
Next, the above-described resin composition of the present invention is rolled and pressure-bonded to the other surface by calendering. This resin composition layer does not require vulcanization and is annealed (heat cured) as necessary.
The annealing conditions are not particularly limited, but in general, the annealing conditions may be maintained at a normal pressure of about 100 to 130 ° C. for about 0.5 to 2 hours.
[0025]
Examples 1-2 , 7-9, Comparative Examples 1-6
[Preparation of TPU composition]
The components shown in Tables 1 and 2 were blended in the formulations shown in Tables 1 and 2 and introduced into a Brabender machine in which the jacket and rotor temperature were set to 70 ° C., kneaded, and each formulation was evaluated.
The machine volume ratio at this time was 60% in terms of the resin component amount.
[0026]
The above evaluation was carried out by measuring the time until the resin entangled with the rotor and the torque starts to increase (kneading time (1)) and the time until heat is generated and the torque is stabilized (kneading time (2)). . These results are shown in Tables 1 and 2. It can be said that both the kneading time (1) and the kneading time (2) are blended in a short time and the workability is good.
Moreover, the state after completion of kneading of each composition was visually observed to observe whether or not there was discoloration. These results are also shown in Tables 1 and 2. If a kneaded state without discoloration can be obtained, it means that uniform kneading has been performed quickly, and if there is discoloration, it means that kneading has been performed at a considerably high temperature.
[0027]
[Preparation of film]
Using the TPU composition prepared as described above, a TPU film having a thickness of 0.3 mm was formed on a release paper by a calendar method.
The end of this film was bent to a width of 1 cm, the bent portion was fused with a high frequency welder, and the range of frequencies that can be fused with high frequency was evaluated according to the following criteria. The results are shown in Tables 1 and 2 below. It was.
[0028]
○: High frequency fusion is possible in a fairly wide range of frequencies ×: High frequency fusion is possible only in a specific narrow range of frequencies [0029]
(Preparation of laminate)
By calendering, a layer of TPU composition prepared as described above is formed on one surface of a nylon base fabric (420 denier × 420 denier / 40 × 40 plain weave) via a polyurethane adhesive. It formed so that it might become 2 mm.
For this laminate, as in the case of the above film, the end portion was bent at a width of 1 cm, and the range of frequencies that can be fused by high frequency was evaluated according to the above criteria, and the results are shown in Table 1 and Table 2. It was.
[0030]
In Table 1 and Table 2,
TPU: Thermoplastic polyurethane elastomer (trade name “Pandex T8175N” manufactured by DIC Byer)
EVA (1): E-VA copolymer (VA: 40% by weight)
EVA (2): E-VA copolymer (VA: 26% by weight)
EVACO: E-VA-CO terpolymer (trade name “Elvalloy 741” manufactured by DuPont Dow Elastomer Co., Ltd.)
EMACO: E-MA-CO terpolymer (trade name “Elvalloy 4051” manufactured by DuPont Dow Elastomer Co., Ltd.)
EAAECO; E-AAE-CO terpolymer (trade name “Elvalloy HP443” manufactured by DuPont Dow Elastomer Co., Ltd.)
EAEMAH: E-AE-MAH terpolymer (trade name “Bondaine” manufactured by Sumitomo Chemical Co., Ltd.)
EGMA: E-GMA copolymer (trade name “Bond First E” manufactured by Sumitomo Chemical Co., Ltd.)
LLDPE: Low density polyethylene (Density: 0.89)
EMMA: E-MMA (ethylene-methyl methacrylate)
Antioxidant: Hindered phenol (trade name “Irganox 1010” manufactured by Ciba Geigy)
UV absorber: benzotriazole (trade name “Tinuvin 327” manufactured by Ciba Geigy)
Light stabilizer: hindered amine (trade name “Sanol LS770” manufactured by Sankyo)
Adhesion inhibitor: calcium carbonate kneading time {circle over (1)}, {circle around (2)} seconds high frequency fusion property {circle around (1)}: high frequency fusion property of film high frequency fusion property {circle around (2)}: means high frequency fusion property of laminate.
[0031]
[Table 1]
[Table 2]
【The invention's effect】
According to the resin composition of the present invention, the following effects can be obtained.
(1) Since the resin component can be kneaded at a relatively low temperature and quickly at the time of kneading the resin composition, problems such as oxidative deterioration, roll slippage reduction, and coloring of the resin composition at the time of kneading are eliminated. It can be avoided.
(2) As a result of the above, a product (film, laminate, etc.) obtained from the resin composition of the present invention has very good processability.
Claims (3)
（Ａ）熱可塑性ポリウレタンエラストマーと、
（Ｂ）（Ｂ１）エチレン−酢酸ビニル−一酸化炭素三元共重合体と酢酸ビニルモノマー部が４０重量％以上のエチレン−酢酸ビニル共重合体のいずれか一方または双方、
若しくは
（Ｂ２）エチレン−酢酸ビニル−一酸化炭素三元共重合体とエチレン−メタクリル酸エステル−一酸化炭素三元共重合体
を含む熱可塑性ポリウレタンエラストマー組成物層を設けてなり、優れた高周波融着性を有することを特徴とする積層体。On at least one side of the fibrous base material,
(A) a thermoplastic polyurethane elastomer;
(B) (B1) One or both of an ethylene-vinyl acetate-carbon monoxide terpolymer and an ethylene-vinyl acetate copolymer having a vinyl acetate monomer portion of 40% by weight or more,
Or (B2) an ethylene - vinyl acetate - carbon monoxide terpolymer and an ethylene - methacrylic acid ester - carbon monoxide terpolymer will be provided including thermoplastic polyurethane elastomer composition layer, excellent high-frequency A laminate having a fusibility.
（Ａ）熱可塑性ポリウレタンエラストマーと、
（Ｂ）（Ｂ１）エチレン−酢酸ビニル−一酸化炭素三元共重合体と酢酸ビニルモノマー部が４０重量％以上のエチレン−酢酸ビニル共重合体のいずれか一方または双方、
若しくは
（Ｂ２）エチレン−酢酸ビニル−一酸化炭素三元共重合体とエチレン−メタクリル酸エステル−一酸化炭素三元共重合体
を混合し、該混合物の軟化、溶融と略同時に、あるいは軟化、溶融の直前または直後に、
（Ｃ）有機系又は／及び無機系の機能性添加剤を混合する熱可塑性ポリウレタンエラストマー組成物を設けてなり、優れた高周波融着性を有することを特徴とする積層体の製造方法。 On at least one side of the fibrous base material,
(A) a thermoplastic polyurethane elastomer;
(B) (B1) One or both of an ethylene-vinyl acetate-carbon monoxide terpolymer and an ethylene-vinyl acetate copolymer having a vinyl acetate monomer portion of 40% by weight or more,
Or (B2) An ethylene-vinyl acetate-carbon monoxide terpolymer and an ethylene-methacrylate-carbon monoxide terpolymer are mixed, and the mixture is softened or melted almost simultaneously, or softened or melted. Immediately before or after
(C) organic or / and be provided with inorganic functional additives thermoplastic polyurethane elastomer composition you mixed excellent method for producing a laminate characterized by having a high frequency fusibility.
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| US20120088054A1 (en) | 2010-03-04 | 2012-04-12 | Avery Dennison Corporation | Non-PVC Film and Non-PVC Film Laminate |
| US9752022B2 (en) | 2008-07-10 | 2017-09-05 | Avery Dennison Corporation | Composition, film and related methods |
| PL2817157T3 (en) | 2012-02-20 | 2016-12-30 | Multilayer film for multi-purpose inkjet systems | |
| MX2016007964A (en) | 2013-12-30 | 2016-09-09 | Avery Dennison Corp | Polyurethane protective film. |
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