JP4413640B2 - Thermoplastic polyurethane composition for calendering and film / sheet comprising the same - Google Patents
Thermoplastic polyurethane composition for calendering and film / sheet comprising the same Download PDFInfo
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- JP4413640B2 JP4413640B2 JP2004039643A JP2004039643A JP4413640B2 JP 4413640 B2 JP4413640 B2 JP 4413640B2 JP 2004039643 A JP2004039643 A JP 2004039643A JP 2004039643 A JP2004039643 A JP 2004039643A JP 4413640 B2 JP4413640 B2 JP 4413640B2
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- Prior art keywords
- thermoplastic polyurethane
- mass
- calendering
- film
- parts
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- 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.)
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- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims description 51
- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims description 48
- 239000000203 mixture Substances 0.000 title claims description 32
- 238000003490 calendering Methods 0.000 title claims description 31
- 229920005989 resin Polymers 0.000 claims description 32
- 239000011347 resin Substances 0.000 claims description 32
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 24
- -1 diisocyanate compound Chemical class 0.000 claims description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 18
- 229920005862 polyol Polymers 0.000 claims description 14
- 150000003077 polyols Chemical class 0.000 claims description 13
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 11
- 229920000570 polyether Polymers 0.000 claims description 11
- 150000007524 organic acids Chemical class 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 7
- 239000000178 monomer Substances 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 230000000903 blocking effect Effects 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 8
- 238000005452 bending Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 229920003002 synthetic resin Polymers 0.000 description 6
- 239000000057 synthetic resin Substances 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 230000000379 polymerizing effect Effects 0.000 description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 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
- 238000013329 compounding Methods 0.000 description 4
- 239000010985 leather Substances 0.000 description 4
- 239000004611 light stabiliser Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 230000002087 whitening effect Effects 0.000 description 4
- 239000003242 anti bacterial agent Substances 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 238000010410 dusting Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004358 Butane-1, 3-diol Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- UYFMQPGSLRHGFE-UHFFFAOYSA-N cyclohexylmethylcyclohexane;isocyanic acid Chemical class N=C=O.N=C=O.C1CCCCC1CC1CCCCC1 UYFMQPGSLRHGFE-UHFFFAOYSA-N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 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
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- NXFQHRVNIOXGAQ-YCRREMRBSA-N nitrofurantoin Chemical compound O1C([N+](=O)[O-])=CC=C1\C=N\N1C(=O)NC(=O)C1 NXFQHRVNIOXGAQ-YCRREMRBSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 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
- 239000002994 raw material Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、カレンダー加工性が優れた熱可塑性ポリウレタン組成物に関し、またこれをカレンダー成形して得たブロッキングしないフィルム・シートに関する。 The present invention relates to a thermoplastic polyurethane composition having excellent calendar processability, and to a non-blocking film / sheet obtained by calendering the same.
従来より、熱可塑性ポリウレタンは、高弾性率を有し、耐屈曲性、耐摩耗性に優れ、高周波ウェルダー加工が可能であり、耐油性がよいなどの特性を有するため、そのフィルム・シートは、文具、包装材、床ずれ防止エアーマットや自動車の車両内装材の素材として、或は袋物や家具の表皮材などの合成樹脂レザーの素材として多用されている。熱可塑性ポリウレタンのフィルム・シートは、カレンダー成形で製造するのが効率的である。しかし、熱可塑性ポリウレタンはカレンダー成形時の加工温度幅が非常に小さく、連続生産が難しく、生産速度が遅い問題点がある。すなわち、加工温度が高いと、粘着性が強くなり、ロールに粘着し成形が円滑に行なえない支障が生じる。また、加工温度を下げると、溶融しにくくなり、均一な製品が得られない支障が生じる。 Conventionally, thermoplastic polyurethane has a high elastic modulus, excellent bending resistance, wear resistance, high frequency welder processing, and good oil resistance. It is widely used as a material for stationery, packaging materials, floor mats to prevent floor slips, and automobile interior materials, or as a material for synthetic resin leather such as bags and furniture skins. It is efficient to manufacture a thermoplastic polyurethane film or sheet by calendering. However, thermoplastic polyurethane has a problem that the processing temperature range at the time of calendar molding is very small, continuous production is difficult, and production speed is slow. That is, when the processing temperature is high, the adhesiveness becomes strong, and there arises a problem that it cannot adhere smoothly to the roll and cannot be molded smoothly. Further, when the processing temperature is lowered, it becomes difficult to melt and a problem that a uniform product cannot be obtained occurs.
熱可塑性ポリウレタンのカレンダー加工性を向上させるためには、従来から種々の手段が提案されている。例えば、カレンダー加工に適する組成物として、特定の熱可塑性ポリウレタンに高級脂肪酸と脂肪族ポリオ−ルとの縮合物を配合した熱可塑性ポリウレタン組成物が提案されている（特許文献１）。また、熱可塑性ポリウレタン樹脂と、脂肪酸とアルコールとのエステル化合物で、その脂肪酸の炭素数が２２以上又はアルコールの炭素数が２２以上であるエステル化合物とからなる熱可塑性ポリウレタン組成物が提案されている（特許文献２） In order to improve the calenderability of thermoplastic polyurethane, various means have been conventionally proposed. For example, as a composition suitable for calendering, a thermoplastic polyurethane composition in which a condensation product of a higher fatty acid and an aliphatic polyol is blended with a specific thermoplastic polyurethane has been proposed (Patent Document 1). In addition, a thermoplastic polyurethane composition comprising a thermoplastic polyurethane resin and an ester compound of a fatty acid and an alcohol, the fatty acid having 22 or more carbon atoms or an alcohol having 22 or more carbon atoms has been proposed. (Patent Document 2)
また、熱可塑性ポリウレタンの成形加工温度は、熱可塑性ポリウレタンの加水分解が進む温度域であるため、空気と接触する雰囲気下で行なうカレンダー加工は困難で、高分子量でショアＡ硬度９０以上の粘着性の低いものに限られていた。そこで、ショアＡ硬度９０以下の熱可塑性ポリウレタン或いは熱可塑性ポリウレタンを主体とする他の樹脂例えばアクリル系軟質樹脂との混合樹脂をも、カレンダーで円滑に且つ高品質なシートに成形できるようにするため、メラミンシアヌレートを配合することが提案されている（特許文献３）。
本発明は、かかる事情に鑑みなされたもので、カレンダー加工性に優れた熱可塑性ポリウレタン組成物を提供すること、更に粉振りしなくてもブロッキングすることのなく、取り扱い易い熱可塑性ポリウレタンフィルム・シートを提供することを目的とする。 The present invention has been made in view of such circumstances, and provides a thermoplastic polyurethane composition excellent in calendar workability, and further, is easy to handle without blocking even without dusting. The purpose is to provide.
すなわち、本発明は、ポリエーテル系ポリオールとジイソシアネート化合物を反応させて得た熱可塑性ポリウレタン１００質量部に対し、平均粒径０．３〜１．５μｍの炭酸カルシウム１〜４０質量部及び有機酸金属塩０．１〜１．５質量部を配合したことを特徴とするカレンダー加工用熱可塑性ポリウレタン組成物である。上記のポリエーテル系ポリオールとジイソシアネート化合物を反応させて得た熱可塑性ポリウレタンは、ポリエーテル系ポリオールとジイソシアネート化合物を反応させて得た熱可塑性ポリウレタン５０〜９５質量％と、硬度がショアＡで５０〜８０のアクリル系軟質樹脂５０〜５質量％からなる混合樹脂であってもよい。また本発明は、上記のカレンダー加工用熱可塑性ポリウレタン組成物をカレンダー成形してなるフィルム・シートである。
That is, in the present invention, 1 to 40 parts by mass of calcium carbonate having an average particle size of 0.3 to 1.5 μm and an organic acid metal with respect to 100 parts by mass of thermoplastic polyurethane obtained by reacting a polyether polyol and a diisocyanate compound. It is a thermoplastic polyurethane composition for calendering, characterized by blending 0.1 to 1.5 parts by weight of salt. The thermoplastic polyurethane obtained by reacting the polyether polyol and the diisocyanate compound is 50 to 95% by mass of the thermoplastic polyurethane obtained by reacting the polyether polyol and the diisocyanate compound, and the hardness is 50 to 50 on Shore A. The mixed resin which consists of 50-5 mass% of 80 acrylic soft resins may be sufficient. The present invention is also a film / sheet formed by calendering the above-mentioned calendered thermoplastic polyurethane composition.
本発明のカレンダー加工用熱可塑性ポリウレタン組成物は、カレンダー加工性に優れている。また、カレンダー成形したフィルム・シートは、通常ブロッキング防止のために行なっている巻取時のいわゆる粉振りをしなくても、ブロッキングすることなく、解反が円滑にでき取り扱いが容易である。 The thermoplastic polyurethane composition for calendering of the present invention is excellent in calendering properties. In addition, the calendered film or sheet can be smoothly handled and easily handled without blocking without so-called dusting during winding, which is usually performed for preventing blocking.
本発明で用いる熱可塑性ポリウレタンは、カレンダー加工可能な熱可塑性ポリウレタンである。この熱可塑性ポリウレタンは、ジイソシアネート化合物と、ヒドロキシル基を２個以上有する化合物とを反応させて得ることができる。中でも、長鎖ポリオール、ジイソシアネート、鎖伸長剤から構成された、いわゆるソフトセグメントとハードセグメントからなるポリウレタン系熱可塑性エラストマー（ＴＰＵ）が好ましく使用できる。自動車の車両内装材、袋物素材、家具の表皮材に用いられる合成樹脂レザーにおいては、その合成樹脂層の好ましい硬度は、一般に、ショアＡで６０〜８０、より好ましくは６０〜７０とされている。従って、この場合の上記の熱可塑性ポリウレタンとしては、他の添加物と配合物し、カレンダー加工でシートに形成したとき、ショアＡで６０〜８０の硬度になるようなものが使用される。 The thermoplastic polyurethane used in the present invention is a calenderable thermoplastic polyurethane. This thermoplastic polyurethane can be obtained by reacting a diisocyanate compound with a compound having two or more hydroxyl groups. Among these, a polyurethane-based thermoplastic elastomer (TPU) composed of a so-called soft segment and hard segment composed of a long-chain polyol, diisocyanate, and a chain extender can be preferably used. In a synthetic resin leather used for automobile interior materials, bag materials, and furniture skin materials for automobiles, the preferred hardness of the synthetic resin layer is generally 60 to 80, more preferably 60 to 70 for Shore A. . Therefore, as the above-mentioned thermoplastic polyurethane in this case, those having a hardness of 60 to 80 in Shore A when blended with other additives and formed into a sheet by calendering are used.
熱可塑性ポリウレタンを合成するためのジイソシアネート化合物としては、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、ナフタリンジイソシアネート、トリジンジイソシアネート、ヘキサメチレンジイソシアネート、キシリレンジイソシアネート、水添キシリレンジイソシアネート、水添ジシクロヘキシルメタンジイソシアネート、イソホロンジイソイアネートなどが用いられる。 Diisocyanate compounds for the synthesis of thermoplastic polyurethanes include tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, tolidine diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated dicyclohexylmethane diisocyanate, isophorone diisocyanate. Nate is used.
また、ヒドロキシル基を２個以上有する化合物としては、アジピン酸、フタル酸等の二塩基酸とエチレングリコール、１，４−ブタンジオール等のグリコールとの縮合反応物であるポリエステル系ポリオール；エチレンカーボネート等のカーボネートとグリコールとの反応物であるポリカーボネート系ポリオール；ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール、ポリエチレングリコール−ポリプロピレングリコール等のポリエーテル系ポリオール等が挙げられるが、本発明では、ポリエーテル系ポリオールを用いる。本発明のフィルム・シートにおいては、その物性からポリエーテル系ポリオールを用いるのが好ましい。また、ポリエーテル系ポリオールを原料とする熱可塑性ポリウレタンは、耐老化性、カレンダー加工性が良いので、この観点からも好ましい。
Examples of the compound having two or more hydroxyl groups include polyester polyols which are condensation reaction products of dibasic acids such as adipic acid and phthalic acid and glycols such as ethylene glycol and 1,4-butanediol; ethylene carbonate and the like polycarbonate-based polyol is a reaction product of a carbonate and a glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene glycol - although polyether polyols such as polypropylene glycol, in the present invention, polyether polyols Is used. In the film and sheet of the present invention, it is preferable to use a polyether polyol because of its physical properties. In addition, a thermoplastic polyurethane using a polyether-based polyol as a raw material is preferable from this viewpoint because it has good aging resistance and calendar processability.
上記の鎖伸長剤としては、エチレングリコール、１，２−プロピレングリコール、１，３−プロピレングリコール、ブタン１，２ジオール、ブタン１，３ジオール、ブタン１，４ジオール、ブタン２，３ジオール、ヘキサンジオールなどの低分子多価アルコール、或いはジアミン、水が用いられる。 As the chain extender, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, butane 1,2 diol, butane 1,3 diol, butane 1,4 diol, butane 2,3 diol, hexane A low molecular polyhydric alcohol such as diol, diamine, or water is used.
本発明のカレンダー加工性の向上は、上記のポリエーテル系ポリオールとジイソシアネート化合物を反応させて得た熱可塑性ポリウレタンを主体とし、これに他の樹脂を配合した混合樹脂にも適用できる。この他の樹脂としてアクリル系軟質樹脂、ＡＢＳ樹脂、ＭＢＳ樹脂などを用いることができる。特に、熱可塑性ポリウレタン５０〜９５質量％とアクリル系軟質樹脂５０〜５質量％からなる混合樹脂が好ましく用いることができる。
The improvement of the calender processability of the present invention can also be applied to a mixed resin composed mainly of a thermoplastic polyurethane obtained by reacting the above polyether polyol and a diisocyanate compound, and blended with another resin. As other resins, acrylic soft resins, ABS resins, MBS resins, and the like can be used. In particular, a mixed resin composed of 50 to 95% by mass of thermoplastic polyurethane and 50 to 5% by mass of an acrylic soft resin can be preferably used.
上記のアクリル系軟質樹脂は、常温で軟質ポリ塩化ビニルの如く柔軟性を示す樹脂である。このアクリル系軟質樹脂は、多層構造重合体、すなわち２種以上のアクリル系重合体がコア−シェル型の多層構造を形成している重合体が好ましい。このアクリル系軟質樹脂は、特開平６−２６３８２８号公報、特開平９−１００３８５号公報、特開平１１−７１４３７号公報などに記載されている。このアクリル系軟質樹脂は常温で良好な柔軟性を示し、屈曲耐久性を有し、耐候性に優れている。そして、硬度がショアＡで５０〜８０、なかんずく５５〜６５のものが好ましく用いられる。 The acrylic soft resin is a resin exhibiting flexibility like soft polyvinyl chloride at room temperature. The acrylic soft resin is preferably a multilayer structure polymer, that is, a polymer in which two or more kinds of acrylic polymers form a core-shell type multilayer structure. This acrylic soft resin is described in JP-A-6-263828, JP-A-9-100325, JP-A-11-71437, and the like. This acrylic soft resin exhibits good flexibility at room temperature, has bending durability, and excellent weather resistance. And a thing with hardness of 50-80 by Shore A, especially 55-65 is used preferably.
本発明で用いるアクリル系軟質樹脂の一例を示す。炭素数１〜１２のアルキル基を持つ少なくとも一種のアクリル酸アルキルエステル３０〜９９．９質量％、炭素数１〜８のアルキル基を持つ少なくとも一種のメタクリル酸アルキルエステル０〜７０質量％、共重合可能な不飽和単量体０〜３０質量％、多官能架橋性単量体及び／又は多官能性グラフト単量体０．１〜１０質量％からなる単量体混合物を重合してなるＴｇが３０℃以下である少なくとも１層の重合体層［Ａ］１０〜９０質量部と、炭素数１〜１２のアルキル基を持つ少なくとも一種のアクリル酸アルキルエステル３０〜９９質量％、炭素数１〜８のアルキル基を持つ少なくとも一種のメタクリル酸アルキルエステル１〜７０質量％、共重合可能な不飽和単量体０〜３０質量％からなる単量体混合物を重合してなるＴｇが−２０〜５０℃である少なくとも１層の重合体層［Ｂ］９０〜１０質量部との組合せからなる多層構造重合体であり、且つ最外層が重合体層［Ｂ］であるアクリル系軟質多層構造樹脂である。 An example of the acrylic soft resin used in the present invention is shown. 30 to 99.9% by mass of at least one alkyl acrylate ester having 1 to 12 carbon atoms, 0 to 70% by mass of at least one alkyl methacrylate having 1 to 8 alkyl groups, copolymerization Tg formed by polymerizing a monomer mixture consisting of 0 to 30% by mass of a possible unsaturated monomer, 0.1 to 10% by mass of a polyfunctional crosslinkable monomer and / or a polyfunctional graft monomer. 10 to 90 parts by mass of at least one polymer layer [A] having a temperature of 30 ° C. or less, 30 to 99% by mass of at least one alkyl acrylate ester having an alkyl group having 1 to 12 carbon atoms, and 1 to 8 carbon atoms. Tg formed by polymerizing a monomer mixture consisting of 1 to 70% by mass of an alkyl ester having at least one alkyl group and 0 to 30% by mass of a copolymerizable unsaturated monomer is -20 An acrylic soft multi-layer structure resin comprising a combination of 90 to 10 parts by mass of at least one polymer layer [B] at 50 ° C., and the outermost layer being a polymer layer [B]. is there.
アクリル系軟質樹脂の他の例を示す。炭素数１〜８のアルキル基を持つアクリル酸アルキルエステル６０〜９９．５質量％、共重合可能ビニル基を１個有する単官能性単量体０〜３９．５質量％、及びビニル基又はビニリデン基を少なくとも２個有する多官能性単量体０．５〜５質量％を重合して得られるゴム層３０〜８０質量部と、メタアクリル酸メチル４０〜１００質量％、炭素数１〜８のアルキル基を持つアクリル酸アルキルエステル０〜６０質量％、及び共重合可能なビニル基又はビニリデン基を有する単量体０〜２０質量％を重合して得られる硬質樹脂層２０〜７０質量部とから構成され、且つ最外層が硬質樹脂層であるアクリル系軟質多層構造樹脂である。この樹脂は滑剤を添加すると、カレンダー成形が円滑になる。 Another example of the acrylic soft resin is shown. 60 to 99.5% by mass of an acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms, 0 to 39.5% by mass of a monofunctional monomer having one copolymerizable vinyl group, and a vinyl group or vinylidene 30 to 80 parts by mass of a rubber layer obtained by polymerizing 0.5 to 5% by mass of a polyfunctional monomer having at least two groups, 40 to 100% by mass of methyl methacrylate, and 1 to 8 carbon atoms From 20 to 70 parts by mass of a hard resin layer obtained by polymerizing 0 to 60% by mass of an alkyl acrylate ester having an alkyl group and 0 to 20% by mass of a monomer having a copolymerizable vinyl group or vinylidene group It is an acrylic soft multilayer structure resin that is configured and whose outermost layer is a hard resin layer. When a lubricant is added to this resin, calendar molding becomes smooth.
更に、アクリル系軟質樹脂の他の例を示す。（Ａ）メチルメタクリレート８０〜９８．９９質量％、炭素数１〜８のアルキル基を持つアクリル酸アルキルエステル１〜２０質量％、多官能性グラフト剤０．０１〜１質量％及び多官能性架橋剤０〜０．５質量％からなる単量体混合物を重合してなる最内層の硬質重合体層５〜３０質量部；（Ｂ）炭素数１〜８のアルキル基を持つアクリル酸アルキルエステル７０〜９９．５質量％、メチルメタクリレート０〜３０質量％、多官能性グラフト剤０．５〜５質量％及び多官能性架橋剤０〜５質量％からなる単量体混合物を重合してなる中間層の硬質重合体層２０〜４５質量部；（Ｃ）メチルメタクリレート９０〜９９質量％及び炭素数１〜８のアルキル基を持つアクリル酸アルキルエステル１０〜１質量％からなる単量体混合物を重合してなる最外層の硬質重合体層５０〜７５質量部からなり、平均粒度が０．０１〜０．３μｍのアクリル系軟質多層構造樹脂である。 Furthermore, other examples of acrylic soft resins are shown. (A) Methyl methacrylate 80 to 98.9% by mass, 1 to 20% by mass of an acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms, 0.01 to 1% by mass of a multifunctional grafting agent, and multifunctional crosslinking 5-30 parts by mass of the innermost hard polymer layer obtained by polymerizing a monomer mixture comprising 0-0.5% by mass of the agent; (B) alkyl acrylate 70 having an alkyl group having 1-8 carbon atoms -99.5% by mass, methyl methacrylate 0-30% by mass, polyfunctional grafting agent 0.5-5% by mass and polyfunctional crosslinking agent 0-5% by mass 20 to 45 parts by mass of a hard polymer layer; (C) a monomer mixture consisting of 90 to 99% by mass of methyl methacrylate and 10 to 1% by mass of an alkyl acrylate ester having an alkyl group having 1 to 8 carbon atoms. Do it It consists outermost hard polymer layer 50 to 75 parts by weight, an average particle size of the acrylic soft multilayer resin 0.01 to 0.3 [mu] m.
本発明において、熱可塑性ポリウレタン１００質量部に対し、平均粒径０．３〜１．５μｍの炭酸カルシウム１〜４０質量部及び有機酸金属塩０．１〜１．５質量部を配合することにより熱可塑性ポリウレタン或いは熱可塑性ポリウレタン樹脂を主体とする樹脂混合物のカレンダー加工性が向上し、生産性を上げることができる。そして、カレンダー成形して得られるフィルム・シートは、通常ブロッキング防止のために行なっている巻取時のいわゆる粉振りをしなくても、ブロッキングすることなく、解反しやすく取り扱いが容易である。炭酸カルシウムは平均粒径０．３〜１．５μｍの範囲のものを使用する必要があり、この範囲を外れると、本発明の目的、効果を達成することができない。炭酸カルシウムの特に好ましい平均粒径は０．５〜１．０μｍの範囲である。また、炭酸カルシウムの配合量は、熱可塑性ポリウレタン１００質量部に対し、１〜２０質量部、好ましくは５〜１５質量部である。 In the present invention, by blending 1 to 40 parts by weight of calcium carbonate having an average particle size of 0.3 to 1.5 μm and 0.1 to 1.5 parts by weight of organic acid metal salt with respect to 100 parts by weight of thermoplastic polyurethane. The calendar processability of a resin mixture mainly composed of thermoplastic polyurethane or thermoplastic polyurethane resin is improved, and productivity can be increased. The film and sheet obtained by calendering are easy to disassemble and easy to handle without blocking without so-called dusting during winding, which is usually performed to prevent blocking. It is necessary to use calcium carbonate having an average particle diameter in the range of 0.3 to 1.5 μm. A particularly preferred average particle diameter of calcium carbonate is in the range of 0.5 to 1.0 μm. Moreover, the compounding quantity of calcium carbonate is 1-20 mass parts with respect to 100 mass parts of thermoplastic polyurethane, Preferably it is 5-15 mass parts.
また、本発明では、炭酸カルシウムと共に有機酸金属塩を配合する必要がある。炭酸カルシウム単独でも、また有機酸金属塩単独でもカレンダー加工性を十分に向上させることはできない。有機酸金属塩としては、脂肪酸金属塩、芳香族カルボン酸金属塩が用いられる。この脂肪酸としてはステアリン酸、パルミチン酸、ラウリン酸などの飽和脂肪酸、オレイン酸、リノール酸などの不飽和脂肪酸が挙げられ、芳香族カルボン酸としては安息香酸などが挙げられる。また塩の金属としてはバリウム、亜鉛、カルシウムなどが挙げられる。有機酸金属塩の配合量は、熱可塑性ポリウレタン１００質量部に対し、０．１〜１．５質量部、好ましくは０．４〜１質量部である。 Moreover, in this invention, it is necessary to mix | blend organic acid metal salt with calcium carbonate. Calender workability cannot be sufficiently improved even with calcium carbonate alone or with an organic acid metal salt alone. As the organic acid metal salt, a fatty acid metal salt or an aromatic carboxylic acid metal salt is used. Examples of the fatty acid include saturated fatty acids such as stearic acid, palmitic acid, and lauric acid, and unsaturated fatty acids such as oleic acid and linoleic acid, and examples of the aromatic carboxylic acid include benzoic acid. Examples of the salt metal include barium, zinc, and calcium. The compounding quantity of organic acid metal salt is 0.1-1.5 mass parts with respect to 100 mass parts of thermoplastic polyurethane, Preferably it is 0.4-1 mass part.
また、本発明のカレンダー加工用熱可塑性ポリウレタン組成物には、（メタ）アクリル系重合体を配合することによってカレンダー加工時の溶融張力が調整でき、カレンダー加工を円滑にすることができる。この（メタ）アクリル系重合体は、例えば、メタクリル酸メチル５０〜９０質量％及びこれと共重合可能な他のエチレン系不飽和単量体５０〜５質量％を共重合して得られる分子量５０〜５００万の共重合体が好ましい。他のエチレン系不飽和単量体は、例えば、炭素数２〜１８のアルコールのメタクリル酸エステル、炭素数２〜１８のアルコールのアクリル酸エステル、スチレン、α−メチルスチレン、アクリロニトリル、マレイン酸、イタコン酸などである。（メタ）アクリル系重合体の配合量は、熱可塑性ポリウレタン或いは熱可塑性ポリウレタンを主体とする混合樹脂１００質量部に対し０〜３０質量部、好ましくは１〜１０質量部である。 In addition, by blending a (meth) acrylic polymer with the calendering thermoplastic polyurethane composition of the present invention, the melt tension at the time of calendering can be adjusted, and the calendering can be made smooth. The (meth) acrylic polymer has, for example, a molecular weight of 50 obtained by copolymerizing 50 to 90% by mass of methyl methacrylate and 50 to 5% by mass of another ethylenically unsaturated monomer copolymerizable therewith. ~ 5 million copolymers are preferred. Other ethylenically unsaturated monomers include, for example, methacrylic acid esters of alcohols having 2 to 18 carbon atoms, acrylic acid esters of alcohols having 2 to 18 carbon atoms, styrene, α-methylstyrene, acrylonitrile, maleic acid, itacon. Such as acids. The compounding amount of the (meth) acrylic polymer is 0 to 30 parts by mass, preferably 1 to 10 parts by mass with respect to 100 parts by mass of thermoplastic polyurethane or a mixed resin mainly composed of thermoplastic polyurethane.
更に、本発明のカレンダー加工用熱可塑性ポリウレタン組成物には、酸化アンチモン、コロイド状シリカ、ケイ酸マグネシウム、水酸化マグネシウムどの無機物質粉末を配合することにより、カレンダー加工時の粘着性を低下させて、カレンダー加工を円滑にすることができる。無機物質粉末の配合量は、熱可塑性ポリウレタン或いは熱可塑性ポリウレタンを主体とする混合樹脂１００質量部に対し０〜３０質量部、好ましくは５〜２０質量部である。 Furthermore, the thermoplastic polyurethane composition for calendering of the present invention is blended with an inorganic substance powder such as antimony oxide, colloidal silica, magnesium silicate, magnesium hydroxide to reduce the adhesiveness during calendering. , Calendar processing can be made smooth. The compounding amount of the inorganic substance powder is 0 to 30 parts by mass, preferably 5 to 20 parts by mass with respect to 100 parts by mass of thermoplastic polyurethane or a mixed resin mainly composed of thermoplastic polyurethane.
本発明のカレンダー加工用熱可塑性ポリウレタン組成物には、更に必要に応じて、通常合成樹脂の配合に使用される滑剤、紫外線吸収剤、光安定剤、顔料、抗菌剤などが配合されていてもよい。滑剤にはポリエチレンワックス、ステアリン酸、アルキレンビス脂肪酸アミドなどが用いられる。紫外線吸収剤としては２−（２’−ヒドロキシ−５’−メチルフェニル）ベンゾトリアゾールなどのベンゾトリアゾール系紫外線吸収剤等が用いられる。光安定剤としてはビス−（２，２，６，６−テトラメチル−４−ピペリジル）セバケートなどのヒンダードアミン系光安定剤等が用いられる。抗菌剤としては銀系無機抗菌剤などが用いられる。 The calendering thermoplastic polyurethane composition of the present invention may further contain a lubricant, an ultraviolet absorber, a light stabilizer, a pigment, an antibacterial agent, etc., which are usually used for blending synthetic resins, if necessary. Good. For the lubricant, polyethylene wax, stearic acid, alkylenebisfatty acid amide, etc. are used. As the ultraviolet absorber, a benzotriazole-based ultraviolet absorber such as 2- (2'-hydroxy-5'-methylphenyl) benzotriazole is used. As the light stabilizer, hindered amine light stabilizers such as bis- (2,2,6,6-tetramethyl-4-piperidyl) sebacate are used. As the antibacterial agent, a silver-based inorganic antibacterial agent or the like is used.
本発明のカレンダー加工用熱可塑性ポリウレタン組成物は、通常使用されているカレンダー装置を用いてフィルム・シートに成形でき、高品質のフィルム・シートを得ることができる。そしてカレンダー加工により得られたフィルム・シートは種々の製品の素材として、例えば文具、包装材、床ずれ防止エアーマットなどの素材として有用である。また、このフィルム・シート自体が成形材料として用いられ、真空成形など二次成形して製品とされる。また、このフィルム・シートを基材と接着剤を用いるなどして積層して合成樹脂レザーにすることができる。自動車の車両内装材、袋物素材、家具の表皮材に用いられる合成樹脂レザーにおいては、そのフィルム・シートの硬度は、ショアＡで６０〜８０が好ましく、より好ましくは６０〜７０である。また、本発明の組成物をカレンダー加工してフィルム・シートは、一般的なウレタン系樹脂又はアクリル系樹脂をバインダーに用いた艶調整剤やインキとの親和性がよいため、この点からも利用性が大きい。 The thermoplastic polyurethane composition for calendering of the present invention can be formed into a film or sheet using a commonly used calendering device, and a high-quality film or sheet can be obtained. Films and sheets obtained by calendering are useful as materials for various products, such as stationery, packaging materials, and floor slip prevention air mats. Further, the film / sheet itself is used as a molding material, and is formed into a product by secondary molding such as vacuum molding. Further, the film / sheet can be laminated by using a base material and an adhesive to form a synthetic resin leather. In a synthetic resin leather used for automobile interior materials, bag materials, and furniture skin materials for automobiles, the hardness of the film / sheet is preferably 60 to 80 on Shore A, more preferably 60 to 70. In addition, the composition of the present invention is calendered and the film / sheet is also used from this point because it has a good affinity with gloss adjusting agents and inks using a general urethane resin or acrylic resin as a binder. The nature is great.
実施例
次に実施例、比較例を示し、本発明を更に詳しく説明する。
実施例１〜７、比較例１〜４
表１に示す成分、すなわち、熱可塑性ポリウレタン（ＵＥ９０Ａ：三菱化学株式会社製）、アクリル系軟質樹脂（ＳＡ−ＦＸＬ５１３８：ローム・アンド・ハース社製）、炭酸カルシウム（平均粒径０．９７μｍ：日東粉化工業社製ＮＩＴＯＲＥＸ２３Ｐ、平均粒径０．７４μｍ：日東粉化工業社製ＮＩＴＯＲＥＸ３０Ｐ、平均粒径１．５μｍ：白石カルシウム社製ホワイトンＳＳＢ、平均粒径２．１μｍ：日東粉化工業社製ＮＳ−Ａ、平均粒径０．１２μｍ：白石工業社製白艶華ＣＣＲ）、有機酸金属塩（Ｂａ−Ｚｎ脂肪酸塩：旭電化社製ＡＣ−２９４）、高分子アクリル系加工助剤（メタブレンＰ−５３０Ａ：三菱レイヨン株式会社製）、酸化防止剤（フェノール系）、紫外線防止剤（ベンゾトリアゾール系）、光安定剤（ヒンダードアミン系）、ポリエチレンワックス加工助剤、及び顔料を、表１に示す割合(数字は質量部を示す)で配合し、樹脂組成物を作成した。
これらの樹脂配合物について、カレンダー加工性、折り曲げ白化性、スリップ性、ブロッキング性を試験し評価した。その結果も併せて表１に示す。
Examples Next, the present invention will be described in more detail with reference to Examples and Comparative Examples.
Examples 1-7, Comparative Examples 1-4
The components shown in Table 1, namely, thermoplastic polyurethane (UE90A: manufactured by Mitsubishi Chemical Corporation), acrylic soft resin (SA-FXL5138: manufactured by Rohm and Haas), calcium carbonate (average particle size: 0.97 μm: Nitto) NITREX23P manufactured by Flour Industries Co., Ltd., average particle size 0.74 μm: NITREX 30P manufactured by Nitto Flour Industries Co., Ltd., average particle size 1.5 μm: Whiten SSB manufactured by Shiraishi Calcium Co., Ltd. NS-A, average particle size 0.12 μm: White Shiraka CCR manufactured by Shiraishi Kogyo Co., Ltd., organic acid metal salt (Ba-Zn fatty acid salt: AC-294 manufactured by Asahi Denka Co., Ltd.), polymer acrylic processing aid (methabrene P- 530A: manufactured by Mitsubishi Rayon Co., Ltd., antioxidant (phenolic), ultraviolet light inhibitor (benzotriazole), light stabilizer (hindered amine) System), a polyethylene wax processing aid, and a pigment were blended in the proportions shown in Table 1 (numbers indicate parts by mass) to prepare a resin composition.
These resin blends were tested and evaluated for calendering properties, folding whitening properties, slip properties, and blocking properties. The results are also shown in Table 1.
カレンダー加工性は、テストロール（１７０℃）で滑性（粘着性）を評価した。○はロール剥がれが３０分以上良好であった、△はロール剥がれが２０〜３０分で低下した、×は１０分前後でロール剥がれが低下した、を表す。
折り曲げ白化性は、各組成物をカレンダーで厚さ０．３ｍｍのフィルムに成形し、折り曲げて評価した。軟質ポリ塩化ビニルフィルムと同等のものを○とし、やや劣るものを△、大いに劣るものを×と評価した。
スリップ性は、各組成物をカレンダーで厚さ０．３ｍｍのフィルムに成形して評価した。軟質ポリ塩化ビニルフィルムと同等のものを○とし、やや劣るものを△、大いに劣るものを×と評価した。
ブロッキング性は、各組成物をカレンダーで厚さ０．３ｍｍのフィルムに成形し巻取り、その解反性で評価した。軟質ポリ塩化ビニルフィルムと同等のものを○とし、やや劣るものを△、大いに劣るものを×と評価した。
The calendering property was evaluated for lubricity (adhesiveness) with a test roll (170 ° C.). ○ indicates that the roll peeling is good for 30 minutes or more, Δ indicates that the roll peeling is reduced in 20 to 30 minutes, and x indicates that the roll peeling is reduced in about 10 minutes.
Bending whitening property was evaluated by forming each composition into a 0.3 mm thick film with a calender and bending it. A film equivalent to a soft polyvinyl chloride film was evaluated as ◯, a slightly inferior film was evaluated as △, and a very poor film was evaluated as ×.
The slip property was evaluated by molding each composition into a 0.3 mm thick film using a calendar. A film equivalent to a soft polyvinyl chloride film was evaluated as ◯, a slightly inferior film was evaluated as △, and a very poor film was evaluated as ×.
The blocking property was evaluated by the resolving property of each composition formed into a 0.3 mm thick film with a calender and wound. A film equivalent to a soft polyvinyl chloride film was evaluated as ◯, a slightly inferior film was evaluated as △, and a very poor film was evaluated as ×.
表１から分かるように、本発明のカレンダー加工用熱可塑性ポリウレタン組成物である実施例１〜７は、いずれもカレンダー加工性、折り曲げ白化性、スリップ性、ブロッキング性がよかった。しかし、炭酸カルシウムの平均粒径が本発明で規定する範囲より大きい比較例１は折り曲げ白化が大いに劣った。炭酸カルシウムの平均粒径が本発明で規定する範囲より小さい比較例２はカレンダー加工性及びスリップ性が大いに劣った。炭酸カルシウムを配合しない比較例３は、カレンダー加工性、スリップ性及びブロッキング性が大いに劣った。また、有機酸金属塩を配合しない比較例４は、カレンダー加工性が大いに劣った。 As can be seen from Table 1, Examples 1 to 7, which are the thermoplastic polyurethane compositions for calendering of the present invention, all had good calendering properties, bending whitening properties, slip properties, and blocking properties. However, Comparative Example 1 in which the average particle size of calcium carbonate is larger than the range specified in the present invention was greatly inferior in bending whitening. Comparative Example 2 in which the average particle size of the calcium carbonate was smaller than the range specified in the present invention was greatly inferior in calendar workability and slip property. The comparative example 3 which does not mix | blend calcium carbonate was very inferior in calendering property, slip property, and blocking property. Moreover, the comparative example 4 which does not mix | blend organic acid metal salt was inferior in calendar workability.
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