WO2011065433A1 - ポリシロキサン変性ポリヒドロキシポリウレタン樹脂及びその製造方法、該樹脂を用いた感熱記録材料、擬革、熱可塑性ポリオレフィン樹脂表皮材、ウェザーストリップ用材料及びウェザーストリップ - Google Patents
ポリシロキサン変性ポリヒドロキシポリウレタン樹脂及びその製造方法、該樹脂を用いた感熱記録材料、擬革、熱可塑性ポリオレフィン樹脂表皮材、ウェザーストリップ用材料及びウェザーストリップ Download PDFInfo
- Publication number
- WO2011065433A1 WO2011065433A1 PCT/JP2010/071038 JP2010071038W WO2011065433A1 WO 2011065433 A1 WO2011065433 A1 WO 2011065433A1 JP 2010071038 W JP2010071038 W JP 2010071038W WO 2011065433 A1 WO2011065433 A1 WO 2011065433A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin
- polysiloxane
- heat
- modified
- modified polyhydroxypolyurethane
- Prior art date
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 297
- 239000011347 resin Substances 0.000 title claims abstract description 297
- 239000000463 material Substances 0.000 title claims abstract description 179
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 51
- 229920002397 thermoplastic olefin Polymers 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 42
- 239000010985 leather Substances 0.000 title claims abstract description 14
- -1 cyclic carbonate compound Chemical class 0.000 claims abstract description 94
- 150000001875 compounds Chemical class 0.000 claims abstract description 64
- 239000011342 resin composition Substances 0.000 claims abstract description 47
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 116
- 239000010410 layer Substances 0.000 claims description 63
- 239000002649 leather substitute Substances 0.000 claims description 61
- 239000001569 carbon dioxide Substances 0.000 claims description 58
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 58
- 239000011241 protective layer Substances 0.000 claims description 45
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 37
- 239000003431 cross linking reagent Substances 0.000 claims description 34
- 239000002335 surface treatment layer Substances 0.000 claims description 28
- 239000011230 binding agent Substances 0.000 claims description 25
- 229920000642 polymer Polymers 0.000 claims description 25
- 239000000126 substance Substances 0.000 claims description 24
- 239000004593 Epoxy Substances 0.000 claims description 21
- 239000004744 fabric Substances 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 19
- 238000004132 cross linking Methods 0.000 claims description 9
- 239000006224 matting agent Substances 0.000 claims description 8
- 229920002545 silicone oil Polymers 0.000 claims description 7
- 229920005645 diorganopolysiloxane polymer Polymers 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 239000010408 film Substances 0.000 description 57
- 239000002585 base Substances 0.000 description 54
- 238000000576 coating method Methods 0.000 description 48
- 239000011248 coating agent Substances 0.000 description 44
- 239000002245 particle Substances 0.000 description 31
- 230000007613 environmental effect Effects 0.000 description 28
- 238000000034 method Methods 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 26
- 230000000694 effects Effects 0.000 description 26
- 238000005299 abrasion Methods 0.000 description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 21
- 229920001228 polyisocyanate Polymers 0.000 description 21
- 239000005056 polyisocyanate Substances 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000000976 ink Substances 0.000 description 15
- 239000003973 paint Substances 0.000 description 14
- 239000000758 substrate Substances 0.000 description 14
- 238000012546 transfer Methods 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 12
- 239000012461 cellulose resin Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 238000007639 printing Methods 0.000 description 10
- 230000009467 reduction Effects 0.000 description 10
- 229920002050 silicone resin Polymers 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000007666 vacuum forming Methods 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 229920000178 Acrylic resin Polymers 0.000 description 9
- 239000004925 Acrylic resin Substances 0.000 description 9
- 239000004743 Polypropylene Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 229920001225 polyester resin Polymers 0.000 description 9
- 239000004645 polyester resin Substances 0.000 description 9
- 229920001155 polypropylene Polymers 0.000 description 9
- 238000010792 warming Methods 0.000 description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 8
- 229920000877 Melamine resin Polymers 0.000 description 8
- 239000004640 Melamine resin Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 239000013013 elastic material Substances 0.000 description 8
- 239000011737 fluorine Substances 0.000 description 8
- 229910052731 fluorine Inorganic materials 0.000 description 8
- 239000005011 phenolic resin Substances 0.000 description 8
- 230000003068 static effect Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000000975 dye Substances 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 6
- 238000011109 contamination Methods 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000012855 volatile organic compound Substances 0.000 description 6
- 230000002087 whitening effect Effects 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 239000005062 Polybutadiene Substances 0.000 description 5
- 229920000180 alkyd Polymers 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 5
- 229920006122 polyamide resin Polymers 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 239000004800 polyvinyl chloride Substances 0.000 description 5
- 229920000915 polyvinyl chloride Polymers 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229920000298 Cellophane Polymers 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 239000008199 coating composition Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000005431 greenhouse gas Substances 0.000 description 4
- 230000033001 locomotion Effects 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229920002725 thermoplastic elastomer Polymers 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229920002943 EPDM rubber Polymers 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 235000015278 beef Nutrition 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 150000005676 cyclic carbonates Chemical group 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012943 hotmelt Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012778 molding material Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000000859 sublimation Methods 0.000 description 3
- 230000008022 sublimation Effects 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 238000007646 gravure printing Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000011968 lewis acid catalyst Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 235000009518 sodium iodide Nutrition 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229920005792 styrene-acrylic resin Polymers 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- OSNILPMOSNGHLC-UHFFFAOYSA-N 1-[4-methoxy-3-(piperidin-1-ylmethyl)phenyl]ethanone Chemical compound COC1=CC=C(C(C)=O)C=C1CN1CCCCC1 OSNILPMOSNGHLC-UHFFFAOYSA-N 0.000 description 1
- NFDXQGNDWIPXQL-UHFFFAOYSA-N 1-cyclooctyldiazocane Chemical compound C1CCCCCCC1N1NCCCCCC1 NFDXQGNDWIPXQL-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
- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical compound C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 208000032544 Cicatrix Diseases 0.000 description 1
- 241000283070 Equus zebra Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- POJOORKDYOPQLS-UHFFFAOYSA-L barium(2+) 5-chloro-2-[(2-hydroxynaphthalen-1-yl)diazenyl]-4-methylbenzenesulfonate Chemical compound [Ba+2].C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S([O-])(=O)=O.C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S([O-])(=O)=O POJOORKDYOPQLS-UHFFFAOYSA-L 0.000 description 1
- 239000000981 basic dye Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- WXCZUWHSJWOTRV-UHFFFAOYSA-N but-1-ene;ethene Chemical compound C=C.CCC=C WXCZUWHSJWOTRV-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- HGAZMNJKRQFZKS-UHFFFAOYSA-N chloroethene;ethenyl acetate Chemical compound ClC=C.CC(=O)OC=C HGAZMNJKRQFZKS-UHFFFAOYSA-N 0.000 description 1
- 210000000078 claw Anatomy 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 239000000982 direct dye Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 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
- 239000001023 inorganic pigment Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 150000004714 phosphonium salts 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
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000007763 reverse roll coating Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 230000037387 scars Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 description 1
- AFCAKJKUYFLYFK-UHFFFAOYSA-N tetrabutyltin Chemical compound CCCC[Sn](CCCC)(CCCC)CCCC AFCAKJKUYFLYFK-UHFFFAOYSA-N 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
- C08G71/04—Polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/42—Intermediate, backcoat, or covering layers
- B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds
- B41M5/443—Silicon-containing polymers, e.g. silicones, siloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
- C08G18/8029—Masked aromatic polyisocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/458—Block-or graft-polymers containing polysiloxane sequences containing polyurethane sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
- B41M2205/02—Dye diffusion thermal transfer printing (D2T2)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
- B41M2205/06—Printing methods or features related to printing methods; Location or type of the layers relating to melt (thermal) mass transfer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
- B41M2205/36—Backcoats; Back layers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/04—Properties of the materials having electrical or magnetic properties
- D06N2209/046—Anti-static
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/10—Properties of the materials having mechanical properties
- D06N2209/105—Resistant to abrasion, scratch
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/10—Properties of the materials having mechanical properties
- D06N2209/108—Slipping, anti-blocking, low friction
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
- Y10T428/31587—Hydrocarbon polymer [polyethylene, polybutadiene, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
Definitions
- the present invention relates to a novel polysiloxane-modified polyhydroxypolyurethane resin, a method for producing the same, and a technology for using the resin. More specifically, it is a novel material useful as a raw material for films, molding materials, various coating materials, various binders, etc., which has excellent properties such as lubricity, abrasion resistance, chemical resistance, non-adhesiveness, antistatic property, and heat resistance.
- the present invention relates to provision of a polysiloxane-modified polyhydroxypolyurethane resin and a technique for using the resin. Since the above-mentioned resin can use carbon dioxide as a raw material for production, the carbon dioxide reduction effect which is a problem on a global scale can be obtained.
- Specific usage forms include the following. (1) A heat-sensitive recording material useful for a hot melt type thermal transfer system or a sublimation type thermal transfer system, in which the heat-resistant protective layer on the back is made of a polysiloxane-modified polyhydroxypolyurethane resin. (2) A fake leather excellent in texture, lubricity, scratch resistance, abrasion resistance, and chemical resistance, obtained by using a composition mainly composed of polysiloxane-modified polyhydroxypolyurethane resin.
- the surface used for automobile interior materials and home appliance parts using polysiloxane-modified polyhydroxypolyurethane resin for the formation of the topcoat layer has a smooth surface, surface feel, scratch resistance, abrasion resistance, Thermoplastic polyolefin resin skin material with excellent chemical properties and capable of forming a uniform matte film.
- Weather strip with a surface treatment layer with excellent heat resistance and weather resistance.
- Non-Patent Documents 1 and 2 polyhydroxy polyurethane resin using carbon dioxide as a raw material has been known for a long time, but its application development has not progressed. This is because the above known resins are clearly inferior to conventional polyurethane resins, which are petrochemical polymers (petrolithic plastics), in terms of their characteristics (Patent Documents 1 and 2). reference).
- the global warming phenomenon which is thought to result from the ever-increasing carbon dioxide emissions, has become a global problem in recent years, and the reduction of carbon dioxide emissions is an important issue worldwide. Therefore, there is a long-awaited technology that can use carbon dioxide as a raw material for production. Furthermore, from the viewpoint of exhaustible petrochemical resources (petroleum), the shift to renewable resources such as biomass and methane has become a global trend.
- Thermal recording material Conventionally, a dye or pigment is supported on one surface of a substrate sheet such as a polyester film with a binder resin to form a heat-sensitive recording layer (ink layer), and the ink layer is heated from the back surface in a pattern shape.
- a substrate sheet such as a polyester film with a binder resin
- the ink layer is heated from the back surface in a pattern shape.
- heat-melting type heat-sensitive recording materials that are transferred to a transfer material
- further sublimation transfer recording materials that use a heat-sublimable dye as the dye, and similarly sublimate transfer only the dye to the transfer material.
- the above resins are thermally cross-linked using various cross-linking agents, or inorganic fillers or fluororesin powders are used on these resins. Attempts have been made to add, for example. However, although heat resistance can be obtained by these methods, it is insufficient as a countermeasure for improving the slipperiness and non-adhesiveness with respect to the thermal head.
- the only silicone resins in the resins listed above are slippery and non-adhesive, but in the heating process performed to completely crosslink the resin, a thin film usually about 2-5 ⁇ m thick is used. There is another problem of damaging the base sheet.
- the present inventors examined methods for solving these problems, and by using various silicone polyurethane copolymer resins, an excellent heat-resistant protective layer having heat resistance, slipperiness, non-adhesiveness, etc. was obtained. It has been proposed that a heat-sensitive recording material having the above can be obtained (see Patent Documents 4 to 6). However, these have not been studied from the viewpoint of global environmental conservation, which has become a global problem in recent years, and there is a demand for a review of technology from such a new viewpoint.
- Artificial leather has a structure that most closely resembles natural leather among artificial leather, and uses non-woven fabric for the base fabric.
- a general method for producing artificial leather there are the following methods. First, after impregnating a nonwoven fabric with a dimethylformamide (hereinafter referred to as DMF) solution of a polyurethane resin, it is solidified and dried in a porous state by wet film formation (solidification in water). After that, there are a method in which a surface is further provided with a polyurethane resin coating or laminate layer to make it smooth, and a method in which the surface is ground and raised to give a suede tone.
- DMF dimethylformamide
- Synthetic leather uses a fabric such as a woven fabric or a raised fabric as a base fabric, and is generally divided into dry synthetic leather and wet synthetic leather.
- a method for producing dry synthetic leather a polyurethane resin is directly applied to a base cloth and dried, and after applying a polyurethane resin on a release paper, it is dried and filmed, and the base cloth is bonded with an adhesive. There is a method of pasting together.
- wet synthetic leather can be produced by impregnating or coating a base fabric with the DMF solution of polyurethane resin described above, and then solidifying and drying in water to form a porous layer.
- each surface obtained by the dry or wet methods as described above is coated with a polyurethane resin or provided with a layer by lamination, or the surface is ground and brushed. There is a method of suede tone.
- thermoplastic polyolefin resin Vehicle interior materials (instrument panels, door trims, etc.) and household electrical appliance parts are strongly desired to be recycled in order to reduce waste materials after use as much as possible in view of recent dust problems and environmental problems.
- thermoplastic polyolefins such as polypropylene (PP), ABS resin, AS resin, polyolefin-based thermoplastic elastomer (TPO) and the like have been used as skin materials for vehicle interior materials and home appliance parts.
- PP polypropylene
- AS resin polyolefin-based thermoplastic elastomer
- these thermoplastic polyolefins have poor surface adhesion, scratch resistance, abrasion resistance, and chemical resistance compared to vinyl chloride resins that have been used in the past. It is necessary to apply.
- thermoplastic polyolefin base material in order to give a high-class feeling, it is necessary to consider not only the design property but also the anti-glare property for the driver in the case of automobile interior materials. For this reason, by giving various coatings to the thermoplastic polyolefin base material to form a topcoat layer, a function is imparted to the surface in order to obtain a better skin material.
- a chlorinated polypropylene-modified acrylic resin having good adhesion to polyolefin resins such as PP resin and TPO resin is used as a binder resin, and glossy inorganic pigments (silica, talc), acrylic resin particles, etc.
- Methods have been proposed in which a paint containing a quencher is used, or a chlorinated polypropylene primer is applied and a paint having a polyester resin or a polyurethane resin is applied thereon.
- Weather strip material Conventionally, materials for forming weather strips such as glass runs, door weather strips, body side weather strips, inside seals, and outside seals for automobiles and buildings include chloroprene rubber, styrene-butadiene rubber, nitrile rubber, EPDM rubber, etc. A polymer elastic material is used. And in order to give these surfaces performances such as lubricity, abrasion resistance, mold release, heat resistance, water resistance and weather resistance, a surface treatment layer may be formed by a method such as coating or impregnation. Has been done.
- a material for forming such a surface treatment layer a material obtained by adding silicone oil to a thermosetting polyurethane resin (see Patent Document 13) or a material containing organopolysiloxane in a thermosetting polyurethane resin (see Patent Document 14) ), And paints made of urethane prepolymer and silicone oil, hydrophobic silica, polyisocyanate (see Patent Document 15) and the like have been proposed.
- the object of the present invention is to provide environmentally friendly products that can satisfy the properties required for each application and that can use carbon dioxide as a raw material for production, which is also excellent from the viewpoint of global environmental conservation. Is to develop a new resin that can be
- the heat-resistant protective layer on the back surface has further heat resistance, slipperiness and non-adhesiveness, as well as when the film is peeled off. Countermeasures against generated static electricity are required.
- conventional heat-sensitive recording media materials are difficult to recycle products after use, and it is necessary to improve on the fact that they have become a large amount of waste.
- development of technology capable of providing excellent environmentally-friendly products is required from the viewpoint of global environmental conservation even though it is a heat-sensitive recording material having a heat-resistant protective layer with excellent heat resistance, slipperiness and non-adhesiveness. Yes.
- thermoplastic polyolefin resin skin material For thermoplastic polyolefin resin skin materials used for vehicle interior materials and home appliance parts, it is possible to achieve even more surface scratch resistance, abrasion resistance and chemical resistance, and even a matte effect if necessary. In addition, the development of environmentally friendly products with environmental conservation on a global scale is demanded. That is, in addition to the above-described thermoplastic polyolefin resin skin material having excellent characteristics, development of a technology capable of providing a thermoplastic polyolefin resin skin material that is an excellent environment-friendly product is required.
- a surface treatment layer provided on a weather strip of an automobile or a building by a method such as coating or impregnation has excellent basic characteristics such as lubricity, wear resistance, heat resistance and weather resistance, and also has a global environment. It would be very useful if it could be an environmentally friendly product with maintainability. Therefore, although the material for forming the surface treatment layer in the sliding contact portion that is in sliding contact with other parts of the polymeric elastic material constituting the weather strip is a material that contributes to environmental conservation, the formed surface treatment layer is Therefore, there is a need for a technique for providing a useful material having excellent lubricity, wear resistance, heat resistance, and weather resistance.
- the present invention provides a polysiloxane-modified polyhydroxypolyurethane resin which is derived from a reaction between a 5-membered cyclic carbonate compound and an amine-modified polysiloxane compound.
- the present invention is derived from the reaction of a 5-membered cyclic carbonate compound obtained by reacting an epoxy compound and carbon dioxide with an amine-modified polysiloxane compound, A method for producing a polyhydroxy polyurethane resin is provided.
- the present invention also includes a base sheet, a heat-sensitive recording layer provided on at least one surface of the base sheet, and a heat-resistant protective layer provided on the back surface in contact with the thermal head on the other surface.
- a resin composition containing at least the polysiloxane-modified polyhydroxypolyurethane resin described above.
- the present invention also provides artificial leather characterized by filling or laminating a base fabric with a resin composition mainly composed of the above polysiloxane-modified polyhydroxypolyurethane resin.
- the present invention has either a thermoplastic polyolefin resin sheet, a topcoat layer formed directly on the sheet, or a topcoat layer formed via a primer layer formed on the sheet.
- the topcoat layer comprises the above-described polysiloxane-modified polyhydroxypolyurethane resin as a main component, and a thermoplastic polyolefin resin skin material is provided.
- the present invention also provides a weather strip material for coating and / or impregnating a polymer elastic material to form a surface treatment layer in a sliding contact portion that is in sliding contact with another component, the polysiloxane modified as described above
- a weatherstrip material characterized by being a resin composition comprising a polyhydroxy polyurethane resin.
- the weather strip material is coated and / or impregnated with a polymer elastic body material, and a surface treatment layer is formed at a sliding contact portion which is in sliding contact with other parts, and the surface treatment layer is formed from the weather strip material.
- the weather strip is formed by crosslinking with a crosslinking agent that reacts with a hydroxyl group in the structure of the polysiloxane-modified polyhydroxypolyurethane resin.
- the polysiloxane-modified polyhydroxypolyurethane resin provided by the present invention can form a film excellent in lubricity, abrasion resistance, chemical resistance, non-adhesiveness, antistatic property, heat resistance, etc. It can be substituted.
- the resin provided in the present invention can use carbon dioxide as a raw material for production, the present invention makes it possible to provide a global environment-friendly product that can contribute to the reduction of carbon dioxide, which is a greenhouse gas. More specifically, the following products can be provided.
- the heat-resistant protective layer has heat resistance, slipperiness, non-adhesiveness, and adhesion to a base sheet, Furthermore, it is possible to provide a heat-sensitive recording material that is also excellent in an antistatic effect.
- the above resin can provide such an excellent thermal recording material, and at the same time, carbon dioxide can be used as a raw material, and carbon dioxide can be incorporated into the resin, so it can be used as an environmentally friendly product that contributes to reducing greenhouse gases. It is possible to provide a useful thermal recording material.
- the artificial leather which has the texture which is not inferior to the conventional artificial leather, and is excellent in surface slipperiness, abrasion resistance, abrasion resistance, and chemical resistance is provided.
- a resin in which carbon dioxide is incorporated and fixed in the resin as a material for forming artificial leather, contributing to the reduction of carbon dioxide, which is regarded as a global problem as a warming gas. From the standpoint of conservation, an environmentally friendly artificial leather is provided.
- thermoplastic polyolefin resin skin material In the present invention, by using a specific polysiloxane-modified polyhydroxypolyurethane resin as a material for forming the topcoat layer constituting the thermoplastic polyolefin resin skin material, its surface, lubricity, surface feel, scratch resistance, abrasion resistance As a result, it is possible to provide a thermoplastic polyolefin resin skin material excellent in uniform matting effect as required. At the same time, it is also an environmentally friendly product that can contribute to the reduction of carbon dioxide, which is regarded as a global problem as a greenhouse gas, because a resin in which carbon dioxide is incorporated and fixed in the resin can be used as a material for forming the topcoat layer. A thermoplastic polyolefin resin skin material is provided.
- a useful material for forming a surface treatment layer in a sliding contact portion that is in sliding contact with other components of a polymer elastic body material that is a base material for a weather strip of an automobile or a building is environmentally safe.
- a useful material in which the formed surface treatment layer is excellent in lubricity, wear resistance, heat resistance, and weather resistance is provided.
- a composition comprising a polysiloxane-modified polyhydroxypolyurethane resin is used as the coating composition for the surface treatment of the polymer elastic body, so that the formed surface treatment layer has the basic characteristics described above.
- carbon dioxide which is considered to be a global warming gas, can be used as a raw material for its production, so it is also useful from the viewpoint of global environmental conservation, and the environment that uses this material Products can be provided.
- the infrared absorption spectrum of an epoxy compound (Epicoat 828).
- GPC elution curve of 5-membered cyclic carbonate compound (mobile phase: THF, column: TSK-Gel GMHXL + G2000HXL + G3000HXL, detector: IR).
- the polysiloxane-modified polyhydroxypolyurethane resin of the present invention (hereinafter sometimes simply referred to as “resin of the present invention” or “resin used in the present invention”) is a 5-membered cyclic carbonate compound, an amine-modified polysiloxane compound, It was derived from the reaction of The 5-membered cyclic carbonate compound can be produced, for example, by reacting an epoxy compound and carbon dioxide as shown by the following [Formula-A].
- the epoxy compound is reacted with carbon dioxide in the presence or absence of an organic solvent and in the presence of a catalyst at a temperature of 40 ° C. to 150 ° C. at normal pressure or slightly elevated pressure for 10-20 hours. It is obtained by reacting.
- Examples of the epoxy compound that can be used in the present invention include the following compounds.
- the epoxy compounds listed above are preferred compounds used in the present invention, and the present invention is not limited to these exemplified compounds. Accordingly, not only the above-exemplified compounds but also other compounds that are currently commercially available and can be easily obtained from the market can be used in the present invention.
- the 5-membered cyclic carbonate compound used in the present invention can be obtained by the reaction of the above epoxy compound and carbon dioxide.
- the catalyst used in this case include a base catalyst and a Lewis acid catalyst.
- the base catalyst include tertiary amines such as triethylamine and tributylamine, cyclic amines such as diazabicycloundecene, diazabicyclooctane, and pyridine, lithium chloride, lithium bromide, lithium fluoride, and sodium chloride.
- Alkali metal salts alkaline earth metal salts such as calcium chloride, quaternary ammonium salts such as tetrabutylammonium chloride, tetraethylammonium bromide, benzyltrimethylammonium chloride, carbonates such as potassium carbonate and sodium carbonate, zinc acetate, lead acetate
- Metal acetates such as copper acetate and iron acetate, metal oxides such as calcium oxide, magnesium oxide and zinc oxide, and phosphonium salts such as tetrabutylphosphonium chloride.
- examples of the Lewis acid catalyst include tin compounds such as tetrabutyltin, dibutyltin dilaurate, dibutyltin diacetate, and dibutyltin octoate.
- These catalysts may be used in an amount of 0.1 to 100 parts by weight, preferably 0.3 to 20 parts by weight, per 50 parts by weight of the epoxy compound. If the amount used is less than 0.1 parts by mass, the effect as a catalyst is small, and if it is too much, various performances of the final resin may be deteriorated. Therefore, when the residual catalyst causes a serious performance deterioration, it may be removed by washing with pure water.
- organic solvent examples include dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, and tetrahydrofuran.
- organic solvents and other poor solvents such as methyl ethyl ketone, xylene, toluene, tetrahydrofuran, diethyl ether, and cyclohexanone may be used in a mixed system.
- the resin of the present invention comprises a 5-membered cyclic carbonate compound obtained by the above reaction and an amine-modified polysiloxane compound in the presence of an organic solvent at 20 ° C. to 150 ° C. It can be obtained by reacting at a temperature of ° C.
- Examples of the amine-modified polysiloxane compound used in the above reaction include the following compounds.
- the lower alkylene group in the following formula means one having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms.
- the amine-modified polysiloxane compounds listed here are preferred compounds used in the present invention, and the present invention is not limited to these exemplified compounds. Accordingly, not only the above-exemplified compounds but also other compounds that are currently commercially available and can be easily obtained from the market can be used in the present invention.
- the polysiloxane-modified polyhydroxypolyurethane resin of the present invention obtained as described above is such that the proportion of the polysiloxane segment in the resin is 1 to 75% by mass with respect to the resin molecule content.
- it exceeds 75% by mass the performance of the polyhydroxyurethane resin such as mechanical strength and abrasion resistance becomes insufficient, which is not preferable. More preferably, it is 2 to 60% by mass, and further preferably 5 to 30% by mass.
- the resin of the present invention preferably has a number average molecular weight (standard polystyrene conversion value measured by GPC) of about 2,000 to 100,000. Further, it is more preferably about 5,000 to 70,000.
- the resin of the present invention is derived from a reaction between a 5-membered cyclic carbonate compound and an amine-modified polysiloxane compound.
- generated when the 5-membered cyclic carbonate group in the structure of this resin reacts with an amine-modified polysiloxane compound brings about the further improvement of performance to this resin. That is, since the hydroxyl group has hydrophilicity, the adhesion to the substrate can be remarkably improved, and furthermore, an antistatic effect that cannot be achieved by the conventional product can be obtained.
- by utilizing the reaction between the hydroxyl group in the resin structure and the crosslinking agent added to the resin it becomes possible to further improve heat resistance, wear resistance, chemical resistance, etc. For example, it is useful when a surface treatment layer or the like is formed.
- the hydroxyl value of the resin of the present invention is preferably 20 to 300 mgKOH / g.
- the hydroxyl value is less than the above range, it is difficult to say that the carbon dioxide reduction effect is sufficiently obtained.
- the hydroxyl value exceeds the above range, various physical properties such as mechanical properties as a polymer compound are insufficient.
- the polysiloxane-modified polyhydroxypolyurethane resin provided by the present invention can be used as it is, but it can also be used as a crosslinked resin using a crosslinking agent.
- a crosslinking agent that can be used at this time, any crosslinking agent that reacts with a hydroxyl group in the resin structure can be used. Examples include alkyl titanate compounds and polyisocyanate compounds. Conventionally known polyisocyanate compounds used for crosslinking of polyurethane resins are preferred, but not particularly limited. Examples include adducts of polyisocyanates having the following structural formula and other compounds.
- the resin of the present invention when used for various uses and film formation, it is conventionally known in order to improve the coating suitability for the base material, the film forming property, or the content of the polysiloxane segment.
- Various binder resins can be mixed and used.
- the binder resin used at this time is preferably one that can chemically react with a crosslinking agent such as the above-mentioned polyisocyanate adduct, but one having no reactivity can also be used.
- various resins conventionally used as a binder resin can be used and are not particularly limited.
- acrylic resin, polyurethane resin, polyester resin, polybutadiene resin, silicone resin, melamine resin, phenol resin, polyvinyl chloride resin, cellulose resin, alkyd resin, modified cellulose resin, fluorine resin, polyvinyl butyral resin, epoxy resin, polyamide resin Etc. can be used.
- resins obtained by modifying these various resins with silicone or fluorine can be used.
- the binder resin is used in combination, the amount used is 5 to 90 parts by weight, more preferably about 10 to 60 parts by weight, based on 100 parts by weight of the polysiloxane-modified polyhydroxypolyurethane resin of the present invention.
- the polysiloxane segment in the resin structure is oriented on the surface of the film, so that the film has heat resistance, slipperiness, non-adhesive properties that are characteristic of the polysiloxane segment. Sex is imparted.
- the hydroxyl group in the structure of the resin strongly interacts with the substrate on which the film is formed at the interface, thereby providing excellent adhesion and flexibility to the substrate and an antistatic effect. For this reason, the product of the outstanding performance can be obtained by using the resin of this invention.
- the 5-membered cyclic carbonate compound constituting the resin of the present invention can incorporate carbon dioxide into the resin by using carbon dioxide as a raw material for production. For this reason, the present invention provides an environmentally friendly material that was useful from the viewpoint of reducing carbon dioxide, which is a cause of global warming, and could not be achieved by conventional products.
- the polysiloxane-modified polyhydroxypolyurethane resin of the present invention is used as various molding materials, synthetic leather and artificial leather materials, fiber coating materials, surface treatment materials, thermal recording materials, releasable materials, paints, binders for printing inks, and the like. It is very useful and its utilization is expected.
- various products using the polysiloxane-modified polyhydroxy polyurethane resin of the present invention will be specifically described.
- a heat-sensitive recording layer is provided on one surface of a base sheet, and a heat-resistant protective layer is formed on the other back surface. It is characterized by being a polysiloxane-modified polyhydroxypolyurethane resin. That is, the heat-sensitive recording material of the present invention comprises a heat-resistant protective layer comprising the polysiloxane-modified polyhydroxypolyurethane resin of the present invention derived from a reaction between a 5-membered cyclic carbonate compound and an amine-modified polysiloxane compound, or It consists of a resin composition containing resin.
- the heat-resistant protective layer constituting the heat-sensitive recording material of the present invention can be formed as a film made of the above-described polysiloxane-modified polyhydroxypolyurethane resin, but can also be formed into a crosslinked film using a crosslinking agent.
- a crosslinking agent that can be used at this time, any crosslinking agent that reacts with a hydroxyl group in the resin structure can be used. Examples include alkyl titanate compounds and polyisocyanate compounds. Any known polyisocyanate compound conventionally used for crosslinking polyurethane resins is not particularly limited. Examples thereof include adducts of polyisocyanates having the structural formulas listed above with other compounds.
- the coating suitability for the base material sheet, the improvement of film formability, and the content of the polysiloxane segment are adjusted.
- various conventionally known binder resins can be added and used.
- the binder resin used at this time those capable of chemically reacting with a crosslinking agent such as the above-mentioned polyisocyanate adduct are preferable, but those having no reactivity can also be used in the present invention.
- the binder resin used at this time is not particularly limited, and any binder resin conventionally used for forming the heat-resistant protective layer on the back surface constituting the heat-sensitive recording material can be used.
- any binder resin conventionally used for forming the heat-resistant protective layer on the back surface constituting the heat-sensitive recording material can be used.
- acrylic resin, polyurethane resin, polyester resin, polybutadiene resin, silicone resin, melamine resin, phenol resin, polyvinyl chloride resin, cellulose resin, alkyd resin, modified cellulose resin, fluorine resin, polyvinyl butyral resin, epoxy resin, polyamide resin Etc. can be used.
- resins obtained by modifying these resins with silicone or fluorine can be used.
- the amount used is 5 to 90 parts by weight, more preferably about 10 to 60 parts by weight, based on 100 parts by weight of the polysiloxane-modified polyhydroxypolyurethane resin.
- the method for forming the heat-resistant protective layer constituting the heat-sensitive recording material of the present invention is not particularly limited.
- the above-described polysiloxane-modified polyhydroxypolyurethane resin is dissolved or dispersed in an appropriate organic solvent, and this is, for example, a wire bar method, a gravure printing method, a screen printing method, a reverse roll coating method using a gravure plate, or the like. It can be formed by coating with a forming means and drying. The drying temperature at this time is preferably in the range of 50 to 100 ° C.
- the thickness of the heat-resistant protective layer is preferably 0.001 to 2.00 ⁇ m, particularly preferably 0.05 to 0.7 ⁇ m.
- the base sheet used in the heat-sensitive recording material of the present invention includes polycarbonate, polyarylate, polyetherimide, polysulfone, polyphenyl ether, polyamideimide, polyimide, polyethylene naphthalate, polyphenyl sulfide, polyether ketone, and fluororesin.
- films such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polybutylene naphthalate (PBN), polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyamide, etc. can be used.
- PET polyethylene terephthalate
- PBT polybutylene terephthalate
- PBN polybutylene naphthalate
- polyethylene polypropylene
- polystyrene polyvinyl chloride
- polyvinylidene chloride polyamide
- the thickness of the substrate is preferably 6 ⁇ m or less, and more preferably
- the ink layer in the heat-sensitive recording material of the present invention a conventionally known ink layer is used as it is, and is not particularly limited. That is, the ink layer used in the present invention is composed of additives such as colorants, waxes, resins and lubricants, and surfactants. Examples of the colorant include pigments and dyes such as carbon black, petal, lake red C, benzidine yellow, phthalocyanine green, phthalocyanine blue, direct dyes, oil dyes, and basic dyes.
- the present invention is not limited to these exemplary compounds. Therefore, not only the compounds exemplified above, but also any compounds that are currently used in the hot melt thermal transfer system or the sublimation thermal transfer system and can be easily obtained from the market can be used in the present invention.
- the heat-sensitive recording material of the present invention uses the above-described polysiloxane-modified polyhydroxypolyurethane resin of the present invention for the resin composition for forming the heat-resistant protective layer provided on the back surface of the base sheet.
- the siloxane segment will be oriented on the surface of the protective layer.
- the formed heat-resistant protective layer is given heat resistance, slipperiness and non-adhesiveness to the thermal head of the polysiloxane segment.
- the hydroxyl group in the structure of the polysiloxane-modified polyhydroxypolyurethane resin forming the heat-resistant protective layer strongly interacts with the substrate sheet at the interface, so that excellent adhesion to the substrate and flexibility are achieved.
- the heat-sensitive recording material can have a better performance.
- the 5-membered cyclic carbonate compound constituting the resin used in the present invention can incorporate carbon dioxide into the resin by using carbon dioxide as a production raw material. Therefore, according to the present invention, it is possible to provide a heat-sensitive recording material as an environmentally-friendly product, which is useful from the viewpoint of reducing carbon dioxide, which is a cause of global warming, and cannot be achieved by conventional products.
- the artificial leather of the present invention comprises a resin composition mainly composed of the polysiloxane-modified polyhydroxypolyurethane resin of the present invention derived from the reaction between the 5-membered cyclic carbonate compound and the amine-modified polysiloxane compound described above.
- the base fabric is filled or laminated.
- the base resin is filled or laminated with the resin composition mainly composed of the polysiloxane-modified polyhydroxypolyurethane resin of the present invention, but the film made of the resin is used as it is.
- a crosslinked film can also be formed using a crosslinking agent.
- Any crosslinking agent that can react with a hydroxyl group in the resin structure can be used as the crosslinking agent that can be used in this case.
- an alkyl titanate compound, a polyisocyanate compound, etc. are mentioned.
- Any known cross-linking agent conventionally used for cross-linking polyurethane resins is not particularly limited. Examples thereof include adducts of polyisocyanates having the structural formulas listed above with other compounds.
- the resin composition mainly composed of the polysiloxane-modified polyhydroxypolyurethane resin of the present invention used for forming the artificial leather of the present invention is suitable for workability such as impregnation, coating and coating, and the texture and various performances of the resulting artificial leather.
- various conventionally known resins can be mixed and used.
- Other resins used for mixing are preferably those capable of chemically reacting with a crosslinking agent such as the above polyisocyanate adduct, but those having no reactivity can also be used in the present invention.
- the resin used in combination with the above resin is preferably a polyurethane resin conventionally used as a material for forming artificial leather, but is not particularly limited.
- a polyurethane resin conventionally used as a material for forming artificial leather
- An epoxy resin, a polyamide resin, or the like can be used.
- resins obtained by modifying various resins with silicone or fluorine can be used. When these resins are used in combination, the amount used is from 5 to 90 parts by weight, more preferably from about 10 to 60 parts by weight, based on 100 parts by weight of the polysiloxane-modified polyhydroxypolyurethane resin. Use it.
- the resin composition mainly composed of the polysiloxane-modified polyhydroxypolyurethane resin used in the present invention includes, in addition to the above various resins, an antioxidant, an ultraviolet absorber, a hydrolysis inhibitor, a pigment, a dye, a flame retardant, You may mix
- the artificial leather of the present invention is characterized in that the base composition is filled or laminated with the resin composition mainly composed of the polysiloxane-modified polyhydroxypolyurethane resin described above.
- the method for producing the artificial leather of the present invention is not limited at all, and known methods for producing artificial leather and synthetic leather can be used.
- the artificial leather of the present invention is provided with a vinyl chloride resin layer containing a plasticizer on a base fabric sheet, and a resin layer mainly composed of a polysiloxane-modified polyhydroxypolyurethane resin characterizing the present invention. The formed one is also included.
- any base fabric (base material sheet) conventionally used in the manufacture of artificial leather can be used and is not particularly limited.
- the artificial leather of the present invention uses a specific polyloxane-modified polyhydroxypolyurethane resin as a main component so that the artificial leather excellent in flexibility, lubricity, scratch resistance, abrasion resistance, and chemical resistance can be obtained. Can be provided.
- the hydroxyl group of the polysiloxane-modified polyhydroxypolyurethane resin interacts strongly with the base fabric (base sheet) at the interface, thereby providing excellent adhesion and flexibility to the base fabric, and antistatic effect. The excellent performance of being imparted can be obtained, and the performance of artificial leather can be improved.
- combination of resin used by this invention can take in a carbon dioxide in resin by making a carbon dioxide into a manufacturing raw material.
- thermoplastic polyolefin resin skin material of the present invention has a topcoat layer formed by coating directly on the thermoplastic polyolefin resin sheet, or a primer layer coated on the resin sheet, and on the primer layer And a top coat layer formed by coating. Then, as the polymer compound constituting the top coat layer, the above-described polysiloxane-modified polyhydroxy polyurethane resin of the present invention, which is derived from the reaction between a 5-membered cyclic carbonate compound and an amine-modified polysiloxane compound, is used. It is characterized by that.
- the thermoplastic polyolefin resin skin material of the present invention is matte in consideration of antiglare properties and the like depending on the application.
- An agent may be blended.
- the matting agent a substance composed of one kind or a combination of two or more kinds selected from organic fine powder or inorganic fine powder can be used.
- the organic fine powder used in this case is not particularly limited, and examples thereof include acrylic resin particles, styrene resin particles, styrene-acrylic resin particles, phenol resin particles, melamine resin particles, acrylic-polyurethane resin particles, Polyurethane resin particles, polyester resin particles, nylon resin particles, silicone resin particles, polyethylene resin particles, and the like can be used. These powders preferably have an average particle diameter in the range of 0.1 to 10 ⁇ m. Moreover, since the matte property of the coating film to be formed is particularly excellent, a spherical or substantially spherical shape is practically preferable.
- inorganic fine powders include talc, mica, calcium carbonate, barium sulfate, magnesium carbonate, clay, alumina, silica, carbon fiber, glass fiber, metal fiber, carbon black, titanium oxide, molybdenum, magnesium hydroxide, bentonite. And graphite.
- talc mica, calcium carbonate, barium sulfate, magnesium carbonate, clay, alumina, silica, carbon fiber, glass fiber, metal fiber, carbon black, titanium oxide, molybdenum, magnesium hydroxide, bentonite.
- carbon black carbon black
- titanium oxide titanium oxide
- molybdenum magnesium hydroxide
- the amount of the matting agent used as described above is 1 to 150 parts by mass, preferably 3 to 100 parts by mass with respect to 100 parts by mass of the polysiloxane-modified polyhydroxypolyurethane resin. If it is less than 1 part by mass, the matting effect is not sufficient, and if it exceeds 150 parts by mass, the mechanical properties of the coating film are greatly reduced, which is not preferable.
- the polysiloxane-modified polyhydroxypolyurethane resin used in the present invention is derived from a reaction between a 5-membered cyclic carbonate compound and an amine-modified polysiloxane compound, and a hydroxyl group is generated during this reaction.
- the generated hydroxyl group brings about further improvement in performance with respect to the thermoplastic polyolefin resin skin material of the present invention having a top coat layer formed using the above resin. That is, since the hydroxyl group has hydrophilicity, the hydroxyl group can improve the adhesion to the thermoplastic polyolefin resin sheet, and can also provide an antistatic effect that could not be achieved with conventional products.
- thermoplastic polyolefin resin if a reaction between a hydroxyl group in the structure of the resin and a crosslinking agent added to the resin is used, in the surface product of the thermoplastic polyolefin resin, further surface scratch resistance, abrasion resistance, Improvements in chemical properties can be achieved.
- a composition comprising a polysiloxane-modified hydroxypolyurethane resin as a main component, and a composition containing a matting agent depending on the application (hereinafter abbreviated as “resin composition”) are used as they are.
- a film can be formed on a thermoplastic polyolefin resin to provide a topcoat layer.
- a crosslinked film can also be formed by including a crosslinking agent in the resin composition. Any crosslinking agent that can react with a hydroxyl group in the resin structure can be used as the crosslinking agent that can be used in this case.
- an alkyl titanate compound or a polyisocyanate compound may be mentioned, but there is no particular limitation as long as it is a known crosslinking agent conventionally used for crosslinking polyurethane resins.
- an adduct of a polyisocyanate having a structural formula as exemplified above with another compound can be used.
- the resin composition used in the present invention is different from the resin in order to improve sprayability and coating suitability for the thermoplastic polyolefin resin and film formability. May be included.
- various binder resins can be mixed and used.
- the binder resin is preferably one that can chemically react with the above-mentioned polyisocyanate adduct and other crosslinking agents, but those having no reactivity can also be used in the present invention.
- binder resins conventionally used for the surface of thermoplastic polyolefin resins can be used, and are not particularly limited.
- acrylic resin, polyurethane resin, polyester resin, polybutadiene resin, silicone resin, melamine resin, phenol resin, polyvinyl chloride resin, cellulose resin, alkyd resin, modified cellulose resin, fluorine resin, polyvinyl butyral resin, epoxy resin, polyamide resin Etc. can be used.
- the amount used is 5 to 90 parts by weight, more preferably 10 parts by weight based on 100 parts by weight of the polysiloxane-modified polyhydroxypolyurethane resin that characterizes the present invention. It is good to use in the range of about ⁇ 60 parts by mass.
- the resin composition used in the present invention may contain various coating additives such as a coating surface adjusting agent, a fluidity adjusting agent, an ultraviolet absorber, a dispersing agent, and an anti-settling agent, if necessary. Also good.
- thermoplastic polyolefin resin sheet constituting the skin material of the present invention is not particularly limited, but for example, those made of the following materials can be used.
- low density to high density polyethylene LDPE, LLDPE, HDPE, etc.
- polypropylene polypropylene such as propylene-ethylene copolymer, ethylene-propylene rubber (EPR), ethylene-butene rubber (EBR), ethylene-propylene-di
- EPR ethylene-propylene rubber
- EBR ethylene-butene rubber
- At least 1 sort (s) of resin chosen from the group which consists of thermoplastic polyolefin resin, such as an enter polymer (EDPM) can be used.
- EDPM enter polymer
- thermoplastic polyolefin resin constituting the sheet is inactive, and therefore often has poor adhesion to a coated product on the surface. For this reason, it is preferable to form the topcoat layer by directly applying the resin composition described above after physically or chemically activating the surface by corona discharge treatment or the like. Also, after applying a chlorinated polyolefin resin or polyester resin and a polyisocyanate compound, or a polyurethane resin and a polyisocyanate compound to form a primer layer, the resin composition described above is applied, It is preferable to form a topcoat layer.
- the resin composition described above can be applied to a thermoplastic polyolefin resin sheet directly or on the primer layer by a known coating method such as brush coating, spraying, roll coating, gravure, dipping, etc. so that the thickness after drying is about 3 to 20 ⁇ m.
- the film can be formed by coating the film and heat-treating it at a temperature of about 50 to 120 ° C. after drying.
- the sheet-shaped thermoplastic polyolefin resin skin material of the present invention formed as described above is molded into a predetermined shape by, for example, vacuum forming, and is used as, for example, a vehicle interior material or a home appliance part.
- thermoplastic polyolefin resin skin material of the present invention uses the polysiloxane-modified polyhydroxypolyurethane resin of the present invention as the material for forming the topcoat layer, so that the surface thereof is slippery, surface feel, scratch resistance, and scratch resistance. It is excellent in wear and chemical resistance, and also in a uniform matte effect.
- the hydroxyl group of the resin of the present invention used for forming the topcoat layer strongly interacts with the base sheet at the interface, thereby providing excellent adhesion and flexibility to the base material and antistatic effect.
- the performance of the thermoplastic polyolefin resin skin material can be improved.
- the 5-membered cyclic carbonate compound used for the synthesis of the resin used in the present invention can use carbon dioxide as a raw material for production and can fix carbon dioxide in the resin, it causes global warming. Therefore, it is possible to provide a thermoplastic polyolefin resin skin material that is useful from the viewpoint of reducing carbon dioxide and is an environmentally friendly material product that could not be achieved with conventional products.
- the weatherstrip material of the present invention is a material for coating and / or impregnating a polymer elastic body material to form a surface treatment layer in a sliding contact portion that is in sliding contact with other components.
- a resin composition comprising the polysiloxane-modified polyhydroxypolyurethane resin of the present invention derived from a reaction between a compound and an amine-modified polysiloxane compound.
- the weatherstrip material of the present invention comprises a resin composition comprising the polysiloxane-modified polyhydroxypolyurethane resin of the present invention described above, and a polymer elastic material is coated and / or impregnated with the resin composition.
- the surface treatment layer is formed in the sliding contact portion that is in sliding contact with the other components.
- a more preferred form of the resin composition is a diorganopoly having an average degree of polymerization of 5,000 to 100,000 as an additive with respect to 100 parts by mass of the polysiloxane-modified polyhydroxypolyurethane resin of the present invention described above. Examples include those obtained by adding siloxane and / or silicone oil having a viscosity of 100 to 1,000 CS at a ratio of 1 to 100 parts by mass.
- the diorganopolysiloxane to be blended with the above resin it is preferable to use a linear non-flowable rubbery silicone having an average degree of polymerization of 5,000 to 10,000. Such materials are readily available from the market.
- the silicone oil blended with the polysiloxane-modified polyhydroxy polyurethane resin of the present invention preferably has a viscosity in the range of 100 to 1,000 CS.
- the silicone oil used in this case may have, for example, an active hydrogen group that reacts with a polyisocyanate that is a crosslinking agent, or may not have an active hydrogen group.
- CS means centistokes, which is a unit of kinematic viscosity, and is usually marketed with this value as one specification.
- the addition amount of the above-mentioned diorganopolysiloxane and / or silicone oil is 1 to 100 parts by mass, preferably about 3 to 70 parts by mass with respect to 100 parts by mass of the polysiloxane-modified polyhydroxypolyurethane resin. Good. If the addition amount is less than 1 part by mass, the effect of addition is small, while if it exceeds 100 parts by mass, the mechanical properties of the coating film tend to be reduced, which is not preferable.
- a matting agent is used as an additive in order to improve the matting, wear and lubricity of the treatment layer surface.
- a matting agent is used as an additive in order to improve the matting, wear and lubricity of the treatment layer surface.
- a matting agent is used as an additive in order to improve the matting, wear and lubricity of the treatment layer surface.
- 100 parts by mass of the resin used in the present invention 1 to 150 parts by mass of a substance consisting of one or a combination of two or more selected from organic fine powders or inorganic fine powders as a matting agent.
- the resin composition is preferably added at a ratio of parts.
- the organic fine powder used in this case is not particularly limited.
- Polyurethane resin particles, polyester resin particles, nylon resin particles, silicone resin particles, polyethylene resin particles, and the like can be used.
- These powders preferably have an average particle diameter of about 0.1 to 10 ⁇ m.
- the shape of the particles is practically preferred to be spherical or substantially spherical because the matte property of the coating film to be formed is particularly excellent.
- the inorganic fine powder examples include talc, mica, calcium carbonate, barium sulfate, magnesium carbonate, clay, alumina, silica, carbon fiber, glass fiber, metal fiber, carbon black, titanium oxide, molybdenum, and magnesium hydroxide. , Bentonite, graphite and the like.
- the average particle size of the particles constituting these inorganic fine powders is 10 ⁇ m or less, which is suitable for the purpose of the present invention, but is preferably a powder having a particle size as small as possible.
- the addition amount of the matting agent mentioned above is about 1 to 150 parts by mass, preferably 3 to 60 parts by mass with respect to 100 parts by mass of the polysiloxane-modified polyhydroxypolyurethane resin. If the amount is less than 1 part by mass, the matte effect cannot be sufficiently obtained. On the other hand, if it exceeds 150 parts by mass, the mechanical properties of the coating film tend to be greatly reduced, which is not preferable.
- the polysiloxane-modified polyhydroxypolyurethane resin used in the present invention is derived from a reaction between a 5-membered cyclic carbonate compound and an amine-modified polysiloxane compound. For this reason, when the surface treatment layer is formed by coating and / or impregnating a polymer elastic material with the material of the present invention containing the resin, a 5-membered cyclic carbonate group in the structure of the resin.
- the hydroxyl group produced by reacting with an amine compound provides a further improvement in performance relative to the surface of the polymer elastic body.
- the hydroxyl group has hydrophilicity, the adhesion to the polymer elastic material can be improved, and an antistatic effect that cannot be achieved by the conventional product can be obtained. And if the surface treatment layer is formed by utilizing the reaction between the hydroxyl group in the resin and the crosslinking agent, it is possible to further improve the heat resistance, wear resistance and chemical resistance of the surface.
- a resin composition containing the polysiloxane-modified hydroxypolyurethane resin of the present invention or a resin composition comprising the resin and various additives as mentioned above (hereinafter referred to as “resin composition”).
- a film (surface treatment layer) formed by abbreviated as “product” can obtain a sufficient effect as it is, but it is also possible to form a crosslinked film using a crosslinking agent.
- any crosslinking agent that reacts with a hydroxyl group in the resin structure can be used, and is not particularly limited.
- an alkyl titanate compound or a polyisocyanate compound can be mentioned, and a known crosslinking agent conventionally used for crosslinking polyurethane resins is preferable.
- an adduct of a polyisocyanate having the structural formula as listed above and another compound can be used.
- the resin composition containing the polysiloxane-modified hydroxypolyurethane resin of the present invention has an adhesive property and a coating film in the case of forming a surface treatment layer by applying it to a polymer elastic body which is a base material of a weather strip.
- various conventionally known binder resins can be further mixed and used.
- the binder resin used at this time those capable of chemically reacting with a crosslinking agent such as the above-mentioned polyisocyanate adduct are preferable, but those having no reactivity can also be used in the present invention.
- binder resins are not particularly limited, and binder resins conventionally used for surface treatment of weatherstrips can be used.
- binder resins conventionally used for surface treatment of weatherstrips
- the amount used is 5 to 90 parts by weight, more preferably about 10 to 60 parts by weight, based on 100 parts by weight of the resin composition used in the present invention. May be added.
- the resin composition used in the present invention may further contain various coating additives such as a coating surface adjusting agent, a fluidity adjusting agent, an ultraviolet absorber, a dispersing agent, and an anti-settling agent, if necessary. May be.
- various coating additives such as a coating surface adjusting agent, a fluidity adjusting agent, an ultraviolet absorber, a dispersing agent, and an anti-settling agent, if necessary. May be.
- the resin composition containing the polysiloxane-modified hydroxypolyurethane resin of the present invention is coated and applied to a polymer elastic body as a weather strip base material by a known coating method such as brush coating, spraying, roll coating, gravure, or dipping.
- a coating method such as brush coating, spraying, roll coating, gravure, or dipping.
- the surface treatment layer can be formed at a desired position of the substrate.
- the slipperiness, abrasion resistance, heat resistance In weatherability and weather resistance a weather strip excellent in uniform matting effect can be obtained.
- the hydroxyl group in the structure of the polysiloxane-modified polyhydroxypolyurethane resin interacts strongly at the interface with the polymer elastic body that is the substrate, so that the formed surface treatment layer is superior to the substrate. Adhesiveness, flexibility, and antistatic effect are imparted. For this reason, the weather strip obtained by forming the surface treatment layer with the material of the present invention has excellent performance.
- the polysiloxane modified polyhydroxy polyurethane resin used in the present invention is obtained by reacting an epoxy compound and carbon dioxide with a 5-membered cyclic carbonate compound used for synthesis, carbon dioxide is taken into the resin. be able to.
- a weather strip that is useful from the viewpoint of reducing greenhouse gases and that has not been achieved with conventional products, and that is compatible with environmental conservation.
- the obtained solution was gradually added to 300 parts of n-hexane with high-speed stirring at 300 rpm, and the resulting powdery product was filtered through a filter, further washed with methanol, N-methylpyrrolidone and Sodium iodide was removed. Thereafter, the powder was dried in a drier to obtain 118 parts (yield 95%) of a white powder 5-membered cyclic carbonate compound (1-A).
- Examples 1 to 3 (Production of polysiloxane-modified polyhydroxypolyurethane resin) A reaction vessel equipped with a stirrer, a thermometer, a gas introduction tube and a reflux condenser was replaced with nitrogen, to which was added the 5-membered cyclic carbonate compound obtained in the previous Production Examples 1 to 3, and a solid content of 35 % N-methylpyrrolidone was added and dissolved uniformly. Next, a predetermined equivalent of the amine-modified polysiloxane compound shown in Table 1 was added, and the mixture was stirred at a temperature of 90 ° C. for 10 hours, and reacted until no amine-modified polysiloxane compound could be confirmed. Properties of the three types of polysiloxane-modified polyhydroxypolyurethane resins of Examples 1 to 3 obtained above are as shown in Table 1.
- a conventional polysiloxane-modified polyurethane resin of Comparative Example 3 was synthesized from diol and diamine as follows. Specifically, 150 parts of polydimethylsiloxane diol represented by the following formula (D) and having an average molecular weight of about 3,200 and 10 parts of 1,4-butanediol are mixed with 200 parts of methyl ethyl ketone and 50 parts of dimethyl ester. A mixed organic solvent composed of formamide was added, and 40 parts of water-added MDI dissolved in 120 parts of dimethylformamide was gradually added dropwise.
- D polydimethylsiloxane diol represented by the following formula (D) and having an average molecular weight of about 3,200 and 10 parts of 1,4-butanediol are mixed with 200 parts of methyl ethyl ketone and 50 parts of dimethyl ester.
- a mixed organic solvent composed of formamide was added, and 40 parts of water-added MDI dissolved in 120 parts of dimethyl
- This solution has a solid content of 35% and a viscosity of 1.6 MPa ⁇ s (25 ° C.).
- a film obtained from this solution has a breaking strength of 21 MPa and a breaking elongation of 250%, and the heat softening temperature is 135. ° C.
- Examples 4 to 9 and Comparative Examples 4 to 9> (Formation of heat-resistant protective layer) Using each of the polyurethane resin solutions (solid content 35%) of Examples 1 to 3 and Comparative Examples 1 to 3 prepared previously, a heat-resistant protective layer was formed on the surface of the base sheet.
- the resin solution is diluted with a solvent so that the thickness after drying becomes 0.2 ⁇ m, and a crosslinking agent is added as necessary as shown in Table 2 to add a coating composition (resin composition And the composition was applied to the surface of a polyethylene terephthalate film (manufactured by Toray) having a thickness of 3.5 ⁇ m by gravure printing and dried in a dryer to form a heat-resistant protective layer on the surface of the base sheet. . Further, a heat-sensitive recording layer (transfer ink layer) is formed on the surface of the base film (sheet) opposite to the formed heat-resistant protective layer to produce the heat-sensitive recording materials of Examples 4 to 9 and Comparative Examples 4 to 9. did. The formation of the transfer ink layer will be described later.
- thermosensitive recording layer (transfer ink layer) was formed on the surface of the base film (sheet) opposite to the formed heat-resistant protective layer to obtain a thermosensitive recording material of Comparative Example 10.
- a transfer ink layer was formed on the surface opposite to the polyethylene terephthalate film surface having the heat-resistant protective layer obtained above, and thermal recording materials of Examples 4 to 9 and Comparative Examples 4 to 10 were obtained. Specifically, an ink composition having the following composition is heated to 100 ° C. on the surface opposite to the surface of the polyethylene terephthalate film having the heat-resistant protective layer so that the coating thickness becomes 5 ⁇ m by a roll coating method using hot melt. was applied to form a transfer ink layer. As described above, thermal recording materials of Examples 4 to 9 and Comparative Examples 4 to 10 using the resins of Examples and Comparative Examples were obtained.
- Printing conditions for mounting test of thermal recording material Printer: Zebra 100XiIIIPlus Thermal head: Kyocera KPA-106-12TA (flat) Printing energy: 25 mJ / mm 2 Printing speed: 100mm / sec Platen pressing: 350 gf / cm Receiving paper; cast coated paper (manufactured by Lintec) Printing pattern: CODE39 vertical bar code under printing conditions of 30mm wide and 40mm long
- the contamination of the thermal head was evaluated by visually observing the contamination state of the thermal head after being subjected to a thermal recording mounting test.
- the evaluation standard was 5 with the least contamination and 1 with the least contamination, with a relative 5-level evaluation.
- Adhesiveness In the adhesion test, a 10 ⁇ 10 grid cellophane tape peeling test was performed on the “heat-resistant protective layer” formed on the back surface of the heat-sensitive recording material, and the remaining number after peeling was evaluated.
- Examples 10 to 12, Comparative Examples 11 to 13; artificial leather First, the obtained artificial leather paint was applied onto a nonwoven fabric made of polystyrene-polyester fibers so as to have a thickness of 1 mm. This was immersed in an aqueous solution of DMF 10% at 25 ° C. and solidified. After washing, it was dried by heating to obtain an artificial leather having a porous layer sheet.
- Examples 13 to 15, Comparative Examples 14 to 16; synthetic leather A polyurethane-based resin solution (trade name: Rezamin UD-602S, manufactured by Dainichi Seika Kogyo Co., Ltd.) is applied onto the woven fabric as an adhesive layer and dried to a thickness of 10 ⁇ m. A leather base fabric sheet was prepared. On the other hand, the artificial leather paint containing each resin obtained in Examples 1 to 3 and Comparative Examples 1 to 3 was applied on a release paper and dried to form a film having a thickness of about 15 ⁇ m. Each synthetic leather was obtained by pasting it on the base fabric sheet obtained in the above.
- a polyurethane-based resin solution trade name: Rezamin UD-602S, manufactured by Dainichi Seika Kogyo Co., Ltd.
- thermoplastic polyolefin resin skin material ⁇ Examples 16 to 21, Comparative Examples 17 to 22>
- thermoplastic polyolefin resin skin material Using the resins of Examples 1 to 3 and Comparative Examples 1 to 3, the main coating compositions described in Tables 6 and 7 were prepared, respectively, and using them, thermoplastic polyolefin resins were used as follows. A skin material was prepared. Each obtained skin material was evaluated by the following method.
- the molded product made of each skin material obtained above has moldability, gloss (glossiness), coefficient of friction, adhesion, scratch resistance, oil resistance, chemical resistance, surface wear resistance, and environmental compatibility. Evaluation was performed by the following methods and criteria. In particular, the surface (topcoat layer) of the molded product made of each sheet was evaluated. The results are shown in Tables 6 and 7.
- Beef oil (Nacalai Tech Co., Ltd.) was applied to a 2 cm radius on the surface of the sheet after vacuum forming, and allowed to stand at 80 ° C. for 5 days. After that, the beef oil was removed, and a peel test using a grid cellophane tape was performed on the removed beef oil application surface for evaluation.
- the surface friction tester (made by Shinto Kagaku) evaluated the static friction coefficient and the dynamic friction coefficient of each weatherstrip material (paint) with the glass member.
- the contact angle of water in the film portion of the measurement sample obtained above was measured with a contact angle meter (manufactured by Kyowa Interface Chemical Co., Ltd.) and used as the contact angle of water on the coating film surface made of each weatherstrip material.
- the film portion of the measurement sample obtained above was subjected to a peel test using a cross cellophane tape, and the adhesion of the coating film surface made of each weather strip material was evaluated according to the following criteria. ⁇ : Good (no peeling part on the coating surface) X: Defect (there is a peeling site on the coating surface)
- the present invention it is excellent in lubricity, abrasion resistance, chemical resistance, non-adhesiveness, antistatic property, heat resistance, etc., and can be substituted for conventional petrochemical plastic, film / molding material, various coating materials,
- a novel polysiloxane-modified polyhydroxypolyurethane resin useful as a binder or the like is provided. Since the resin provided in the present invention can use carbon dioxide as a production raw material, the present invention makes it possible to provide a global environment-friendly product that can contribute to the reduction of carbon dioxide, which is a warming gas. Its wide use is expected. For example, it can be used in the following fields, and by using the resin of the present invention, it is a product compatible with the global environment, but is comparable to or more than when using conventional petrochemical plastic materials. A product with the new performance can be obtained.
- the polysiloxane segment in the resin is oriented on the surface, whereby the heat resistance, slipping property of the polysiloxane segment, Non-adhesiveness to the thermal head can be imparted.
- the hydroxyl group of the polysiloxane-modified polyhydroxypolyurethane resin strongly interacts with the substrate sheet at the interface, thereby providing excellent adhesion and flexibility to the substrate of the heat-resistant protective layer and antistatic effect.
- a heat-sensitive recording material having a heat-resistant protective layer exhibiting excellent performance can be obtained.
- the resin composition having the resin main component of the present invention as the artificial leather, it is possible to achieve excellent flexibility, lubricity, scratch resistance, abrasion resistance, and chemical resistance.
- the hydroxyl group in the structure of the polysiloxane-modified polyhydroxypolyurethane resin interacts strongly with the base fabric (base sheet) at the interface, resulting in excellent adhesion and flexibility to the base fabric, and antistatic effect. Excellent performance can be obtained.
- composition containing the polysiloxane-modified polyhydroxypolyurethane resin of the present invention for the topcoat layer of the thermoplastic polyolefin resin sheet constituting the outer surface material made of thermoplastic polyolefin resin used as a vehicle interior material, etc., from the sheet
- the resulting molded product has a polysiloxane segment in the resin oriented on the surface, excellent in lubricity, surface feel, scratch resistance, abrasion resistance and chemical resistance, and also in a uniform matte effect It becomes.
- the hydroxyl group of the polysiloxane-modified polyhydroxypolyurethane resin forming the topcoat layer interacts strongly with the base sheet at the interface, thereby exhibiting excellent adhesion and flexibility and antistatic properties. An excellent performance that an effect is imparted can be obtained.
- the resin composition containing the polysiloxane-modified polyhydroxypolyurethane resin of the present invention When the material for weatherstrip is coated and / or impregnated with a polymer elastic material (base sheet) by using the resin composition containing the polysiloxane-modified polyhydroxypolyurethane resin of the present invention. It is possible to form a film with excellent slipperiness, wear resistance, heat resistance, weather resistance and uniform matte effect, and the hydroxyl group of the polysiloxane-modified polyhydroxypolyurethane resin strongly interacts with the base sheet at the interface. By acting, it is possible to obtain a film with excellent performance imparted with excellent adhesion and flexibility and antistatic effect.
Abstract
Description
(1)背面の耐熱保護層がポリシロキサン変性ポリヒドロキシポリウレタン樹脂からなる、熱溶融型熱転写方式や昇華型熱転写方式に有用である感熱記録材料。
(2)ポリシロキサン変性ポリヒドロキシポリウレタン樹脂を主成分とする組成物を使用して得られる、風合い、滑性、耐擦傷性、耐摩耗性、耐薬品性に優れる擬革。
(3)トップコート層の形成にポリシロキサン変性ポリヒドロキシポリウレタン樹脂を用いた自動車の内装材や家電部品などに使用される、表面が、滑性、表面感触、耐擦傷性、耐摩耗性、耐薬品性に優れ、また、均一な艶消し皮膜を形成し得る熱可塑性ポリオレフィン樹脂製表皮材。
(4)高分子弾性体材料を基材とするウェザーストリップの、他部品と摺接する摺接部に形成する表面処理層にポリシロキサン変性ポリヒドロキシポリウレタン樹脂を用いることで、滑性、耐摩耗性、耐熱性、耐候性に優れた表面処理層が形成されたウェザーストリップ。
一方、増加の一途をたどる二酸化炭素の排出に起因すると考えられる地球の温暖化現象が、近年、世界的な問題となっており、二酸化炭素の排出量低減は、全世界的に重要な課題となっており、二酸化炭素を製造原料とできる技術は待望されている。更に、枯渇性石化資源(石油)問題の観点からも、バイオマス、メタンなどの再生可能資源への転換が世界的潮流となっている。
従来より、ポリエステルフィルムなどの基材シートの一方の面に、染料又は顔料をバインダー樹脂などで担持させて感熱記録層(インク層)を形成し、その裏面からパターン状に加熱してインク層を被転写材に転写する熱溶融型感熱記録材料や、更には、染料として加熱昇華性の染料を使用し、同様に染料のみを被転写材に昇華転写する昇華転写記録材料が公知である。
従来、袋物、鞄、靴、家具、衣料、車両内装材、電化製品などに擬革が使用されているが、この擬革用樹脂として、広くポリウレタン系樹脂が使用されている。この「擬革」とは、天然皮革に似せて製造される皮革状製品の総称で、一般的には、人工皮革、合成皮革、塩化ビニルレザーに大別される。
車両内装材(インストルメントパネル、ドアトリムなど)や家電部品は、近年のゴミ問題及び環境問題に鑑み、使用後の廃材をできるだけ低減するため、これら部材のリサイクル化が強く望まれている。この観点から、近年、熱可塑性ポリオレフィン、例えば、ポリプロピレン(PP)、ABS樹脂、AS樹脂、ポリオレフィン系熱可塑性エラストマー(TPO)等が、車両内装材や家電部品の表皮材として使用されている。しかしながら、これらの熱可塑性ポリオレフィンは、表面の接着性、耐擦傷性、耐摩耗性、耐薬品性が、従来使用されていた塩化ビニル樹脂などに比べ劣るため、これらの性能向上を目的として塗装を施す必要がある。また、高級感を与えるために意匠性を持たせたり、特に自動車内装材の場合には、意匠性だけでなく、運転者への防眩性の配慮などを考える必要もある。このため、熱可塑性ポリオレフィン基材に種々の塗装を施してトップコート層を形成することで、より良好な表皮材とするための表面への機能付与が行われている。
従来、自動車や建築物の、グラスラン、ドアウェザーストリップ、ボディサイドウェザーストリップ、インサイドシール、アウトサイドシールなどのウェザーストリップの形成材料としては、クロロプレンゴム、スチレン-ブタジエンゴム、ニトリルゴム、EPDMゴムなどの高分子弾性体材料が用いられている。そして、これらの表面には、滑性、耐摩耗性、離型性、耐熱性、耐水性、耐候性などの性能を持たせるため、塗布または含浸などの方法によって表面処理層を形成することが行われている。
したがって、本発明の目的は、それぞれの用途で要求されている特性を満足でき、しかも、二酸化炭素を製造原料とすることができる、地球環境保全の観点からも優れた環境対応製品の提供を可能にし得る新たな樹脂を開発することにある。
近年の印字の高速化に伴うサーマルヘッドの高温化や基材シートの薄膜化に伴い、背面の耐熱保護層には、更なる耐熱性、滑り性及び非粘着性、更にはフィルム剥離時などに発生する静電気対策などが求められる。それと共に、従来の感熱記録媒体(材料)は、使用後の商品のリサイクルも難しく、大量の廃棄物となっていた点について改善する必要がある。
すなわち、耐熱性、滑り性及び非粘着性に優れた耐熱保護層を有する感熱記録材料でありながら、地球環境保全の観点からも、優れた環境対応製品を提供し得る技術の開発が求められている。
擬革に関しては、より一層の柔軟性、更には、表面の滑性、耐擦傷性、耐摩耗性、耐薬品性に優れると共に、地球規模での環境保全性を持った環境対応製品の開発が要望される。
車両内装材や家電部品に使用される熱可塑性ポリオレフィン樹脂表皮材に関しては、より一層の表面の、耐擦傷性、耐摩耗性及び耐薬品性、更には、必要に応じて均一な艶消し効果にも優れると共に、地球規模での環境保全性を持った環境対応製品の開発が要望されている。
すなわち、上記した優れた特性を有する熱可塑性ポリオレフィン樹脂表皮材であることに加え、優れた環境対応製品である熱可塑性ポリオレフィン樹脂表皮材を提供し得る技術の開発が求められている。
自動車や建築物のウェザーストリップに、塗布または含浸などの方法によって設けられる表面処理層を、特に、滑性、耐摩耗性、耐熱性及び耐候性などの基本特性に優れると共に、地球規模での環境保全性を持った環境対応製品とできれば、非常に有用である。
したがって、ウェザーストリップを構成する高分子弾性体材料の、他部品と摺接する摺接部に表面処理層を形成するための材料が、環境保全性に資する材料でありながら、形成した表面処理層が、滑性、耐摩耗性、耐熱性、耐候性に優れたものとなる有用な材料を提供する技術が求められている。
本発明では、背面の耐熱保護層を、ポリシロキサン変性ポリヒドロキシポリウレタン樹脂を用いて形成することにより、該耐熱保護層の、耐熱性、滑り性、非粘着性、及び基材シートに対する接着性、更に帯電防止効果などにも優れる感熱記録材料の提供を可能とする。上記の樹脂は、このように優れた感熱記録材料を提供できると同時に、二酸化炭素を原料とし得、樹脂中に二酸化炭素を取り入れることができるので、温暖化ガス削減に寄与する環境対応製品としても有用な感熱記録材料の提供が可能となる。
本発明によれば、従来品の擬革と遜色がない風合いを持ち、更に、表面の滑性、耐擦傷性、耐摩耗性、耐薬品性に優れる擬革が提供される。これと共に、二酸化炭素を樹脂中に取り入れ固定した樹脂を擬革の形成材料に利用することが可能であり、温暖化ガスとして世界的に問題視されている二酸化炭素削減にも寄与できる、地球環境保全の観点からも優れた環境対応製品の擬革が提供される。
本発明では、熱可塑性ポリオレフィン樹脂表皮材を構成するトップコート層の形成材料に特定のポリシロキサン変性ポリヒドロキシポリウレタン樹脂を用いることで、その表面の、滑性、表面感触、耐擦傷性、耐摩耗性及び耐薬品性、必要に応じて、均一な艶消し効果に優れる熱可塑性ポリオレフィン樹脂表皮材の提供を可能にする。これと共に、二酸化炭素を樹脂中に取り入れ固定した樹脂をトップコート層の形成材料に利用できることから、温暖化ガスとして世界的に問題視されている二酸化炭素削減にも寄与できる、環境対応製品でもある熱可塑性ポリオレフィン樹脂表皮材が提供される。
本発明によれば、自動車や建築物のウェザーストリップの基材である高分子弾性体材料の、他部品と摺接する摺接部に表面処理層を形成するための有用な材料が、環境保全性にも資する材料でありながら、形成した表面処理層が、滑性、耐摩耗性、耐熱性、耐候性に優れたものとなる有用な材料が提供される。より具体的には、本発明では、高分子弾性体の表面処理用塗料組成物として、ポリシロキサン変性ポリヒドロキシポリウレタン樹脂からなる組成物を用いるため、形成した表面処理層が、上記した基本特性に優れたものとなることに加え、その製造原料に、地球温暖化ガスとされている二酸化炭素を利用できるため、地球環境保全の観点からも有用な材料、及び、該材料を用いてなる環境対応製品の提供が可能になる。
<ポリシロキサン変性ポリヒドロキシポリウレタン樹脂>
本発明のポリシロキサン変性ポリヒドロキシポリウレタン樹脂(以下、単に「本発明の樹脂」或いは「本発明で使用する樹脂」と呼ぶ場合もある)は、5員環環状カーボネート化合物とアミン変性ポリシロキサン化合物との反応から誘導されたことを特徴とする。また、この5員環環状カーボネート化合物は、例えば、下記[式-A]で示されるように、エポキシ化合物と二酸化炭素とを反応させて製造することができる。更に詳しくは、エポキシ化合物を、有機溶媒の存在下又は不存在下、及び触媒の存在下、40℃~150℃の温度で常圧又は僅かに高められた圧力下、10~20時間二酸化炭素と反応させることによって得られる。
本発明の感熱記録材料は、基材シートの一方の面に感熱記録層が設けられ、そして他方の背面に耐熱保護層が形成されているが、該耐熱保護層を構成する高分子化合物が上記したポリシロキサン変性ポリヒドロキシポリウレタン樹脂であることを特徴とする。すなわち、本発明の感熱記録材料は、その耐熱保護層が、5員環環状カーボネート化合物とアミン変性ポリシロキサン化合物との反応から誘導された本発明のポリシロキサン変性ポリヒドロキシポリウレタン樹脂からなる、或いは該樹脂を含む樹脂組成物からなることを特徴とする。
本発明の擬革は、先に説明した、5員環環状カーボネート化合物とアミン変性ポリシロキサン化合物との反応から誘導された本発明のポリシロキサン変性ポリヒドロキシポリウレタン樹脂を主成分とする樹脂組成物を、基布に充填或いは積層せしめてなることを特徴とする。
本発明の熱可塑性ポリオレフィン樹脂製表皮材は、熱可塑性ポリオレフィン樹脂シート上に直接、塗布形成されたトップコート層を有するか、或いは、該樹脂シート上に塗布されたプライマー層と、該プライマー層上に塗布形成されたトップコート層とを有するものである。そして、上記トップコート層を構成する高分子化合物として、5員環環状カーボネート化合物とアミン変性ポリシロキサン化合物との反応から誘導される、先に説明した本発明のポリシロキサン変性ポリヒドロキシポリウレタン樹脂を用いることを特徴とする。
本発明のウェザーストリップ用材料は、高分子弾性体材料に被覆及び/または含浸させて、他部品と摺接する摺接部に表面処理層を形成するための材料であって、5員環環状カーボネート化合物と、アミン変性ポリシロキサン化合物との反応から誘導された本発明のポリシロキサン変性ポリヒドロキシポリウレタン樹脂を含んでなる樹脂組成物であることを特徴とする。
(製造例1;5員環環状カーボネート化合物の製造)
攪拌機、温度計、ガス導入管及び還流冷却器を備えた反応容器中に、下記式Aで表される2価エポキシ化合物100部、N-メチルピロリドン100部、ヨウ化ナトリウム1.5部を加え均一に溶解させた。その後、これに、炭酸ガスを、0.5リッター/分の速度でバブリングしながら、80℃で30時間加熱攪拌した。上記で使用した2価エポキシ化合物は、ジャパンエポキシレジン(株)製のエピコート828(エポキシ当量187g/mol)であり、図1にその赤外吸収スペクトルを示した。
本製造例では、先の製造例1で用いた2価エポキシ化合物Aの代わりに、下記式Bで示される2価エポキシ化合物B(東都化成(株)製、YDF-170;エポキシ当量172g/mol)を用いた。そして、これ以外は、製造例1と同様に反応させて、白色粉末の5員環環状カーボネート化合物(1-B)121部(収率96%)を得た。得られた生成物(1-B)を、製造例1の場合と同様に、赤外吸収スペクトル、GPC、NMRで確認した。得られた5員環環状カーボネート化合物(1-B)中には、20.3%の二酸化炭素が固定化されていた。
本製造例では、先の製造例1で用いた2価エポキシ化合物Aの代わりに、下記式Cで示される2価エポキシ化合物C(ナガセケムテックス(株)製、EX-212;エポキシ当量151g/mol)を用いた。そして、これ以外は、製造例1と同様に反応させて、無色透明の液状5員環環状カーボネート化合物(1-C)111部(収率86%)を得た。得られた生成物は、製造例1の場合と同様に、赤外吸収スペクトル、GPC、NMRで確認した。得られた5員環環状カーボネート化合物(1-C)中には、22.5%の二酸化炭素が固定化されていた。
攪拌機、温度計、ガス導入管及び還流冷却器を備えた反応容器を窒素置換し、これに、先の製造例1~3で得られた5員環環状カーボネート化合物を加え、更に固形分が35%になるようにN-メチルピロリドンを加え均一に溶解した。次に、表1に記載のアミン変性ポリシロキサン化合物を所定当量加え、90℃の温度で10時間攪拌し、アミン変性ポリシロキサン化合物が確認できなくなるまで反応させた。
上記で得られた実施例1~3の3種類のポリシロキサン変性ポリヒドロキシポリウレタン樹脂の性状は、表1に記載の通りである。
攪拌機、温度計、ガス導入管及び還流冷却器を備えた反応容器を窒素置換し、これに、先の製造例1で得られた5員環環状カーボネート化合物を加え、更に固形分が35%になるようにN-メチルピロリドンを加え均一に溶解した。次に、ヘキサメチレンジアミンを所定当量加え、90℃の温度で10時間攪拌し、アミン化合物が確認できなくなるまで反応させた。得られたポリシロキサンセグメントを有さないポリヒドロキシポリウレタン樹脂の性状は、表1に記載の通りである。
下記のようにして、ポリエステルとジオールとジアミンとから従来の比較例2のポリエステルポリウレタン樹脂を合成した。攪拌機、温度計、ガス導入管及び還流冷却器を備えた反応容器を窒素置換し、該容器内に、平均分子量約2,000のポリブチレンアジペート150部と、1,4-ブタンジオール15部とを、200部のメチルエチルケトンと、50部のジメチルホルムアミドからなる混合有機溶剤中に溶解した。その後、60℃でよく攪拌しながら、62部の水添加MDIを、171部のジメチルホルムアミドに溶解したものを徐々に滴下し、滴下終了後80℃で6時間反応させた。
この溶液は固形分35%で3.2MPa・s(25℃)の粘度を有していた。この溶液から得られたフィルムは、破断強度45MPaで、破断伸度480%を有し、熱軟化温度は110℃であった。
下記のようにして、ジオールとジアミンとから従来の比較例3のポリシロキサン変性ポリウレタン樹脂を合成した。具体的には、下記式(D)で表され、且つ平均分子量が約3,200であるポリジメチルシロキサンジオール150部及び1,4-ブタンジオール10部を、200部のメチルエチルケトンと50部のジメチルホルムアミドからなる混合有機溶媒を加え、又、40部の水添加MDIを、120部のジメチルホルムアミドに溶解したものを徐々に滴下し、滴下終了後、80℃で6時間反応させた。この溶液は、固形分35%で1.6MPa・s(25℃)の粘度を有し、この溶液から得られたフィルムは破断強度21MPaで破断伸度250%を有し、熱軟化温度は135℃であった。
<実施例4~9及び比較例4~9>
(耐熱保護層の形成)
先に調製した実施例1~3及び比較例1~3の各ポリウレタン樹脂溶液(固形分35%)をそれぞれ用い、基材シート表面に耐熱保護層をそれぞれ形成した。具体的には、乾燥後の厚みが0.2μmになるように上記樹脂溶液を溶剤で希釈して、表2に示したように必要に応じて架橋剤を添加して塗料組成物(樹脂組成物)を得、該組成物を、厚み3.5μmのポリエチレンテレフタレートフィルム(東レ製)の表面に、グラビア印刷により塗布し、乾燥機中で乾燥して基材シート表面に耐熱保護層を形成した。さらに、形成した耐熱保護層の反対側の基材フィルム(シート)面に、感熱記録層(転写インキ層)を形成して実施例4~9及び比較例4~9の各感熱記録材料を作製した。転写インキ層の形成については後述する。
シリコーン樹脂(KS-841、信越化学工業(株)製)100部と、触媒(PL-7、信越化学工業(株)製)1部とをトルエン1,000部に溶解して、シリコーン樹脂の本比較例の塗料組成物を作製した。そして、上記と同様に基材シート上に塗布し耐熱保護層を形成した。さらに、形成した耐熱保護層の反対側の基材フィルム(シート)面に、感熱記録層(転写インキ層)を形成して比較例10の感熱記録材料とした。
以上で得た耐熱保護層を有するポリエチレンテレフタレートフィルム面の反対側の面に、転写インキ層を形成し、実施例4~9及び比較例4~10の各感熱記録材料を得た。具体的には、耐熱保護層を有するポリエチレンテレフタレートフィルム面の反対側の面に、下記組成のインキ組成物を100℃に加熱して、ホットメルトによるロールコート法にて塗布厚みが5μmになるように塗布して、転写インキ層を形成した。以上のようにして実施例及び比較例の各樹脂を用いた実施例4~9及び比較例4~10の感熱記録材料をそれぞれ得た。
・パラフィンワックス 10部
・カルナバワックス 10部
・ポリブテン(日本石油製) 1部
・カーボンブラック 2部
以上ようにして得られたフィルム状の各感熱記録材料を用いて、下記の印字条件で印字を行い、感熱記録の実装試験をした。そして、スティッキング性、サーマルヘッド汚染性、基材への接着性、静止摩擦係数、帯電性、環境対応度等を以下の方法でそれぞれ評価し、感熱記録材料の背面に形成した「耐熱保護層」を評価した。表3に評価結果をまとめて示した。
プリンター;Zebra社100XiIIIPlus
サーマルヘッド;京セラ製 KPA-106-12TA(フラット)
印字エネルギー;25mJ/mm2
印字スピード;100mm/sec
プラテン押圧;350gf/cm
受容紙;キャストコート紙(リンテック社製)
印字パターン;コード巾30mm長さ約40mmの印字条件において、CODE39タテバーコード
スティッキング性は、感熱記録の実装試験に供した場合の、サーマルヘッドとの間の押圧操作時における「耐熱保護層」のサーマルヘッドからの離脱性を目視で観察し、評価した。評価基準は、最も離脱性の良いものを5とし、最も離脱性の悪いものを1とし、相対的に5段階評価した。
サーマルヘッドの汚れは、感熱記録の実装試験に供した後のサーマルヘッドの汚れの状態を目視で観測して評価した。評価基準は、最も汚れの少ないものを5とし、最も汚れのひどいものを1とし、相対的に5段階評価した。
接着性試験は、感熱記録材料の背面に形成されている「耐熱保護層」に対して、10×10個の碁盤目セロハンテープ剥離試験を行って、剥離後の残った個数で評価した。
静止摩擦係数は、「耐熱保護層」について表面性試験機(新東科学製)を用いて測定し、評価した。
更に、帯電性は、フィルム状の感熱記録材料を、巻物の状態から急激に剥離した時に発生する静電気によるフィルム同士のブロッキング性を目視で観測し、ブロッキングが発生した場合を×、発生しない場合を○として評価した。環境対応度は、「耐熱保護層」の形成材料中における二酸化炭素の固定化の有無で、○×判断した。
<実施例10~15、比較例11~16>
先に得た実施例1~3、比較例1~3の各樹脂溶液をそれぞれ使用して、表4、5に記載した主組成の擬革用塗料を作製し、人工皮革及び合成皮革を得た。そして、得られた人工皮革及び合成皮革について評価した。
まず、先に得た擬革用塗料を、厚さ1mmとなるように、ポリスチレン-ポリエステル繊維からなる不織布上に塗布した。これを、25℃のDMF10%の水溶液中に浸漬し、凝固させた。洗浄後、加熱乾燥し、多孔層シートを有する人工皮革を得た。
織布上に接着剤層としてポリウレタン系樹脂溶液(商品名:レザミンUD-602S、大日精化工業(株)製)を、乾燥時の厚さが10μmとなるように塗布及び乾燥して、擬革用基布シートを作成した。一方、実施例1~3及び比較例1~3で得た各樹脂を含む擬革用塗料を、それぞれ離型紙上に塗布及び乾燥させ、約15μmの厚さのフィルムを形成し、これを上記で得た基布シートに貼り合せて、各合成皮革を得た。
上記で得た各人工皮革及び合成皮革の各擬革について、下記の方法及び基準で評価した。人工皮革については表4に、合成皮革については表5に、それぞれ評価結果をまとめて示した。
各擬革について、手の感触により判定し、下記の基準で評価した。
○;軟らかい
△;やや硬い
×;硬い
上記で得た各人工皮革表面の摩擦係数を、表面性試験機(新東科学製)を用いて測定し、評価した。
上記で得た各合成皮革表面に、トルエンをそれぞれ滴下し、常に濡れている状態を保つため溶剤を追加滴下し、1時間後に拭き取った。拭き取った滴下部分を目視で観察して、下記の基準で評価した。
○;塗布面に滴下痕が全く見られない
△;僅かに滴下痕が認められるが目立たない
×;滴下痕が明らかに認められる
上記で得た各合成皮革について、平面摩耗試験機を用い、6号帆布を荷重1kgfで、擦り傷が発生するまでの回数を測定した。
○;5,000回以上
△;2,000回以上~5,000回未満
×;2,000回未満
各擬革について、使用した樹脂中における二酸化炭素の固定化の有無によって、○×判断した。
<実施例16~21、比較例17~22>
[熱可塑性ポリオレフィン樹脂表皮材の製造]
実施例1~3、比較例1~3の各樹脂を使用し、表6、7に記載した主配合の表皮用塗料をそれぞれに作製し、これを用いて下記のようにして熱可塑性ポリオレフィン樹脂表皮材を作製した。得られた各表皮材を下記の方法で評価した。
上記で得た各表皮材からなる成型品について、成形性、グロス性(光沢性)、摩擦係数、接着性、耐擦傷性、耐油性、耐薬品性、耐表面摩耗性、環境対応性をそれぞれ下記の方法及び基準で評価した。特に、各シートからなる成型品の表面(トップコート層)について評価した。結果を表6、表7に示した。
真空成形後のシート表面を目視で観察し評価した。
○;良好(成型割れや白化現象なし)
×;不良(成型割れ又は白化現象のどちらかが認められる)
真空成形後のシート表面の光沢を、JIS K5600に準じたグロスメーターにて測定し、グロス値が1.2以下(業界の求める基準値)を合格とする。
真空成形後のシート表面の摩擦係数を、表面性試験機(新東科学製)で測定し、評価した。摩擦係数が低い程、車内装材の表面同士の擦れによる異音(きしみ音)が少なくなるので、0.2以下が望ましいとした。
真空成形後のシート表面に対し、碁盤目セロハンテープによる剥離試験を行って下記の基準で評価した。
○;良好(塗布面に剥離部分がない)
×;不良(塗布面に剥離部位がある)
真空成形後のシート表面を爪でこすり、傷跡や白化が生じないかを目視判定で、下記の基準で評価した。
○;良好(塗布面の爪傷・白化を判別し難い)
×;不良(塗布面の爪傷・白化跡が明瞭に判別できる)
真空成形後のシート表面に牛油(ナカライテク(株))を2cm半径に塗布し、80℃雰囲気で5日間放置した。その後に牛油を除去し、除去した牛油の塗布面に対して、碁盤目セロハンテープによる剥離試験を行って評価した。
真空成形後のシート表面にエタノールをそれぞれ滴下し、常に濡れている状態を保つため溶剤を追加滴下し、1時間後に拭き取った。拭き取った部分を目視で観察して、下記の基準で評価した。
○;塗布面に滴下痕が全く見られない
△;僅かに滴下痕が認められるが目立たない
×;滴下痕が明らかに認められる
真空成形後のシート表面を、平面摩耗試験機を用い、6号帆布を荷重1kgfで擦り傷が発生するまでの回数を測定し、下記の基準で評価した。
○;5000回以上
△;2000回以下~5000回未満
×;2000回未満
表皮材のトップコート層の形成に使用した樹脂中における二酸化炭素の固定化の有無によって、○×判断した。
<実施例22~27、比較例23~26>
実施例1~3、比較例2、3の各ポリウレタン樹脂を使用して、表2に記載の主配合で塗料をそれぞれ作成し、実施例22~27、比較例23~26の各ウェザーストリップ用材料とした。また、これらの塗料を、EPDMゴムシート上にエアースプレーガンを用いて塗工した後、100℃で10分間乾燥させて20μmの皮膜を形成した。このようにして得られた塗膜面を有するEPDMゴムシートを、各ウェザーストリップ用材料によって形成した表面処理層(塗膜面)を評価するための測定用試料とした。
上記で調製した各ウェザーストリップ用材料及び各測定用試料について、静止摩擦係数、動摩擦係数、接触角、接着性、磨耗耐久性、耐候性などを以下の方法でそれぞれ測定し、実施例及び比較例の材料について評価した。評価結果を表8にまとめて示した。
各ウェザーストリップ用材料(塗料)の、ガラス部材との静止摩擦係数、動摩擦係数を表面性試験機(新東科学製)で評価した。
上記で得た測定用試料の皮膜部分における水の接触角を、接触角計(協和界面化学社製)で測定し、各ウェザーストリップ用材料からなる塗膜面の水の接触角とした。
上記で得た測定用試料の皮膜部分に対して、碁盤目セロハンテープによる剥離試験を行って、各ウェザーストリップ用材料からなる塗膜面の接着性を、下記の基準で評価した。
○;良好(塗膜面に剥離部分がない)
×;不良(塗膜面に剥離部位がある)
上記で得た測定用試料の皮膜部分に、9.8Nの荷重を加えたガラス板を当接し、該ガラス板を往復運動させることによる塗膜の裂傷などが生じるまでの往復運動回数を、表面性試験機(新東科学製)で測定した。そして、得られた往復運動回数で、各ウェザーストリップ用材料からなる塗膜面の磨耗耐久性を評価した。
サンシャインカーボンアーク耐候試験機(スガ試験機)を用い、上記で得た測定用試料の皮膜部分にパネル温度83℃で200時間照射後、その塗膜面の状態を目視で観察し、各ウェザーストリップ用材料からなる塗膜面の耐候性を、下記の基準で評価した。
3:表面状態変化なし
2:表面状態少し変化あり
1:大きな変化及び白化現象
各ウェザーストリップ用材料(塗料)中における二酸化炭素の固定化の有無によって、○×で評価した。
Claims (24)
- 5員環環状カーボネート化合物とアミン変性ポリシロキサン化合物との反応から誘導されてなることを特徴とするポリシロキサン変性ポリヒドロキシポリウレタン樹脂。
- 前記5員環環状カーボネート化合物が、エポキシ化合物と二酸化炭素とを反応させて得られたものである請求項1に記載のポリシロキサン変性ポリヒドロキシポリウレタン樹脂。
- 原料由来の二酸化炭素を1~25質量%含有してなる請求項2に記載のポリシロキサン変性ポリヒドロキシポリウレタン樹脂。
- 前記樹脂の分子中に占めるポリシロキサンセグメントの含有量が、1~75質量%である請求項1乃至3のいずれか1項に記載のポリシロキサン変性ポリヒドロキシポリウレタン樹脂。
- 請求項1乃至4のいずれか1項に記載のポリシロキサン変性ポリヒドロキシポリウレタン樹脂と、他の樹脂を混合してなることを特徴とするポリシロキサン変性ポリヒドロキシポリウレタン樹脂含有組成物。
- 請求項1乃至4のいずれか1項に記載のポリシロキサン変性ポリヒドロキシポリウレタン樹脂と、該樹脂の構造中に存在する水酸基と反応する架橋剤とを含むことを特徴とするポリシロキサン変性ポリヒドロキシポリウレタン樹脂組成物。
- エポキシ化合物と二酸化炭素とを反応させて得られた5員環環状カーボネート化合物と、アミン変性ポリシロキサン化合物との反応から誘導することを特徴とするポリシロキサン変性ポリヒドロキシポリウレタン樹脂の製造方法。
- 基材シート、該基材シートの少なくとも一方の面に設けた感熱記録層及び他の面のサーマルヘッドと当接する背面に耐熱保護層を有し、該耐熱保護層が、請求項1乃至4のいずれか1項に記載のポリシロキサン変性ポリヒドロキシポリウレタン樹脂を少なくとも含む樹脂組成物によって形成されていることを特徴とする感熱記録材料。
- 前記樹脂組成物が、更に他の樹脂を含む請求項8に記載の感熱記録材料。
- 前記耐熱保護層が、ポリシロキサン変性ポリヒドロキシポリウレタン樹脂の構造中に存在する水酸基と、該水酸基と反応する架橋剤との反応によって架橋してなる皮膜である請求項8又は9に記載の感熱記録材料。
- 前記基材シートの厚みが、2.5μm~4.5μmで表せる範囲のものである請求項8乃至10のいずれか1項に記載の感熱記録材料。
- 前記耐熱保護層の厚みが、0.001~2.00μmの範囲である請求項8乃至11のいずれか1項に記載の感熱記録材料。
- 請求項1乃至4のいずれか1項に記載のポリシロキサン変性ポリヒドロキシポリウレタン樹脂を主成分とする樹脂組成物を、基布に、充填或いは積層せしめてなることを特徴とする擬革。
- 前記樹脂組成物が、更に他の樹脂を含む請求項13に記載の擬革。
- 基布に充填或いは積層せしめた前記樹脂組成物中の前記ポリシロキサン変性ポリヒドロキシポリウレタン樹脂が、該樹脂の構造中に存在する水酸基と、該水酸基と反応する架橋剤との反応によって架橋されている請求項13又は14に記載の擬革。
- 熱可塑性ポリオレフィン樹脂シートと、該シート上に直接形成されたトップコート層、又は、上記シート上に形成されたプライマー層を介して形成されたトップコート層のいずれかを有し、且つ、トップコート層が、請求項1乃至4のいずれか1項に記載のポリシロキサン変性ポリヒドロキシポリウレタン樹脂を主成分としてなることを特徴とする熱可塑性ポリオレフィン樹脂製表皮材。
- 前記トップコート層が、前記ポリシロキサン変性ポリヒドロキシポリウレタン樹脂100質量部に対して、艶消剤として、有機系微粉末或いは無機系微粉末から選ばれる一種又は二種以上の組み合わせからなる物質を1~150質量部の割合で配合した組成物によって形成されている請求項16に記載の熱可塑性ポリオレフィン樹脂製表皮材。
- 前記トップコート層が、前記ポリシロキサン変性ポリヒドロキシポリウレタン樹脂に加えて、該樹脂と異なる他の樹脂を含む樹脂組成物によって形成されている請求項16又は17に記載の熱可塑性ポリオレフィン樹脂製表皮材。
- 前記トップコート層が、ポリシロキサン変性ポリヒドロキシポリウレタン樹脂の構造中に存在する水酸基と、該水酸基と反応する架橋剤との反応によって架橋された皮膜である請求項16乃至18のいずれか1項に記載の熱可塑性ポリオレフィン樹脂製表皮材。
- 高分子弾性体材料に被覆及び/または含浸させて、他部品と摺接する摺接部に表面処理層を形成するためのウェザーストリップ用材料であって、請求項1乃至4のいずれか1項に記載のポリシロキサン変性ポリヒドロキシポリウレタン樹脂を含んでなる樹脂組成物であることを特徴とするウェザーストリップ用材料。
- 前記樹脂組成物が、ポリシロキサン変性ポリヒドロキシポリウレタン樹脂100質量部に対して、平均重合度5,000~100,000のジオルガノポリシロキサン及び/または粘度が100~1,000CSのシリコーンオイルを、1~100質量部の割合で配合されてなる請求項20に記載のウェザーストリップ用材料。
- 前記樹脂組成物が、前記ポリシロキサン変性ポリヒドロキシポリウレタン樹脂100質量部に対して、艶消剤として、有機系微粉末或いは無機系微粉末から選ばれる一種又は二種以上の組み合わせからなる物質を1~150質量部の割合で添加してなる請求項20又は21に記載のウェザーストリップ用材料。
- 前記樹脂組成物が、更に、ポリシロキサン変性ポリヒドロキシポリウレタン樹脂以外のバインダー樹脂を含む請求項20乃至22のいずれか1項に記載のウェザーストリップ用材料。
- 請求項20乃至23のいずれか1項に記載のウェザーストリップ用材料を高分子弾性体材料に被覆及び/または含浸させて、他部品と摺接する摺接部に表面処理層が形成されてなり、該表面処理層が、ウェザーストリップ用材料中のポリシロキサン変性ポリヒドロキシポリウレタン樹脂の構造中の水酸基と反応する架橋剤で架橋されて形成されていることを特徴とするウェザーストリップ。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/510,583 US8703648B2 (en) | 2009-11-26 | 2010-11-25 | Polysiloxane-modified polyhydroxy polyurethane resin, method for producing same, heat-sensitive recording material using the resin, imitation leather, thermoplastic polyolefin resin skin material, material for weather strip, and weather strip |
RU2012120610/04A RU2518095C2 (ru) | 2009-11-26 | 2010-11-25 | Полигидрокси-полиуретановая смола, модифицированная полисилоксаном, способ ее получения, содержащий эту смолу термочувствительный материал для записи, искусственная кожа, кожеподобный материал из термопластичной полиолефиновой смолы, материал для уплотнителя и уплотнитель |
EP10833279.2A EP2505600B1 (en) | 2009-11-26 | 2010-11-25 | Polysiloxane-modified polyhydroxy polyurethane resin, method for producing same, heat-sensitive recording material using the resin, imitation leather, thermoplastic polyolefin resin skin material, material for weather strip, and weather strip |
CN201080053428.2A CN102666654B (zh) | 2009-11-26 | 2010-11-25 | 聚硅氧烷改性聚羟基聚氨酯树脂及其制造方法、以及其应用 |
KR1020127016359A KR101434764B1 (ko) | 2009-11-26 | 2010-11-25 | 폴리실록산 변성 폴리히드록시 폴리우레탄 수지 및 그 제조방법, 상기 수지를 이용한 감열 기록 재료, 인조 피혁, 열가소성 폴리올레핀 수지 표피재, 웨더스트립용 재료 및 웨더스트립 |
Applications Claiming Priority (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009-268433 | 2009-11-26 | ||
JP2009268452 | 2009-11-26 | ||
JP2009-268437 | 2009-11-26 | ||
JP2009268433 | 2009-11-26 | ||
JP2009-268435 | 2009-11-26 | ||
JP2009268437 | 2009-11-26 | ||
JP2009268435 | 2009-11-26 | ||
JP2009-268452 | 2009-11-26 | ||
JP2010-105854 | 2010-04-30 | ||
JP2010105854A JP5534924B2 (ja) | 2010-04-30 | 2010-04-30 | ウェザーストリップ用材料およびウェザーストリップ |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011065433A1 true WO2011065433A1 (ja) | 2011-06-03 |
Family
ID=44066538
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2010/071038 WO2011065433A1 (ja) | 2009-11-26 | 2010-11-25 | ポリシロキサン変性ポリヒドロキシポリウレタン樹脂及びその製造方法、該樹脂を用いた感熱記録材料、擬革、熱可塑性ポリオレフィン樹脂表皮材、ウェザーストリップ用材料及びウェザーストリップ |
Country Status (6)
Country | Link |
---|---|
US (1) | US8703648B2 (ja) |
EP (1) | EP2505600B1 (ja) |
KR (1) | KR101434764B1 (ja) |
CN (1) | CN102666654B (ja) |
RU (1) | RU2518095C2 (ja) |
WO (1) | WO2011065433A1 (ja) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012026338A1 (ja) * | 2010-08-26 | 2012-03-01 | 大日精化工業株式会社 | 自己架橋型ポリシロキサン変性ポリヒドロキシポリウレタン樹脂、該樹脂を含む樹脂材料、該樹脂の製造方法、該樹脂を用いてなる擬革及び熱可塑性ポリオレフィン表皮材 |
JP2012041452A (ja) * | 2010-08-19 | 2012-03-01 | Hitachi Chem Co Ltd | ポリヒドロキシウレタン化合物及びその製造方法、並びに、硬化性樹脂組成物、感光性エレメント、レジストパターンの形成方法及びプリント配線板の製造方法 |
JP2012046631A (ja) * | 2010-08-26 | 2012-03-08 | Dainichiseika Color & Chem Mfg Co Ltd | 自己架橋型ポリシロキサン変性ポリヒドロキシポリウレタン樹脂およびその製造方法 |
JP2012132124A (ja) * | 2010-12-22 | 2012-07-12 | Dainichiseika Color & Chem Mfg Co Ltd | 擬革 |
WO2012137726A1 (ja) * | 2011-04-04 | 2012-10-11 | 大日精化工業株式会社 | 自己架橋型ポリシロキサン変性ポリヒドロキシポリウレタン樹脂、該樹脂の製造方法、該樹脂を含む樹脂材料および該樹脂を利用した擬革 |
JP2013170320A (ja) * | 2012-02-20 | 2013-09-02 | Dainichiseika Color & Chem Mfg Co Ltd | 擬革 |
JP2013170234A (ja) * | 2012-02-21 | 2013-09-02 | Dainichiseika Color & Chem Mfg Co Ltd | 反応性ポリシロキサン化合物、塗料組成物およびポリシロキサン変性樹脂フィルム |
US8703648B2 (en) | 2009-11-26 | 2014-04-22 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Polysiloxane-modified polyhydroxy polyurethane resin, method for producing same, heat-sensitive recording material using the resin, imitation leather, thermoplastic polyolefin resin skin material, material for weather strip, and weather strip |
US8951933B2 (en) | 2009-11-25 | 2015-02-10 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Polysiloxane-modified polyhydroxy polyurethane resin, method for producing same, heat-sensitive recording material using the resin, imitation leather, thermoplastic polyolefin resin skin material, material for weather strip, and weather strip |
US8975420B2 (en) | 2009-11-25 | 2015-03-10 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Five-membered cyclocarbonate polysiloxane compound and process for preparation of same |
US9701783B2 (en) | 2012-10-29 | 2017-07-11 | 3M Innovative Properties Company | Polydiorganosiloxane polyurethane |
US10066048B2 (en) | 2010-06-24 | 2018-09-04 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Self-crosslinkable polyhydroxy polyurethane resin, resinaceous material that contains the resin, process for production of the resin, and imitation leather, surfacing material and weatherstrip material, using the resin |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI422607B (zh) * | 2011-06-29 | 2014-01-11 | Univ Tamkang | 功能性聚胺酯預聚物、利用其製備聚胺酯之方法及其應用方法 |
US20140256874A1 (en) * | 2013-03-05 | 2014-09-11 | Ppg Industries Ohio, Inc. | Curable solid particulate compositions |
WO2018042030A1 (de) * | 2016-09-05 | 2018-03-08 | Merz+Benteli Ag | Verwendung eines organcarbonat modifizierten praepolymers als edukt zur herstellung von isocyanatfreien und isothiocyanatfreien alkoxysilan-polymeren |
FR3068037B1 (fr) * | 2017-06-27 | 2020-09-11 | Valeo Systemes De Controle Moteur | Procede de synthese d'un materiau slicone/polyurethane |
GB2604452B (en) | 2018-01-24 | 2022-12-28 | Nike Innovate Cv | A resin composition |
JP7405077B2 (ja) * | 2018-06-27 | 2023-12-26 | Dic株式会社 | ウレタン樹脂組成物、表面処理剤、及び、物品 |
EP4154750A1 (en) * | 2019-07-24 | 2023-03-29 | NIKE Innovate C.V. | Polyolefin-based synthetic leather and articles formed therefrom |
US11678721B2 (en) | 2019-07-24 | 2023-06-20 | Nike, Inc. | Polyolefin-based synthetic leather and articles formed therefrom |
WO2021016231A1 (en) * | 2019-07-24 | 2021-01-28 | Nike Innovate C.V. | Artificial leather composition and upper for article of footwear comprising said artificial leather composition |
CN112691871A (zh) * | 2020-04-20 | 2021-04-23 | 法国圣戈班玻璃公司 | 一种处理汽车密封部件的方法及汽车密封部件 |
Citations (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3072613A (en) | 1957-08-20 | 1963-01-08 | Union Carbide Corp | Multiple cyclic carbonate polymers |
JPS564408A (en) | 1979-06-26 | 1981-01-17 | Meitoo Kk | Waterproof* antiseptic and vermicidal method of wood |
JPS5813359A (ja) | 1981-07-16 | 1983-01-25 | Makoto Tanaka | トウフ保存法 |
JPS61227087A (ja) | 1985-04-01 | 1986-10-09 | Dainichi Seika Kogyo Kk | 感熱記録材料 |
JPS62202786A (ja) | 1986-03-04 | 1987-09-07 | Dainichi Color & Chem Mfg Co Ltd | 感熱記録材料 |
JPH02102096A (ja) | 1988-10-12 | 1990-04-13 | Dainichiseika Color & Chem Mfg Co Ltd | 感熱記録材料 |
JPH08109349A (ja) | 1994-10-12 | 1996-04-30 | Yokohama Rubber Co Ltd:The | 自動車用グラスランのコーティング剤 |
JPH08225670A (ja) | 1994-12-19 | 1996-09-03 | Kinugawa Rubber Ind Co Ltd | 高分子弾性体の表面処理用塗料組成物 |
JPH10251405A (ja) * | 1987-07-16 | 1998-09-22 | Dainippon Ink & Chem Inc | ポリウレタンの製造方法 |
JPH11140182A (ja) * | 1997-11-05 | 1999-05-25 | Nof Corp | 反応性樹脂 |
JP2000319504A (ja) | 1999-05-11 | 2000-11-21 | Japan Chemical Innovation Institute | 新規なポリヒドロキシウレタン及びその製造方法 |
JP2002518532A (ja) * | 1998-06-15 | 2002-06-25 | ユーロテック リミテッド | 混成非イソシアネートポリウレタン網状ポリマー及びそれから製造される組成物 |
JP2004051901A (ja) | 2002-07-23 | 2004-02-19 | Fujikura Kasei Co Ltd | 艶消し塗料組成物、これを用いた塗膜および塗装物 |
JP2005154580A (ja) | 2003-11-26 | 2005-06-16 | Mitsui Chemicals Inc | 自己乳化型水性ポリウレタン樹脂及びその用途 |
JP2005336637A (ja) * | 2004-05-25 | 2005-12-08 | Dainichiseika Color & Chem Mfg Co Ltd | 擬革様シート状物 |
JP2006176615A (ja) | 2004-12-22 | 2006-07-06 | Seikoh Chem Co Ltd | ポリオレフィン系樹脂成形品用コーティング剤およびそれを被覆した成形品 |
JP2006307015A (ja) | 2005-04-28 | 2006-11-09 | Toyota Motor Corp | 耐傷付性樹脂組成物、耐傷付性樹脂組成物の製造方法、及び成形品 |
JP2007501886A (ja) * | 2003-08-13 | 2007-02-01 | ハンツマン・アドヴァンスト・マテリアルズ・(スイッツランド)・ゲーエムベーハー | イソシアネートを使用せずに製造したポリウレタン樹脂またはポリウレタン−エポキシハイブリッド樹脂をベースとするナノ複合材料 |
JP2007270373A (ja) | 2006-03-31 | 2007-10-18 | Nisshinbo Ind Inc | 人工皮革状シートおよびその製造方法 |
JP2007297544A (ja) * | 2006-05-01 | 2007-11-15 | Dai Ichi Kogyo Seiyaku Co Ltd | ポリヒドロキシウレタンの製造方法及びポリヒドロキシウレタン水分散体 |
JP2008056772A (ja) | 2006-08-30 | 2008-03-13 | Seikoh Chem Co Ltd | エチレン−プロピレンゴム用水系コーティング剤 |
JP2008297552A (ja) * | 2008-07-10 | 2008-12-11 | Dainichiseika Color & Chem Mfg Co Ltd | 感熱記録材料、長鎖側鎖含有ポリウレタン及びその製造方法 |
JP2009520082A (ja) * | 2005-12-14 | 2009-05-21 | ロード コーポレーション | 騒音防止及び/又は摩擦軽減特性を有する水性分散塗料組成物 |
JP2009144313A (ja) | 2007-11-22 | 2009-07-02 | Toray Coatex Co Ltd | 植物由来成分からなる合成皮革 |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2300767A1 (fr) * | 1975-02-11 | 1976-09-10 | Rhone Poulenc Ind | Composes silicies polyethyleniques |
US4395527A (en) | 1978-05-17 | 1983-07-26 | M & T Chemicals Inc. | Siloxane-containing polymers |
JPS5813359B2 (ja) | 1978-07-03 | 1983-03-12 | 富士化学紙工業株式会社 | 感熱転写材 |
US4480009A (en) | 1980-12-15 | 1984-10-30 | M&T Chemicals Inc. | Siloxane-containing polymers |
US4499149A (en) | 1980-12-15 | 1985-02-12 | M&T Chemicals Inc. | Siloxane-containing polymers |
US4883854A (en) * | 1988-09-30 | 1989-11-28 | Medtronic, Inc. | Hydroxyl functional monomers |
DE19505892C1 (de) | 1995-02-21 | 1996-03-14 | Goldschmidt Ag Th | Verfahren zur Herstellung von Carbonatgruppen enthaltenden Organopolysiloxanen |
US5686547A (en) | 1996-03-14 | 1997-11-11 | General Electric Company | Carbonate and hydroxy carbamate functionalized silicones |
JPH09278982A (ja) | 1996-04-15 | 1997-10-28 | Dainippon Ink & Chem Inc | 硬化性樹脂組成物ならびにそれらを用いた塗膜形成方法 |
DE19959949A1 (de) | 1999-12-13 | 2001-06-21 | Bayer Ag | Hydrophobierung mit carboxylgruppenhaltigen Polysiloxanen |
JP2004507513A (ja) | 2000-08-28 | 2004-03-11 | アプリリス,インコーポレイテッド | カチオン性重合を行いうる多官能エポキシモノマーを含むホログラフィー蓄積媒体 |
JP3501121B2 (ja) | 2000-12-14 | 2004-03-02 | 日本電気株式会社 | 光ヘッドおよびそれを用いた画像形成装置 |
JP4650627B2 (ja) | 2005-09-14 | 2011-03-16 | 信越化学工業株式会社 | 環状カーボネート変性シロキサン及びその製造方法並びに非水電解液、二次電池及びキャパシタ |
JP2009155407A (ja) | 2007-12-26 | 2009-07-16 | Konishi Co Ltd | 硬化性樹脂組成物及び接着剤組成物 |
US8951933B2 (en) | 2009-11-25 | 2015-02-10 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Polysiloxane-modified polyhydroxy polyurethane resin, method for producing same, heat-sensitive recording material using the resin, imitation leather, thermoplastic polyolefin resin skin material, material for weather strip, and weather strip |
JP2011132208A (ja) | 2009-11-25 | 2011-07-07 | Dainichiseika Color & Chem Mfg Co Ltd | 5員環環状カーボネートポリシロキサン化合物およびその製造方法 |
KR101434764B1 (ko) | 2009-11-26 | 2014-08-26 | 다이니치 세이카 고교 가부시키가이샤 | 폴리실록산 변성 폴리히드록시 폴리우레탄 수지 및 그 제조방법, 상기 수지를 이용한 감열 기록 재료, 인조 피혁, 열가소성 폴리올레핀 수지 표피재, 웨더스트립용 재료 및 웨더스트립 |
KR101483381B1 (ko) | 2010-08-26 | 2015-01-14 | 다이니치 세이카 고교 가부시키가이샤 | 자기 가교형 폴리실록산 변성 폴리히드록시 폴리우레탄 수지, 그 수지를 포함한 수지 재료, 그 수지의 제조방법, 그 수지를 사용하여 이루어진 인조 피혁 및 열가소성 폴리올레핀 표피재 |
-
2010
- 2010-11-25 KR KR1020127016359A patent/KR101434764B1/ko active IP Right Grant
- 2010-11-25 US US13/510,583 patent/US8703648B2/en active Active
- 2010-11-25 WO PCT/JP2010/071038 patent/WO2011065433A1/ja active Application Filing
- 2010-11-25 RU RU2012120610/04A patent/RU2518095C2/ru active
- 2010-11-25 EP EP10833279.2A patent/EP2505600B1/en active Active
- 2010-11-25 CN CN201080053428.2A patent/CN102666654B/zh active Active
Patent Citations (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3072613A (en) | 1957-08-20 | 1963-01-08 | Union Carbide Corp | Multiple cyclic carbonate polymers |
JPS564408A (en) | 1979-06-26 | 1981-01-17 | Meitoo Kk | Waterproof* antiseptic and vermicidal method of wood |
JPS5813359A (ja) | 1981-07-16 | 1983-01-25 | Makoto Tanaka | トウフ保存法 |
JPS61227087A (ja) | 1985-04-01 | 1986-10-09 | Dainichi Seika Kogyo Kk | 感熱記録材料 |
JPS62202786A (ja) | 1986-03-04 | 1987-09-07 | Dainichi Color & Chem Mfg Co Ltd | 感熱記録材料 |
JPH10251405A (ja) * | 1987-07-16 | 1998-09-22 | Dainippon Ink & Chem Inc | ポリウレタンの製造方法 |
JPH02102096A (ja) | 1988-10-12 | 1990-04-13 | Dainichiseika Color & Chem Mfg Co Ltd | 感熱記録材料 |
JPH08109349A (ja) | 1994-10-12 | 1996-04-30 | Yokohama Rubber Co Ltd:The | 自動車用グラスランのコーティング剤 |
JPH08225670A (ja) | 1994-12-19 | 1996-09-03 | Kinugawa Rubber Ind Co Ltd | 高分子弾性体の表面処理用塗料組成物 |
JPH11140182A (ja) * | 1997-11-05 | 1999-05-25 | Nof Corp | 反応性樹脂 |
JP2002518532A (ja) * | 1998-06-15 | 2002-06-25 | ユーロテック リミテッド | 混成非イソシアネートポリウレタン網状ポリマー及びそれから製造される組成物 |
JP2000319504A (ja) | 1999-05-11 | 2000-11-21 | Japan Chemical Innovation Institute | 新規なポリヒドロキシウレタン及びその製造方法 |
JP2004051901A (ja) | 2002-07-23 | 2004-02-19 | Fujikura Kasei Co Ltd | 艶消し塗料組成物、これを用いた塗膜および塗装物 |
JP2007501886A (ja) * | 2003-08-13 | 2007-02-01 | ハンツマン・アドヴァンスト・マテリアルズ・(スイッツランド)・ゲーエムベーハー | イソシアネートを使用せずに製造したポリウレタン樹脂またはポリウレタン−エポキシハイブリッド樹脂をベースとするナノ複合材料 |
JP2005154580A (ja) | 2003-11-26 | 2005-06-16 | Mitsui Chemicals Inc | 自己乳化型水性ポリウレタン樹脂及びその用途 |
JP2005336637A (ja) * | 2004-05-25 | 2005-12-08 | Dainichiseika Color & Chem Mfg Co Ltd | 擬革様シート状物 |
JP2006176615A (ja) | 2004-12-22 | 2006-07-06 | Seikoh Chem Co Ltd | ポリオレフィン系樹脂成形品用コーティング剤およびそれを被覆した成形品 |
JP2006307015A (ja) | 2005-04-28 | 2006-11-09 | Toyota Motor Corp | 耐傷付性樹脂組成物、耐傷付性樹脂組成物の製造方法、及び成形品 |
JP2009520082A (ja) * | 2005-12-14 | 2009-05-21 | ロード コーポレーション | 騒音防止及び/又は摩擦軽減特性を有する水性分散塗料組成物 |
JP2007270373A (ja) | 2006-03-31 | 2007-10-18 | Nisshinbo Ind Inc | 人工皮革状シートおよびその製造方法 |
JP2007297544A (ja) * | 2006-05-01 | 2007-11-15 | Dai Ichi Kogyo Seiyaku Co Ltd | ポリヒドロキシウレタンの製造方法及びポリヒドロキシウレタン水分散体 |
JP2008056772A (ja) | 2006-08-30 | 2008-03-13 | Seikoh Chem Co Ltd | エチレン−プロピレンゴム用水系コーティング剤 |
JP2009144313A (ja) | 2007-11-22 | 2009-07-02 | Toray Coatex Co Ltd | 植物由来成分からなる合成皮革 |
JP2008297552A (ja) * | 2008-07-10 | 2008-12-11 | Dainichiseika Color & Chem Mfg Co Ltd | 感熱記録材料、長鎖側鎖含有ポリウレタン及びその製造方法 |
Non-Patent Citations (2)
Title |
---|
N. KIHARA; T. ENDO, J. ORG. CHEM., vol. 58, 1993, pages 6198 |
N. KIHARA; T. ENDO, J. POLYMERSCI., PART A POLYMER CHEM., vol. 31, no. 11, 1993, pages 2765 |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8975420B2 (en) | 2009-11-25 | 2015-03-10 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Five-membered cyclocarbonate polysiloxane compound and process for preparation of same |
US9394462B2 (en) | 2009-11-25 | 2016-07-19 | Dainichiseika Color & Chemicals Mfg. Co., Ltd | Polysiloxane-modified polyhydroxy polyurethane resin, method for producing same, heat-sensitive recording material using the resin, imitation leather, thermoplastic polyolefin resin skin material, material for weather strip, and weather strip |
US8951933B2 (en) | 2009-11-25 | 2015-02-10 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Polysiloxane-modified polyhydroxy polyurethane resin, method for producing same, heat-sensitive recording material using the resin, imitation leather, thermoplastic polyolefin resin skin material, material for weather strip, and weather strip |
US8703648B2 (en) | 2009-11-26 | 2014-04-22 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Polysiloxane-modified polyhydroxy polyurethane resin, method for producing same, heat-sensitive recording material using the resin, imitation leather, thermoplastic polyolefin resin skin material, material for weather strip, and weather strip |
US10066048B2 (en) | 2010-06-24 | 2018-09-04 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Self-crosslinkable polyhydroxy polyurethane resin, resinaceous material that contains the resin, process for production of the resin, and imitation leather, surfacing material and weatherstrip material, using the resin |
JP2012041452A (ja) * | 2010-08-19 | 2012-03-01 | Hitachi Chem Co Ltd | ポリヒドロキシウレタン化合物及びその製造方法、並びに、硬化性樹脂組成物、感光性エレメント、レジストパターンの形成方法及びプリント配線板の製造方法 |
JP2012046631A (ja) * | 2010-08-26 | 2012-03-08 | Dainichiseika Color & Chem Mfg Co Ltd | 自己架橋型ポリシロキサン変性ポリヒドロキシポリウレタン樹脂およびその製造方法 |
WO2012026338A1 (ja) * | 2010-08-26 | 2012-03-01 | 大日精化工業株式会社 | 自己架橋型ポリシロキサン変性ポリヒドロキシポリウレタン樹脂、該樹脂を含む樹脂材料、該樹脂の製造方法、該樹脂を用いてなる擬革及び熱可塑性ポリオレフィン表皮材 |
US10000609B2 (en) | 2010-08-26 | 2018-06-19 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Self-crosslinking polysiloxane-modified polyhydroxy polyurethane resin, resin material containing same, method for producing same, artificial leather comprising same, and thermoplastic polyolefin skin material comprising same |
JP2012132124A (ja) * | 2010-12-22 | 2012-07-12 | Dainichiseika Color & Chem Mfg Co Ltd | 擬革 |
US9359719B2 (en) | 2011-04-04 | 2016-06-07 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Self-crosslinkable polysiloxane-modified polyhydroxy polyurethane resin, process for producing said resin, resin material comprising said resin, and artificial leather produced utilizing said resin |
WO2012137726A1 (ja) * | 2011-04-04 | 2012-10-11 | 大日精化工業株式会社 | 自己架橋型ポリシロキサン変性ポリヒドロキシポリウレタン樹脂、該樹脂の製造方法、該樹脂を含む樹脂材料および該樹脂を利用した擬革 |
JP2013170320A (ja) * | 2012-02-20 | 2013-09-02 | Dainichiseika Color & Chem Mfg Co Ltd | 擬革 |
JP2013170234A (ja) * | 2012-02-21 | 2013-09-02 | Dainichiseika Color & Chem Mfg Co Ltd | 反応性ポリシロキサン化合物、塗料組成物およびポリシロキサン変性樹脂フィルム |
US9701783B2 (en) | 2012-10-29 | 2017-07-11 | 3M Innovative Properties Company | Polydiorganosiloxane polyurethane |
Also Published As
Publication number | Publication date |
---|---|
EP2505600A4 (en) | 2013-09-18 |
CN102666654A (zh) | 2012-09-12 |
CN102666654B (zh) | 2014-05-28 |
KR101434764B1 (ko) | 2014-08-26 |
EP2505600B1 (en) | 2018-08-22 |
KR20120096041A (ko) | 2012-08-29 |
EP2505600A1 (en) | 2012-10-03 |
US20120237701A1 (en) | 2012-09-20 |
RU2012120610A (ru) | 2014-01-10 |
US8703648B2 (en) | 2014-04-22 |
RU2518095C2 (ru) | 2014-06-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2011065433A1 (ja) | ポリシロキサン変性ポリヒドロキシポリウレタン樹脂及びその製造方法、該樹脂を用いた感熱記録材料、擬革、熱可塑性ポリオレフィン樹脂表皮材、ウェザーストリップ用材料及びウェザーストリップ | |
WO2011065432A1 (ja) | ポリシロキサン変性ポリヒドロキシポリウレタン樹脂およびその製造方法、該樹脂を用いた感熱記録材料、擬革、熱可塑性ポリオレフィン樹脂表皮材、ウェザーストリップ用材料およびウェザーストリップ | |
KR101476559B1 (ko) | 자기 가교형 폴리히드록시 폴리우레탄 수지, 그 수지를 포함하는 수지 재료, 그 수지의 제조방법, 그 수지를 이용하여 이루어진 인조 가죽, 표피재 및 웨더 스트립용 재료 | |
WO2012026338A1 (ja) | 自己架橋型ポリシロキサン変性ポリヒドロキシポリウレタン樹脂、該樹脂を含む樹脂材料、該樹脂の製造方法、該樹脂を用いてなる擬革及び熱可塑性ポリオレフィン表皮材 | |
JP5386468B2 (ja) | 熱可塑性ポリオレフィン樹脂製表皮材 | |
JP5601687B2 (ja) | 熱可塑性ポリオレフィン樹脂製の表皮材 | |
JP5069736B2 (ja) | 熱可塑性ポリオレフィン樹脂表皮材 | |
JP5367680B2 (ja) | 熱可塑性ポリオレフィン樹脂表皮材 | |
JP5456647B2 (ja) | 擬革 | |
JP5534924B2 (ja) | ウェザーストリップ用材料およびウェザーストリップ | |
JP5367679B2 (ja) | 擬革 | |
JP5501850B2 (ja) | ウェザーストリップ用材料及びウェザーストリップ | |
JP5492652B2 (ja) | ウェザーストリップ用材料及びウェザーストリップ |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201080053428.2 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10833279 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13510583 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010833279 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20127016359 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012120610 Country of ref document: RU |