JP6521349B1 - 発泡ウレタンシート、及び、合成皮革 - Google Patents
発泡ウレタンシート、及び、合成皮革 Download PDFInfo
- Publication number
- JP6521349B1 JP6521349B1 JP2019507957A JP2019507957A JP6521349B1 JP 6521349 B1 JP6521349 B1 JP 6521349B1 JP 2019507957 A JP2019507957 A JP 2019507957A JP 2019507957 A JP2019507957 A JP 2019507957A JP 6521349 B1 JP6521349 B1 JP 6521349B1
- Authority
- JP
- Japan
- Prior art keywords
- mass
- urethane resin
- parts
- urethane
- synthetic leather
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000002649 leather substitute Substances 0.000 title claims abstract description 20
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 106
- 239000011342 resin composition Substances 0.000 claims abstract description 34
- 229920002635 polyurethane Polymers 0.000 claims abstract description 21
- 239000004814 polyurethane Substances 0.000 claims abstract description 21
- 239000004094 surface-active agent Substances 0.000 claims abstract description 17
- 125000000129 anionic group Chemical group 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 239000006260 foam Substances 0.000 claims description 27
- 238000005187 foaming Methods 0.000 claims description 19
- 239000005056 polyisocyanate Substances 0.000 claims description 17
- 229920001228 polyisocyanate Polymers 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 11
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- 230000002209 hydrophobic effect Effects 0.000 claims description 3
- GKGXKPRVOZNVPQ-UHFFFAOYSA-N diisocyanatomethylcyclohexane Chemical compound O=C=NC(N=C=O)C1CCCCC1 GKGXKPRVOZNVPQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 abstract description 3
- 239000012736 aqueous medium Substances 0.000 abstract 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 57
- 238000000034 method Methods 0.000 description 33
- 150000003077 polyols Chemical class 0.000 description 28
- 229920005862 polyol Polymers 0.000 description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 21
- -1 glycol compound Chemical class 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- 239000004793 Polystyrene Substances 0.000 description 16
- 239000007788 liquid Substances 0.000 description 16
- 229920002223 polystyrene Polymers 0.000 description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 239000010410 layer Substances 0.000 description 15
- 239000004970 Chain extender Substances 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 13
- 239000003431 cross linking reagent Substances 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000839 emulsion Substances 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 10
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
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- 238000004049 embossing Methods 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000004945 emulsification Methods 0.000 description 6
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- 229920000515 polycarbonate Polymers 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000002562 thickening agent Substances 0.000 description 6
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 6
- 229940088990 ammonium stearate Drugs 0.000 description 5
- JPNZKPRONVOMLL-UHFFFAOYSA-N azane;octadecanoic acid Chemical compound [NH4+].CCCCCCCCCCCCCCCCCC([O-])=O JPNZKPRONVOMLL-UHFFFAOYSA-N 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 239000004745 nonwoven fabric Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000003094 microcapsule Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920005906 polyester polyol Polymers 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- CKFGINPQOCXMAZ-UHFFFAOYSA-N methanediol Chemical compound OCO CKFGINPQOCXMAZ-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 210000003491 skin Anatomy 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
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- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
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- BYPFICORERPGJY-UHFFFAOYSA-N 3,4-diisocyanatobicyclo[2.2.1]hept-2-ene Chemical compound C1CC2(N=C=O)C(N=C=O)=CC1C2 BYPFICORERPGJY-UHFFFAOYSA-N 0.000 description 1
- XJIIBKORMYCKON-UHFFFAOYSA-N 3,6-diamino-2-methylbenzenesulfonic acid Chemical compound CC1=C(N)C=CC(N)=C1S(O)(=O)=O XJIIBKORMYCKON-UHFFFAOYSA-N 0.000 description 1
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- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
(X)前記ウレタン樹脂組成物を起泡させ起泡液を得、この起泡液を離型紙上に塗布し、乾燥させ、前記基材(i)と貼り合わせる方法、
(Y)前記ウレタン樹脂組成物を起泡させ起泡液を得、この起泡液を、離型紙上に作製した表皮層上に塗布し、乾燥させ、前記基材(i)と貼り合わせる方法、
(Z)前記ウレタン樹脂組成物を起泡させ起泡液を得、この起泡液を前記基材(i)上に塗布し、乾燥させ、必要に応じて、その上に、離型紙上に作製した表皮層(iii)を貼り合わせる方法などが挙げられる。
メチルエチルケトン3,281質量部及びオクチル酸第一錫0.1質量部の存在下、ポリカーボネートポリオール(「ニッポラン980R」日本ポリウレタン株式会社製、数平均分子量;2,000)1,000質量部と、2,2−ジメチロールプロピオン酸17質量部と、エチレングリコール47質量部と、ジフェニルメタンジイソシアネート(以下、「MDI」と略記する。)344質量部とを溶液粘度が20,000mPa・sに達するまで70℃で反応させた後、メタノール3質量部を加えて反応を停止させてウレタン樹脂のメチルエチルケトン溶液を得た。このウレタン樹脂溶液にポリオキシエチレンジスチレン化フェニルエーテル(Hydrophile−Lipophile Balance(以下、「HLB」と略記する);14)70質量部と、トリエチルアミン13質量部を混合させた後に、イオン交換水800質量部を加えて転相乳化させることで前記ウレタン樹脂(A−1)が水に分散した乳化液を得た。
次いで、前記乳化液からメチルエチルケトンを留去することによって、ウレタン樹脂(A−1)50質量%を含むウレタン樹脂組成物を得た。
メチルエチルケトン3,281質量部及びオクチル酸第一錫0.1質量部の存在下、ポリエーテルポリオール(「PTMG2000」三菱化型株式会社製、数平均分子量;2,000)1,000質量部と、2,2−ジメチロールプロピオン酸17質量部と、エチレングリコール47質量部と、MDIを344質量部とを溶液粘度が20,000mPa・sに達するまで70℃で反応させた後、メタノール3質量部を加えて反応を停止させてウレタン樹脂のメチルエチルケトン溶液を得た。このウレタン樹脂溶液にポリオキシエチレンジスチレン化フェニルエーテル(HLB;14)70質量部と、トリエチルアミン13質量部を混合させた後に、イオン交換水800質量部を加えて転相乳化させることで前記ウレタン樹脂(A−2)が水に分散した乳化液を得た。
次いで、前記乳化液からメチルエチルケトンを留去することによって、ウレタン樹脂(A−2)50質量%を含むウレタン樹脂組成物を得た。
メチルエチルケトン3,281質量部及びオクチル酸第一錫0.1質量部の存在下、ポリエステルポリオール(「プラクセル220」株式会社ダイセル製、数平均分子量;2,000)1,000質量部と、2,2−ジメチロールプロピオン酸17質量部と、エチレングリコール47質量部と、MDIを344質量部とを溶液粘度が20,000mPa・sに達するまで70℃で反応させた後、メタノール3質量部を加えて反応を停止させてウレタン樹脂のメチルエチルケトン溶液を得た。このウレタン樹脂溶液にポリオキシエチレンジスチレン化フェニルエーテル(HLB;14)70質量部と、トリエチルアミン13質量部を混合させた後に、イオン交換水800質量部を加えて転相乳化させることで前記ウレタン樹脂(A−3)が水に分散した乳化液を得た。
次いで、前記乳化液からメチルエチルケトンを留去することによって、ウレタン樹脂(A−3)50質量%を含むウレタン樹脂組成物を得た。
メチルエチルケトン1,279質量部及びオクチル酸第一錫0.1質量部の存在下、ポリカーボネートポリオール(「ニッポラン980R」日本ポリウレタン株式会社製、数平均分子量;2,000)1,000質量部と、2,2−ジメチロールプロピオン酸17質量部と、ジシクロヘキシルメタンジイソシアネート(以下、「H12MDI」と略記する。)262質量部とを、イソシアネート濃度が1.2質量%に達するまで70℃で反応させてウレタンプレポリマーのメチルエチルケトン溶液を得た。このウレタン樹脂溶液にポリオキシエチレンジスチレン化フェニルエーテル(Hydrophile−Lipophile Balance(以下、「HLB」と略記する);14)64質量部と、トリエチルアミン28質量部を混合させた後に、イオン交換水2,650質量部を加えて転相乳化させることで前記ウレタンプレポリマーが水に分散した乳化液を得た。得られた乳化液にエチレンジアミン21質量部とイオン交換水189部を混合し鎖伸長反応することによってウレタン樹脂組成物を得た。
次いで、ウレタン樹脂組成物からメチルエチルケトンと水分を留去することによって、ウレタン樹脂(A−4)50質量%を含むウレタン樹脂組成物を得た。
メチルエチルケトン1,279質量部及びオクチル酸第一錫0.1質量部の存在下、ポリエーテルポリオール(「PTMG2000」三菱化型株式会社製、数平均分子量;2,000)1,000質量部と、2,2−ジメチロールプロピオン酸17質量部と、H12MDI 262質量部とを、イソシアネート濃度が1.2質量%に達するまで70℃で反応させてウレタン樹脂プレポリマー(A‘−2)のメチルエチルケトン溶液を得た。このウレタン樹脂溶液にポリオキシエチレンジスチレン化フェニルエーテル(Hydrophile−Lipophile Balance(以下、「HLB」と略記する);14)64質量部と、トリエチルアミン28質量部を混合させた後に、イオン交換水2,650質量部を加えて転相乳化させることで前記ウレタンプレポリマーが水に分散した乳化液を得た。得られた乳化液にエチレンジアミン21質量部とイオン交換水189部を混合し鎖伸長反応することによってウレタン樹脂組成物を得た。
次いで、ウレタン樹脂組成物からメチルエチルケトンと水分を留去することによって、ウレタン樹脂(A−5)50質量%を含むウレタン樹脂組成物を得た。
メチルエチルケトン1,279質量部及びオクチル酸第一錫0.1質量部の存在下、ポリエステルポリオール(「プラクセル220」株式会社ダイセル製、数平均分子量;2,000)1,000質量部と、2,2−ジメチロールプロピオン酸17質量部と、H12MDI 262質量部とを、イソシアネート濃度が1.2質量%に達するまで70℃で反応させてウレタン樹脂プレポリマーのメチルエチルケトン溶液を得た。このウレタン樹脂溶液にポリオキシエチレンジスチレン化フェニルエーテル(Hydrophile−Lipophile Balance(以下、「HLB」と略記する);14)64質量部と、トリエチルアミン28質量部を混合させた後に、イオン交換水2,650質量部を加えて転相乳化させることで前記ウレタンプレポリマーが水に分散した乳化液を得た。得られた乳化液にエチレンジアミン21質量部とイオン交換水189部を混合し鎖伸長反応することによってウレタン樹脂組成物を得た。
次いで、ウレタン樹脂組成物からメチルエチルケトンと水分を留去することによって、ウレタン樹脂(A−6)50質量%を含むウレタン樹脂組成物を得た。
合成例1で得られたウレタン樹脂組成物100質量部に、増粘剤(Borchers社製「Borchi Gel ALA」)2質量部、ステアリン酸アンモニウム0.5質量部、架橋剤(日本触媒株式会社製「エポクロスWS−700」)4質量部を加え、メカニカルミキサーを使用して2,000rpmで1分間撹拌し、起泡させ、1.5倍の体積にした起泡液を得た。
これを離型紙に塗布し、80℃で3分間、さらに120℃で2分間乾燥させることで、発泡ウレタンシートを製造した。
用いる水性ウレタン樹脂組成物の種類、及び、ステアリン酸アンモニウムの使用量を表1〜3に示す通りに変更した以外は、実施例1と同様にして発泡ウレタンシートを得た。
合成例1で得られたウレタン樹脂組成物100質量部に、増粘剤(Borchers社製「Borchi Gel ALA」)2質量部、ドデシルベンゼンスルホン酸ナトリウム1.5質量部、架橋剤(日本触媒株式会社製「エポクロスWS−700」)4質量部を加え、メカニカルミキサーを使用して2,000rpmで1分間撹拌し、起泡させ、1.5倍の体積にした起泡液を得た。
これを離型紙に塗布し、80℃で3分間、さらに120℃で2分間乾燥させることで、シートを製造した。
合成例1で得られたウレタン樹脂組成物100質量部に、増粘剤(Borchers社製「Borchi Gel ALA」)2質量部、架橋剤(日本触媒株式会社製「エポクロスWS−700」)4質量部を加え、メカニカルミキサーを使用して2,000rpmで1分間撹拌し、起泡させ、1.5倍の体積にした起泡液を得た。
これを離型紙に塗布し、80℃で3分間、さらに120℃で2分間乾燥させたところ、乾燥工程にて泡が消失したため、ほぼ無孔のシートを形成した
合成例1で得られたウレタン樹脂組成物100質量部に、増粘剤(Borchers社製「Borchi Gel ALA」)2質量部、ドデシルベンゼンスルホン酸ナトリウム1.5質量部、ステアリン酸アンモニウム1質量部、架橋剤(日本触媒株式会社製「エポクロスWS−700」)4質量部を加え、メカニカルミキサーを使用して2,000rpmで1分間撹拌し、起泡させ、7倍の体積にした起泡液を得た。
これを離型紙に塗布し、80℃で3分間、さらに120℃で2分間乾燥させることで、シートを製造した。
合成例で用いたポリオール等の数平均分子量は、ゲル・パーミエーション・カラムクロマトグラフィー(GPC)法により、下記の条件で測定した。
カラム:東ソー株式会社製の下記のカラムを直列に接続して使用した。
「TSKgel G5000」(7.8mmI.D.×30cm)×1本
「TSKgel G4000」(7.8mmI.D.×30cm)×1本
「TSKgel G3000」(7.8mmI.D.×30cm)×1本
「TSKgel G2000」(7.8mmI.D.×30cm)×1本
検出器:RI(示差屈折計)
カラム温度:40℃
溶離液:テトラヒドロフラン(THF)
流速:1.0mL/分
注入量:100μL(試料濃度0.4質量%のテトラヒドロフラン溶液)
標準試料:下記の標準ポリスチレンを用いて検量線を作成した。
東ソー株式会社製「TSKgel 標準ポリスチレン A−500」
東ソー株式会社製「TSKgel 標準ポリスチレン A−1000」
東ソー株式会社製「TSKgel 標準ポリスチレン A−2500」
東ソー株式会社製「TSKgel 標準ポリスチレン A−5000」
東ソー株式会社製「TSKgel 標準ポリスチレン F−1」
東ソー株式会社製「TSKgel 標準ポリスチレン F−2」
東ソー株式会社製「TSKgel 標準ポリスチレン F−4」
東ソー株式会社製「TSKgel 標準ポリスチレン F−10」
東ソー株式会社製「TSKgel 標準ポリスチレン F−20」
東ソー株式会社製「TSKgel 標準ポリスチレン F−40」
東ソー株式会社製「TSKgel 標準ポリスチレン F−80」
東ソー株式会社製「TSKgel 標準ポリスチレン F−128」
東ソー株式会社製「TSKgel 標準ポリスチレン F−288」
東ソー株式会社製「TSKgel 標準ポリスチレン F−550」
合成例で得られた水性ウレタン樹脂組成物を離型紙に塗布し(塗布厚さ150μm)、熱風乾燥機にて70℃、4分間、次いで120℃で2分間乾燥することで乾燥物を得た。この乾燥物を、株式会社島津製作所製フローテスター「CFT−500A」(口径1mm、長さ1mmのダイスを使用、荷重98N、昇温速度3℃/分)を使用して、流動開始温度を測定した。
得られた発泡ウレタンシートを手で触り、以下のように評価した。
「A」:柔軟性に富む。
「B」:やや柔軟性がある。
「C」:柔軟性が劣る。
「D」:硬い。
得られたウレタンシートを幅10mm、長さ60mmに裁断したものを試験片とした。この試験片の両端をチャックで挟み、引張試験機「オートグラフAG−I」(株式会社島津製作所製)を使用して、温度23℃、湿度60%の雰囲気下で、クロスヘッドスピード300mm/分で引張り、100%伸長時における引張強度を測定し、以下のように評価した。
「T」:10N/cm2以上
「F」:10N/cm2未満
合成例1で得られたウレタン樹脂組成物100質量部に、増粘剤(Borchers社製「Borch Gel ALA」)2質量部、ステアリン酸アンモニウム1.5質量部、架橋剤(日本触媒株式会社製「エポクロスWS−700」)4質量部を加え、メカニカルミキサーを使用して2,000rpmで1分間撹拌し、起泡させ、1.5倍の体積にした起泡液を得た。
これをポリエステル繊維不織布に塗布し、80℃で3分間、さらに120℃で2分間乾燥させることで、ポリウレタン層を形成した。次いで、得られたポリウレタン層上に、凹凸パターンが施された離型紙を載置し、180℃で予熱したロールプレスを施すことでエンボス加工された合成皮革を得た。
用いるウレタン樹脂組成物の種類、及び、ステアリン酸アンモニウムの使用量を表4に示す通りに変更した以外は、実施例9と同様にして合成皮革を得た。
得られた合成皮革を手で触り、以下のように評価した。
「A」:柔軟性に富む。
「B」:やや柔軟性がある。
「C」:柔軟性が劣る。
「D」:硬い。
実施例及び比較例で得られた合成皮革を、島津オートグラフ「AG−1」(株式会社島津製作所製)を使用して、フルスケール5kg、ヘッドスピード20mm/分の条件にて剥離強度を測定し、以下のように評価した。
「A」:0.15MPa以上
「B」:0.1MPa以上0.15MPa未満
「C」:0.1MPa未満
実施例及び比較例で得られた合成皮革を目視で観察し、以下のように評価した。
「T」:エンボス加工により形成された表面上のシワが均一に作製できている。
「F」:エンボス加工により形成された表面上のシワが均一でない。
Claims (5)
- 4,4’−ジフェニルメタンジイソシアネート、トルエンジイソシアネート、シクロヘキシルメタンジイソシアネート、及びイソホロンジイソシアネートからなる群より選ばれる1種以上のポリイソシアネートを原料とする、アニオン性基を有するウレタン樹脂(A)、水(B)、及び、芳香環を有さず、かつ炭素原子数が10以上の疎水部を有する界面活性剤(C)を含有するウレタン樹脂組成物により形成された、密度が200〜1,000kg/m3であることを特徴とする発泡ウレタンシート。
- 前記界面活性剤(C)が、ステアリン酸塩である請求項1記載の発泡ウレタンシート。
- 前記ウレタン樹脂(A)の流動開始温度が、80℃以上である請求項1又は2記載の発泡ウレタンシート。
- 少なくとも、基材(i)、及び、ポリウレタン層(ii)を有する合成皮革であって、
前記ポリウレタン層(ii)が、請求項1〜3のいずれか1項記載の発泡ウレタンシートにより形成されているものであることを特徴とする合成皮革。 - 前記ポリウレタン層(ii)が、エンボス加工されているものである請求項4記載の合成皮革。
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KR20200055006A (ko) | 2020-05-20 |
CN111164141B (zh) | 2023-02-17 |
US20210164157A1 (en) | 2021-06-03 |
EP3712203A1 (en) | 2020-09-23 |
TW201922923A (zh) | 2019-06-16 |
WO2019098039A1 (ja) | 2019-05-23 |
KR102409657B1 (ko) | 2022-06-22 |
TWI782129B (zh) | 2022-11-01 |
CN111164141A (zh) | 2020-05-15 |
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