CN114364745A - 发泡片及合成皮革 - Google Patents
发泡片及合成皮革 Download PDFInfo
- Publication number
- CN114364745A CN114364745A CN202080060638.8A CN202080060638A CN114364745A CN 114364745 A CN114364745 A CN 114364745A CN 202080060638 A CN202080060638 A CN 202080060638A CN 114364745 A CN114364745 A CN 114364745A
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- Prior art keywords
- mass
- urethane resin
- water
- manufactured
- content
- 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.)
- Pending
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- 239000002649 leather substitute Substances 0.000 title claims abstract description 12
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 109
- 229920002635 polyurethane Polymers 0.000 claims abstract description 45
- 239000004814 polyurethane Substances 0.000 claims abstract description 45
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- 125000003277 amino group Chemical group 0.000 claims description 28
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- 239000002994 raw material Substances 0.000 claims description 12
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- -1 diol compound Chemical class 0.000 description 22
- 239000007788 liquid Substances 0.000 description 22
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 20
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- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 14
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- 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 13
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- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 6
- 238000004945 emulsification Methods 0.000 description 6
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 6
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 description 6
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- 239000004831 Hot glue Substances 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
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- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
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- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
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- 239000011248 coating agent Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 2
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- 239000007789 gas Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
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- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
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- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- 239000002335 surface treatment layer Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 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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- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- NSMWYRLQHIXVAP-UHFFFAOYSA-N 2,5-dimethylpiperazine Chemical compound CC1CNC(C)CN1 NSMWYRLQHIXVAP-UHFFFAOYSA-N 0.000 description 1
- HSZGXYFZPBCFSP-UHFFFAOYSA-N 2,6-diaminobenzenesulfonic acid Chemical compound NC1=CC=CC(N)=C1S(O)(=O)=O HSZGXYFZPBCFSP-UHFFFAOYSA-N 0.000 description 1
- IVGRSQBDVIJNDA-UHFFFAOYSA-N 2-(2-aminoethylamino)ethanesulfonic acid Chemical compound NCCNCCS(O)(=O)=O IVGRSQBDVIJNDA-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- SPGHPHFQNQIZME-UHFFFAOYSA-N 2-n-ethylethane-1,1,2-triamine Chemical compound CCNCC(N)N SPGHPHFQNQIZME-UHFFFAOYSA-N 0.000 description 1
- YUZJZPMLAIYVGM-UHFFFAOYSA-N 2-n-methylethane-1,1,2-triamine Chemical compound CNCC(N)N YUZJZPMLAIYVGM-UHFFFAOYSA-N 0.000 description 1
- JIRLWRUWVNHTQG-UHFFFAOYSA-N 3,4-diaminobutane-1-sulfonic acid Chemical compound NCC(N)CCS(O)(=O)=O JIRLWRUWVNHTQG-UHFFFAOYSA-N 0.000 description 1
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- 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
- NNLRDVBAHRQMHK-UHFFFAOYSA-N 3-(2-aminoethylamino)propanoic acid Chemical compound NCCNCCC(O)=O NNLRDVBAHRQMHK-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
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- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
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- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 description 1
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- 239000004743 Polypropylene Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
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- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
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- 235000009120 camo Nutrition 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
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
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- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
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- 235000019256 formaldehyde Nutrition 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
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- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
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- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001692 polycarbonate urethane Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920003009 polyurethane dispersion Polymers 0.000 description 1
- 229920006306 polyurethane fiber Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
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- 125000001302 tertiary amino group Chemical group 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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Classifications
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
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Abstract
本发明要解决的课题在于提供泡保持性、手感和剥离强度优异的发泡片。本发明提供一种发泡片,其特征在于,是由氨基甲酸酯树脂(X)的水分散体形成的发泡片,上述水分散体中的氨基甲酸酯树脂(X)的含有率为50~80质量%,且上述水分散体不含有机溶剂。另外,本发明提供一种合成皮革,其特征在于,至少具有基材(i)和聚氨酯层(ii),上述聚氨酯层(ii)由上述发泡片形成。上述发泡片的密度优选为200~1000kg/m3。
Description
技术领域
本发明涉及发泡片及合成皮革。
背景技术
氨基甲酸酯树脂由于其机械强度、手感良好而被广泛用于合成皮革(包括人工皮革。)、涂布剂、粘接剂、手套、衣料等的制造。对于上述氨基甲酸酯树脂而言,迄今为止,含有N,N-二甲基甲酰胺(DMF)的溶剂系的氨基甲酸酯树脂是主流。然而,在欧洲的DMF管制、中国的VOC排出管制的强化、大型服装制造商的DMF管制等背景下,要求基于弱溶剂化、水系化、无溶剂化等的环境调和对策。
在这样的环境下,使氨基甲酸酯树脂分散于水中而得到的氨基甲酸酯树脂水分散体(聚氨酯分散体)开始用于上述用途。然而,上述氨基甲酸酯树脂水分散体无法得到使以往的溶剂系氨基甲酸酯树脂湿式凝固而形成的中间多孔层,因此存在手感、耐弯曲性等不良的问题。作为解决该问题的方法,提出了在氨基甲酸酯树脂水分散体中配合微胶囊的方法、使气体分散的机械发泡法等(例如,参照专利文献1。)。然而,前者的方法中,手感变硬、或微胶囊的膨胀导致的平滑性不良成为问题,另外,后者的方法中,在氨基甲酸酯树脂水分散体的干燥时,配合液中的气泡合为一体、消失,因此极其难以控制泡的尺寸、量。
现有技术文献
专利文献
专利文献1:日本特开2013-119688号公报
发明内容
发明要解决的课题
本发明所要解决的课题在于提供泡保持性、手感和剥离强度优异的发泡片。
用于解决课题的手段
本发明提供一种发泡片,其特征在于,是由氨基甲酸酯树脂(X)的水分散体形成的发泡片,上述水分散体中的氨基甲酸酯树脂(X)的含有率为50~80质量%,且上述水分散体不含有机溶剂。
另外,本发明提供一种合成皮革,其特征在于,至少具有基材(i)和聚氨酯层(ii),上述聚氨酯层(ii)由上述发泡片形成。
发明效果
本发明的发泡片的泡保持性、手感和剥离强度优异。因此,本发明的发泡片可以特别适合用作合成皮革的中间层。
具体实施方式
本发明的发泡片由特定的氨基甲酸酯树脂(X)水分散体形成。
上述氨基甲酸酯树脂水分散体中,氨基甲酸酯树脂(X)的含有率为50~80质量%,且不含有机溶剂。
在本发明中,上述氨基甲酸酯树脂(X)的含有率必须为50~80质量%的范围。这样,通过使水分散体中的所谓的氨基甲酸酯树脂(X)固体成分高,从而即使通过机械发泡、气体导入而掺入泡,泡保持性也优异,且氨基甲酸酯树脂水分散体的干燥性提高,因此在干燥时和/或干燥后发泡片不会产生裂纹等,能够得到优异的手感、平面平滑性和剥离强度。另外,由于氨基甲酸酯树脂(X)固体成分高,所以也能够提高将水干燥时的线速度。作为上述氨基甲酸酯树脂(X)的含有率,从得到更优异的手感、平面平滑性和剥离强度的方面出发,优选为53~70质量%的范围,更优选为55~70质量%的范围,进一步优选为57~65质量%的范围。
上述氨基甲酸酯树脂(X)可以分散于水中,例如可以使用具有阴离子性基团、阳离子性基团、非离子性基团等亲水性基团的氨基甲酸酯树脂;用乳化剂强制性地分散于水中的氨基甲酸酯树脂等。这些氨基甲酸酯树脂可以单独使用,也可以组合使用2种以上。其中,从制造稳定性和水分散稳定性的方面出发,优选使用具有亲水性基团的氨基甲酸酯树脂,更优选具有阴离子性基团和/或非离子性基团的氨基甲酸酯树脂。
作为得到上述具有阴离子性基团的氨基甲酸酯树脂的方法,例如可举出使用选自具有羧基的二醇化合物和具有磺酰基的化合物中的1种以上的化合物作为原料的方法。
作为上述具有羧基的二醇化合物,例如可以使用2,2-二羟甲基丙酸、2,2-二羟甲基丁酸、2,2-二羟甲基酪酸、2,2-二羟甲基丙酸、2,2-戊酸等。这些化合物可以单独使用,也可以组合使用2种以上。
作为上述具有磺酰基的化合物,例如可以使用3,4-二氨基丁磺酸、3,6-二氨基-2-甲苯磺酸、2,6-二氨基苯磺酸、N-(2-氨基乙基)-2-氨基磺酸、N-(2-氨基乙基)-2-氨基乙基磺酸、N-2-氨基乙烷-2-氨基磺酸、N-(2-氨基乙基)-β-丙氨酸;它们的盐。这些化合物可以单独使用,也可以组合使用2种以上。
作为得到上述具有非离子性基团的氨基甲酸酯树脂的方法,例如可举出使用具有氧亚乙基(oxyethylene)结构的化合物作为原料的方法。
作为上述具有氧亚乙基结构的化合物,例如可以使用聚乙二醇、聚氧亚乙基聚氧亚丙基二醇、聚氧亚乙基聚氧四亚甲基二醇、聚乙二醇二甲醚等具有氧亚乙基结构的聚醚多元醇。这些化合物可以单独使用,也可以组合使用2种以上。其中,从能够更简便地控制亲水性的方面出发,优选使用聚乙二醇和/或聚乙二醇二甲醚。
作为为了得到上述具有非离子性基团的氨基甲酸酯树脂而使用的原料的数均分子量,从得到更优异的乳化性和水分散稳定性的方面出发,优选为200~10000的范围,更优选为300~3000的范围,更优选为300~2000的范围。需要说明的是,为了得到上述具有非离子性基团的氨基甲酸酯树脂而使用的原料的数均分子量表示通过凝胶渗透色谱(GPC)法测定的值。
作为得到上述具有阳离子性基团的氨基甲酸酯树脂的方法,例如可举出使用1种或2种以上的具有氨基的化合物作为原料的方法。
作为上述具有氨基的化合物,例如可以使用三亚乙基四胺、二亚乙基三胺等具有伯氨基和仲氨基的化合物;N-甲基二乙醇胺、N-乙基二乙醇胺等N-烷基二烷醇胺、N-甲基二氨基乙基胺、N-乙基二氨基乙基胺等N-烷基二氨基烷基胺等具有叔氨基的化合物等。这些化合物可以单独使用,也可以组合使用2种以上。
作为在得到上述强制性地分散于水中的氨基甲酸酯树脂时可以使用的乳化剂,例如可以使用聚氧亚乙基壬基苯基醚、聚氧亚乙基月桂基醚、聚氧亚乙基苯乙烯基苯基醚、聚氧亚乙基山梨糖醇四油酸酯、聚乙烯·聚丙烯共聚物等非离子性乳化剂;油酸钠等脂肪酸盐、烷基硫酸酯盐、烷基苯磺酸盐、烷基磺基琥珀酸盐、萘磺酸盐、聚氧亚乙基烷基硫酸盐、烷烃磺酸酯钠盐(アルカンスルフォネートナトリウム塩)、烷基二苯基醚磺酸钠盐等阴离子性乳化剂;烷基胺盐、烷基三甲基铵盐、烷基二甲基苄基铵盐等阳离子性乳化剂等。这些乳化剂可以单独使用,也可以组合使用2种以上。
作为上述氨基甲酸酯树脂(X),具体而言,例如可以使用扩链剂(a1)、多元醇(a2)、多异氰酸酯(a3)以及根据需要使用的具有亲水性基团的化合物(a4)(为了得到上述具有阴离子性基团的氨基甲酸酯树脂、具有阳离子性基团的氨基甲酸酯树脂以及具有非离子性基团的氨基甲酸酯树脂而使用的原料)的反应产物。
作为上述扩链剂(a1),可以使用分子量小于500(优选为50~450的范围)的扩链剂,具体而言,可以使用乙二醇、二乙二醇、三乙二醇、丙二醇、二丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、六亚甲基二醇、蔗糖、亚甲基二醇、甘油、山梨糖醇、双酚A、4,4’-二羟基联苯、4,4’-二羟基二苯醚、三羟甲基丙烷等具有羟基的扩链剂;乙二胺、1,2-丙二胺、1,6-六亚甲基二胺、哌嗪、2,5-二甲基哌嗪、异佛尔酮二胺、1,2-环己二胺、1,3-环己二胺、1,4-环己二胺、4,4’-二环己基甲烷二胺、3,3’-二甲基-4,4’-二环己基甲烷二胺、1,4-环己二胺、肼等具有氨基的扩链剂等。这些扩链剂可以单独使用,也可以组合使用2种以上。需要说明的是,上述扩链剂(a1)的分子量表示根据化学式算出的值。
作为上述扩链剂(a1),从即使在30℃以下的比较低的温度下也能够容易地扩链,能够抑制反应时的能量消耗的方面、以及通过导入脲基而得到更优异的机械强度、成膜性、手感和剥离强度的方面出发,优选使用具有氨基的扩链剂(以下简记为“胺系扩链剂”。),从即便使氨基甲酸酯树脂(X)高固体成分化也可以得到更优异的泡保持性、乳化性和水分散稳定性的方面出发,更优选使用分子量为30~250的范围的胺系扩链剂。需要说明的是,在组合使用2种以上作为上述扩链剂的情况下,上述分子量表示其平均值,平均值包含在上述优选的分子量范围内即可。
作为上述扩链剂(a1)的使用比例,从得到更优异的机械强度、成膜性、手感、剥离强度、泡保持性、乳化性、水分散稳定性的方面、氨基甲酸酯树脂(X)的高固体成分化变得更容易的方面出发,在构成氨基甲酸酯树脂(X)的原料的合计质量中进一步优选为0.1~30质量%的范围,特别优选为0.5~10质量%的范围。
作为上述多元醇(a2),例如可以使用聚醚多元醇、聚酯多元醇、聚丙烯酸系多元醇、聚碳酸酯多元醇、聚丁二烯多元醇等。这些多元醇可以单独使用,也可以组合使用2种以上。需要说明的是,在使用上述具有非离子性基团的氨基甲酸酯树脂作为上述氨基甲酸酯树脂(X)的情况下,作为上述多元醇(a2),使用为了得到上述具有非离子性基团的氨基甲酸酯树脂而使用的原料以外的物质。
作为上述多元醇(a2)的数均分子量,从所得到的覆膜的机械强度的方面出发,优选为500~100000的范围,更优选为800~10000的范围。需要说明的是,上述多元醇(a2)的数均分子量表示通过凝胶渗透柱色谱(GPC)法测定的值。
作为上述多元醇(a2)的使用比例,从可以得到更优异的机械强度的方面出发,在构成氨基甲酸酯树脂(X)的原料的合计质量中进一步优选为40~90质量%的范围,特别优选为50~80质量%的范围。
作为上述多异氰酸酯(a3),例如可以使用苯二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、苯二亚甲基二异氰酸酯、萘二异氰酸酯、多亚甲基多苯基多异氰酸酯、碳二亚胺化二苯基甲烷多异氰酸酯等芳香族多异氰酸酯;六亚甲基二异氰酸酯、赖氨酸二异氰酸酯、环己烷二异氰酸酯、异佛尔酮二异氰酸酯、二环己基甲烷二异氰酸酯、苯二亚甲基二异氰酸酯、四甲基苯二亚甲基二异氰酸酯、二聚酸二异氰酸酯、降冰片烯二异氰酸酯等脂肪族多异氰酸酯或脂环式多异氰酸酯等。这些多异氰酸酯可以单独使用,也可以组合使用2种以上。
作为上述多异氰酸酯(a3)的使用比例,从可以得到更优异的机械强度的方面出发,在构成氨基甲酸酯树脂(X)的原料的合计质量中进一步优选为5~40质量%的范围,特别优选为10~35质量%的范围。
作为上述具有亲水性基团的化合物(a4)的使用比例,从可以得到更优异的泡保持性、乳化性、水分散稳定性和成膜性的方面出发,在构成氨基甲酸酯树脂(X)的原料的合计质量中优选为5质量%以下,更优选为2质量%以下,进一步优选为0.25~2质量%的范围,特别优选为0.5~1.8质量%的范围。
作为上述氨基甲酸酯树脂(X)的平均粒径,从可以得到更优异的泡保持性、表面平滑性、手感和成膜性的方面出发,优选为0.01~1μm的范围,更优选为0.05~0.9μm的范围。需要说明的是,上述氨基甲酸酯树脂(X)的平均粒径的测定方法在后述的实施例中记载。
作为本发明中使用的水,可以使用离子交换水、蒸馏水等。这些水可以单独使用,也可以组合使用2种以上。
本发明中使用的氨基甲酸酯树脂水分散体含有上述氨基甲酸酯树脂(X)和水作为必须成分,但也可以根据需要含有其他添加剂。
作为上述其他添加剂,例如可以使用乳化剂、交联剂、中和剂、增稠剂、氨基甲酸酯化催化剂、填充剂、颜料、染料、阻燃剂、流平剂、抗粘连剂、成膜助剂、发泡剂等。这些添加剂可以单独使用,也可以组合使用2种以上。这些添加剂根据使用发泡片的目的适当确定。需要说明的是,本发明中使用的氨基甲酸酯树脂水分散体在其制造工序中不含有机溶剂,但作为上述添加剂,允许包含有机溶剂。
接下来,对本发明中使用的氨基甲酸酯树脂水分散体的制造方法进行说明。
作为本发明中使用的氨基甲酸酯树脂水分散体的制造方法,具有如下工序:使上述多元醇(a2)、上述多异氰酸酯(a3)和上述具有亲水性基团的化合物(a4)在无溶剂下反应,得到具有异氰酸酯基的氨基甲酸酯预聚物(i)(以下简记为“预聚物工序”。),接下来,使氨基甲酸酯预聚物(i)分散于上述水中(以下简记为“乳化工序”。),然后,使上述扩链剂(a1)反应而得到氨基甲酸酯树脂(X)的工序(以下简记为“扩链工序”。)。
上述预聚物工序在无溶剂下进行是重要的。在现有技术中,在预聚物工序时,通常在甲乙酮、丙酮等有机溶剂中进行,但在乳化工序后需要将上述有机溶剂蒸馏除去的脱溶剂工序,在实际生产现场需要几天的生产天数。另外,在上述脱溶剂工序中也难以完全将有机溶剂蒸馏除去,残留一些有机溶剂的情况多,难以完全应对环保对策。另一方面,在本发明的制造方法中,通过在无溶剂下进行上述预聚物工序,能够得到完全不包含有机溶剂的氨基甲酸酯树脂水分散体,并且其生产工序也能够省力化。
另外,在通过使用有机溶剂的现有方法进行预聚物工序的情况下,有时原本就无法将氨基甲酸酯树脂乳化,或者即使能够乳化,所得到的氨基甲酸酯树脂的粒径有时也会变大,能够得到良好的氨基甲酸酯树脂水分散体的区域非常有限。其理由尚未详细阐明,但认为在乳化时,有机溶剂、(用于调整具有阴离子性基团的氨基甲酸酯树脂的酸值的)中和剂等对氨基甲酸酯树脂所具有的亲水性基团的能力产生阻碍是一个原因。
与此相对,在本发明中,通过在无溶剂下进行上述预聚物工序,能够稳定地得到亲水性基团的导入量少、且使扩链剂反应而得到的具有与以往方法同等的平均粒径的氨基甲酸酯树脂的水分散体,该氨基甲酸酯树脂的水分散体是在以往方法中特别困难的区域。
作为上述预聚物工序中的上述多元醇(a2)所具有的羟基以及上述具有亲水性基团的化合物(a4)所具有的羟基和氨基的合计与上述多异氰酸酯(a3)所具有的异氰酸酯基的摩尔比[异氰酸酯基/(羟基和氨基)],从可以得到更优异的泡保持性、表面平滑性、成膜性、手感、剥离强度和机械强度的方面出发,优选为1.1~3的范围,更优选为1.2~2的范围。
上述预聚物工序的反应例如可举出在50~120℃下进行1~10小时。
上述预聚物工序可以通过使用如下装置来进行:具备搅拌叶片的反应釜;捏合机、连续捏合机、锥形辊、单螺杆挤出机、双螺杆挤出机、三螺杆挤出机、万能混合机、Plastmill(プラストミル)、主体型(ボデーダ)混炼机等混炼机;TK均质混合机、Fill Mix(フイルミツクス)、Ebara Milder(エバラマイルダー)、Claire mix(クレアミックス)、ULTRA-TURRAX(ウルトラターラツクス)、乳化分散机(Cavitron)、生物混合器等旋转式分散混合机;超声波式分散装置;在线混合器等没有可动部,能够通过流体自身的流动进行混合的装置等。
上述乳化工序优选在水不蒸发的温度下进行,例如可举出10~90℃的范围,上述乳化工序可以使用与上述预聚物工序相同的设备来进行。其中,从可以简便地得到氨基甲酸酯树脂的含有率高的氨基甲酸酯树脂水分散体的方面出发,优选使用混炼机,更优选双螺杆挤出机。
上述扩链工序是通过上述氨基甲酸酯预聚物(i)所具有的异氰酸酯基与上述扩链剂(a1)的反应,使氨基甲酸酯预聚物(i)高分子量化,从而得到氨基甲酸酯树脂(X)的工序。作为上述扩链工序时的温度,从生产性的方面出发,优选在50℃以下进行。
作为上述扩链工序中的上述氨基甲酸酯预聚物(i)所具有的异氰酸酯基与上述扩链剂(a1)所具有的羟基和氨基的合计的摩尔比[(羟基和氨基)/异氰酸酯基],从可以得到更优异的成膜性和机械强度的方面出发,优选为0.8~1.1的范围,更优选为0.9~1的范围。
上述扩链工序可以使用与上述预聚物工序相同的设备来进行。
接下来,对本发明的发泡片进行说明。
上述发泡片可以通过由上述氨基甲酸酯树脂(X)的水分散体得到泡液,将该泡液涂布于基材并使其干燥来制造。
作为由上述氨基甲酸酯树脂(X)的水分散体得到泡液的方法,例如可举出利用手进行的搅拌、使用机械混合机等混合机的方法、导入空气、非活性气体的方法等。在使用混合机的情况下,例如可举出以500~3000rpm搅拌10秒~3分钟的方法。此时,从容易将发泡氨基甲酸酯片的密度调整为优选的范围的观点出发,在起泡前后,优选为1.3~7倍的体积,更优选为1.2~2倍的体积,进一步优选为1.3~1.7倍的体积。
作为将所得到的泡液涂布于脱模纸等基材的方法,例如可举出使用辊涂机、刮刀涂布机、逗号涂布机、涂抹器等的方法。
作为上述涂布物的干燥方法,例如可举出在60~130℃的温度干燥30秒~10分钟的方法。
作为通过以上的方法得到的发泡片的厚度,例如为5~200μm。
作为上述发泡片的密度,从可以得到更优异的手感和剥离强度的方面出发,优选为200~1000kg/m3的范围,更优选为300~900kg/m3的范围,进一步优选为400~800kg/m3的范围。需要说明的是,上述发泡氨基甲酸酯片的密度表示通过将发泡氨基甲酸酯片的质量除以体积而算出的值。
接下来,对本发明的合成皮革进行说明。
本发明的合成皮革至少具有基材(i)和聚氨酯层(ii),上述聚氨酯层(ii)由上述发泡片形成。
作为上述合成皮革的制造方法,例如可举出:
(X)由上述氨基甲酸酯树脂组合物得到泡液,将该泡液涂布于脱模纸上,使其干燥,与上述基材(i)贴合的方法,
(Y)由上述氨基甲酸酯树脂组合物得到泡液,将该起泡液涂布于在脱模纸上制作的表皮层上,使其干燥,与上述基材(i)贴合的方法,
(Z)由上述氨基甲酸酯树脂组合物得到泡液,将该泡液涂布于上述基材(i)上,使其干燥,根据需要在其上贴合在脱模纸上制作的表皮层(iii)的方法等。
作为上述基材(i),例如可以使用基于聚酯纤维、聚乙烯纤维、尼龙纤维、丙烯酸系纤维、聚氨酯纤维、乙酸酯纤维、人造丝纤维、聚乳酸纤维、棉、麻、丝、羊毛、玻璃纤维、碳纤维、它们的混纺纤维等的无纺布、机织布、针织物等纤维基材;使聚氨酯树脂等树脂浸渗于上述无纺布而得到的基材;在上述无纺布上进一步设置有多孔质层而得到的基材;热塑性氨基甲酸酯(TPU)等树脂基材等。
上述聚氨酯层(ii)由上述发泡片形成,作为其密度,从能够得到兼顾更优异的手感和剥离强度的合成皮革的方面出发,优选为200~1000kg/m3的范围,优选为300~900kg/m3的范围,更优选为400~800kg/m3的范围。需要说明的是,上述聚氨酯层(ii)的密度表示从每10cm见方的合成皮革的重量中减去每10cm见方的基材(i)的重量而得到的值除以聚氨酯层(ii)的厚度而得到的值。需要说明的是,上述聚氨酯层(ii)的密度可以根据上述氨基甲酸酯树脂组合物的起泡情况来调整。
作为上述表皮层(iii),可以利用公知的材料通过公知的方法来形成,例如可以使用溶剂系氨基甲酸酯树脂、水系氨基甲酸酯树脂、有机硅树脂、聚丙烯树脂、聚酯树脂等。在重视柔软的手感、以及耐热性、耐水解性的情况下,优选使用聚碳酸酯系氨基甲酸酯树脂。另外,为了在应对环境时减少DMF,更优选使用水系聚碳酸酯系氨基甲酸酯树脂。
在上述表皮层(iii)上,可以根据需要以提高耐擦伤性等为目的而设置表面处理层(iv)。作为上述表面处理层(iv),可以利用公知的材料通过公知的方法形成。
【实施例】
以下,使用实施例更详细地说明本发明。
[合成例1]
在辛酸亚锡0.1质量份的存在下,将聚醚多元醇(三菱化学株式会社制“PTMG2000”,数均分子量:2000,以下简记为“PTMG2000”。)1000质量份、2,2-二羟甲基丙酸(以下简记为“DMPA”。)24质量份、以及二环己基甲烷二异氰酸酯(以下简记为“HMDI”。)262质量份在100℃下反应,直至NCO%达到2.1质量%,得到氨基甲酸酯预聚物A1。
将加热至70℃的A1和三乙胺、作为乳化剂的十二烷基苯磺酸钠20质量%水溶液(第一工业制药株式会社制“NEOGEN S-20F”)、水同时供给至双螺杆挤出机(TEM-18SS:东芝机械制)并混合,由此得到乳化液。供给液各自的流量为A1:10kg/小时,三乙胺:0.2kg/小时,乳化剂水溶液:2.5kg/小时,水:5.1kg/小时,双螺杆挤出机运转条件为50℃、260rpm。
然后,立即添加相当于NCO基的95%的氨基含量的异佛尔酮二胺(以下简记为“IPDA”。)的水稀释液使其扩链,最终得到氨基甲酸酯树脂的含有率为50质量%的聚氨酯乳液(X-1)。
[合成例2]
在辛酸亚锡0.1质量份的存在下,使1000质量份的PTMG2000、24质量份的DMPA和262质量份的HMDI在100℃下反应,直至NCO%达到2.1质量%,得到氨基甲酸酯预聚物A2。
将加热至70℃的A2和三乙胺、作为乳化剂的聚丙烯聚乙烯共聚物(株式会社ADEKA制“Pluronic L-64”)、水同时供给至双螺杆挤出机(TEM-18SS:东芝机械制)并混合,由此得到乳化液。供给液各自的流量为A2:10kg/小时,三乙胺:0.2kg/小时,L-64:0.5kg/小时,水:7.1kg/小时,双螺杆挤出机运转条件为50℃、260rpm。
然后,立即添加相当于NCO基的95%的氨基含量的IPDA的水稀释液使其扩链,最终得到氨基甲酸酯树脂的含有率为50质量%的聚氨酯乳液(X-2)。
[合成例3]
在辛酸亚锡0.1质量份的存在下,将1000质量份的PTMG2000、24质量份的DMPA和262质量份的HMDI在100℃下反应,直至NCO%达到2.1质量%,得到氨基甲酸酯预聚物A3。
将加热至70℃的A3和三乙胺、水同时供给至双螺杆挤出机(TEM-18SS:东芝机械制)并混合,由此得到乳化液。供给液各自的流量为A3:10kg/小时,三乙胺:0.2kg/小时,水:6.6kg/小时,双螺杆挤出机运转条件为50℃、260rpm。
然后,立即添加相当于NCO基的95%的氨基含量的IPDA的水稀释液使其扩链,最终得到氨基甲酸酯树脂的含有率为50质量%的聚氨酯乳液(X-3)。
[合成例4]
在辛酸亚锡0.1质量份的存在下,将1000质量份的PTMG2000、聚乙二醇(日油株式会社制“PEG600”,数均分子量:600,以下简记为“PEG”。)18质量份和262质量份的HMDI在100℃下反应,直至NCO%达到3.1质量%,得到氨基甲酸酯预聚物A4。
将加热至70℃的A4和作为乳化剂的十二烷基苯磺酸钠20质量%水溶液(第一工业制药株式会社制“NEOGEN S-20F”)、水同时供给至双螺杆挤出机(TEM-18SS:东芝机械制)并混合,由此得到乳化液。供给液各自的流量为A4:10kg/小时,乳化剂水溶液:2.5kg/小时,水:0.1kg/小时,双螺杆挤出机运转条件为50℃、260rpm。
然后,立即添加相当于NCO基的95%的氨基含量的IPDA的水稀释液使其扩链,最终得到氨基甲酸酯树脂的含有率为60质量%的聚氨酯乳液(X-4)。
[合成例5]
在辛酸亚锡0.1质量份的存在下,使1000质量份的PTMG2000、18质量份的PEG和262质量份的HMDI在100℃下反应,直至NCO%达到3.1质量%,得到氨基甲酸酯预聚物A5。
将加热至70℃的A5和作为乳化剂的聚丙烯聚乙烯共聚物(株式会社ADEKA制“Pluronic L-64”)、水同时供给至双螺杆挤出机(TEM-18SS:东芝机械制)并混合,由此得到乳化液。供给液各自的流量为A5:10kg/小时,乳化剂:0.5kg/小时,水:5.8kg/小时,双螺杆挤出机运转条件为50℃、260rpm。
然后,立即添加相当于NCO基的95%的氨基含量的IPDA的水稀释液使其扩链,最终得到氨基甲酸酯树脂的含有率为60质量%的聚氨酯乳液(X-5)。
[合成例6]
在辛酸亚锡0.1质量份的存在下,使1000质量份的PTMG2000、聚乙二醇二甲醚(日油株式会社制“M550”,数均分子量:550,以下简记为“MPEG”。)18质量份和262质量份的HMDI在100℃下反应,直至NCO%达到3.3质量%,得到氨基甲酸酯预聚物A6。
将加热至70℃的A6和水同时供给至双螺杆挤出机(TEM-18SS:东芝机械制)并混合,由此得到乳化液。供给液各自的流量为A6:10kg/小时,水:4.9kg/小时,双螺杆挤出机运转条件为50℃、260rpm。
然后,立即添加相当于NCO基的95%的氨基含量的IPDA的水稀释液使其扩链,最终得到氨基甲酸酯树脂的含有率为50质量%的聚氨酯乳液(X-6)。
[合成例7]
在辛酸亚锡0.1质量份的存在下,使1000质量份的PTMG2000、18质量份的PEG和262质量份的HMDI在100℃下反应,直至NCO%达到3.1质量%,得到氨基甲酸酯预聚物A7。
将加热至70℃的A7和作为乳化剂的十二烷基苯磺酸钠20质量%水溶液(第一工业制药株式会社制“NEOGEN S-20F”)、聚丙烯聚乙烯共聚物(株式会社ADEKA制“Pluronic L-64”)、水同时供给至双螺杆挤出机(TEM-18SS:东芝机械制)并混合,由此得到乳化液。供给液各自的流量为A7:10kg/小时,乳化剂水溶液S-20F:1.3kg/小时,乳化剂L-64:0.3kg/小时,水:1.1kg/小时,双螺杆挤出机运转条件为50℃、260rpm。
然后,立即添加相当于NCO基的95%的氨基含量的乙二胺(以下简记为“EA”。)的水稀释液使其扩链,最终得到氨基甲酸酯树脂的含有率为60质量%的聚氨酯乳液(X-7)。
[比较合成例1]
在辛酸亚锡0.1质量份的存在下,使1000质量份的PTMG2000、34质量份的DMPA和262质量份的HMDI在100℃下反应,直至NCO%达到1.6质量%,得到氨基甲酸酯预聚物A’1。
将加热至70℃的A’1和三乙胺、作为乳化剂的十二烷基苯磺酸钠20质量%水溶液(第一工业制药株式会社制“NEOGEN S-20F”)、水同时供给至双螺杆挤出机(TEM-18SS:东芝机械制)并混合,由此得到乳化液。
需要说明的是,使供给液、双螺杆挤出机运转条件与实施例1相同,尝试制造固体成分浓度为50%的聚氨酯乳液,在所得到的乳化液中立即添加相当于NCO基的95%的氨基含量的IPDA的水稀释液使其扩链,但发生凝胶化,因此无法得到乳液。
因此,增加水量降低固体成分而制造聚氨酯乳液。供给液各自的流量为A’1:10kg/小时,三乙胺:0.2kg/小时,乳化剂水溶液:2.5kg/小时,水:19.6kg/小时,双螺杆挤出机运转条件为50℃、260rpm。
然后,立即添加相当于NCO基的95%的氨基含量的IPDA的水稀释液使其扩链,最终得到氨基甲酸酯树脂的含有率为30质量%的聚氨酯乳液(XR-1)。
[比较合成例2]
在辛酸亚锡0.1质量份的存在下,使1000质量份的PTMG2000、34质量份的DMPA和262质量份的HMDI在100℃下反应,直至NCO%达到1.6质量%,得到氨基甲酸酯预聚物A’2。
将加热至70℃的A’2和三乙胺、作为乳化剂的聚丙烯聚乙烯共聚物(株式会社ADEKA制“Pluronic L-64”)、水同时供给至双螺杆挤出机(TEM-18SS:东芝机械制)并混合,由此得到乳化液。
需要说明的是,使供给液、双螺杆挤出机运转条件与实施例2相同,尝试制造氨基甲酸酯树脂的含有率为50质量%的聚氨酯乳液,在所得到的乳化液中立即添加相当于NCO基的95%的氨基含量的IPDA的水稀释液使其扩链,但发生凝胶化,因此无法得到乳液。
因此,增加水量降低固体成分而制造聚氨酯乳液。供给液各自的流量为A’2:10kg/小时,三乙胺:0.2kg/小时,乳化剂水溶液:0.5kg/小时,水:21.6kg/小时,双螺杆挤出机运转条件为50℃、260rpm。
然后,立即添加相当于NCO基的95%的氨基含量的IPDA的水稀释液使其扩链,最终得到氨基甲酸酯树脂的含有率为30质量%的聚氨酯乳液(XR-2)。
[比较合成例3]
在辛酸亚锡0.1质量份的存在下,使1000质量份的PTMG2000、34质量份的DMPA和262质量份的HMDI在100℃下反应,直至NCO%达到1.6质量%,得到氨基甲酸酯预聚物A’3。
将加热至70℃的A’3和三乙胺、水同时供给至双螺杆挤出机(TEM-18SS:东芝机械制)并混合,由此得到乳化液。
需要说明的是,使供给液、双螺杆挤出机运转条件与实施例3相同,尝试制造氨基甲酸酯树脂的含有率为50质量%的聚氨酯乳液,在所得到的乳化液中立即添加相当于NCO基的95%的氨基含量的IPDA的水稀释液使其扩链,但发生凝胶化,因此无法得到乳液。
因此,增加水量降低固体成分而制造聚氨酯乳液。供给液各自的流量A’3:10kg/小时,三乙胺:0.2kg/小时,乳化剂水溶液:0.5kg/小时,水:20.4kg/小时,双螺杆挤出机运转条件为50℃、260rpm。
然后,立即添加相当于NCO基的95%的氨基含量的IPDA的水稀释液使其扩链,最终得到氨基甲酸酯树脂的含有率为30质量%的聚氨酯乳液(XR-3)。
[比较合成例4]
在辛酸亚锡0.1质量份的存在下,使1000质量份的PTMG2000、75质量份的PEG和262质量份的HMDI在100℃下反应,直至NCO%达到2.4质量%,得到氨基甲酸酯预聚物A’4。
将加热至70℃的A’4和作为乳化剂的十二烷基苯磺酸钠20质量%水溶液(第一工业制药株式会社制“NEOGEN S-20F”)、水同时供给至双螺杆挤出机(TEM-18SS:东芝机械制)并混合,由此得到乳化液。
需要说明的是,使供给液、双螺杆挤出机运转条件与实施例4相同,尝试制造氨基甲酸酯树脂的含有率为60质量%的聚氨酯乳液,在所得到的乳化液中立即添加相当于NCO基的95%的氨基含量的IPDA的水稀释液使其扩链,但发生凝胶化,因此无法得到乳液。
因此,增加水量降低固体成分而制造聚氨酯乳液。供给液各自的流量为A’4:10kg/小时,乳化剂水溶液:2.5kg/小时,水:9.3kg/小时,双螺杆挤出机运转条件为50℃、260rpm。
然后,立即添加相当于NCO基的95%的氨基含量的IPDA的水稀释液使其扩链,最终得到氨基甲酸酯树脂的含有率为40质量%的聚氨酯乳液(XR-4)。
[比较合成例5]
在辛酸亚锡0.1质量份的存在下,使1000质量份的PTMG2000、75质量份的PEG和262质量份的HMDI在100℃下反应,直至NCO%达到2.4质量%,得到氨基甲酸酯预聚物A’5。
将加热至70℃的A’5和作为乳化剂的十二烷基苯磺酸钠20质量%水溶液(第一工业制药株式会社制“NEOGEN S-20F”)、水同时供给至双螺杆挤出机(TEM-18SS:东芝机械制)并混合,得到乳化液。
需要说明的是,使供给液、双螺杆挤出机运转条件与实施例5相同,尝试制造氨基甲酸酯树脂的含有率为50质量%的聚氨酯乳液,在所得到的乳化液中立即添加相当于NCO基的95%的氨基含量的IPDA的水稀释液使其扩链,但发生凝胶化,因此无法得到乳液。
因此,增加水量降低固体成分而制造聚氨酯乳液。供给液各自的流量为A’5:10kg/小时,乳化剂水溶液:0.5kg/小时,水:11.3kg/小时,双螺杆挤出机运转条件为50℃、260rpm。
然后,立即添加相当于NCO基的95%的氨基含量的IPDA的水稀释液使其扩链,最终得到氨基甲酸酯树脂的含有率为40质量%的聚氨酯乳液(XR-5)。
[比较合成例6]
在辛酸亚锡0.1质量份的存在下,将1000质量份的PTMG2000、69质量份的MPEG和262质量份的HMDI在100℃下反应,直至NCO%达到2.8质量%,得到氨基甲酸酯预聚物A’6。
将加热至70℃的A’6和水同时供给至双螺杆挤出机(TEM-18SS:东芝机械制)并混合,由此得到乳化液。
需要说明的是,使供给液、双螺杆挤出机运转条件与实施例6相同,尝试制造氨基甲酸酯树脂的含有率为50质量%的聚氨酯乳液,在所得到的乳化液中立即添加相当于NCO基的95%的氨基含量的IPDA的水稀释液使其扩链,但发生凝胶化,因此无法得到乳液。
因此,增加水量降低固体成分来制造聚氨酯乳液。供给液各自的流量为A’6:10kg/小时、水:10.3kg/小时,双螺杆挤出机运转条件为50℃、260rpm。
然后,立即添加相当于NCO基的95%的氨基含量的IPDA的水稀释液使其扩链,最终得到氨基甲酸酯树脂的含有率为40质量%的聚氨酯乳液(XR-6)。
[实施例1]
将合成例1中得到的聚氨酯乳液(X-1)1000质量份、增稠剂(Borchers公司制“Borchi Gel ALA”)2质量份用机械混合器以2000rpm搅拌,制作配合液。接下来,向转子·定子型的连续式混合器(IKA公司制“MagicLab”)中连续供给上述配合液和空气,进行混合而得到泡液。此时,测定泡液的体积·重量并算出密度,以泡液的密度成为2/3的方式调整空气的供给量。
[泡保持性的评价方法]
(1)外观评价
在聚酯机织布上使用棒涂机以涂布后的厚度成为1000μm的方式涂布所得到的泡液,利用热风干燥机在70℃下干燥2分钟,进一步在120℃下干燥2分钟,形成加工布,如下评价泡保持性。
“A”:聚氨酯层形成有外观上良好的发泡片。
“B”:聚氨酯层中产生裂纹。
“C”:泡从聚氨酯层中消失。
(2)显微镜评价
使用扫描型电子显微镜(Hitachi High-Tech株式会社制“SU3500”,倍率200倍)观察所得到的加工布的截面,如下进行评价。
“T”:在聚氨酯层中确认到气泡。
“F”:在聚氨酯层中未确认到气泡。
[手感的评价方法]
通过触感如下那样评价所得到的加工布。
“A”:富于柔软性。
“B”:稍微有柔软性。
“C”:柔软性差。
“D”:硬。
[剥离强度的评价方法]
在所得到的加工布的聚氨酯层表面载置2.5cm宽度的热熔胶带(SAN CHEMICALS株式会社制“BW-2”),在150℃下加热30秒钟,进行粘接。沿着热熔胶带的宽度切割试样。将该试样的一部分剥离,用卡盘夹持基材和热熔胶带,使用Autograph(株式会社岛津制作所制)测定剥离强度。求出所得到的数据的平均值,换算成1cm宽度,如下进行评价。
“T”:剥离强度为3.0(kgf/cm)以上。
“F”:剥离强度小于3.0(kgf/cm)。
[发泡片密度的评价方法]
将所得到的加工布切成10cm见方后,计量重量。进一步使用厚度计测定厚度。根据同样地进行了计量、测定的聚酯机织布的重量、厚度之差,按照下述式(1)算出发泡片的密度。
[数均分子量等的测定方法]
合成例和比较合成例中使用的多元醇等的数均分子量表示通过凝胶渗透柱色谱(GPC)法在下述条件下测定而得到的值。
测定装置:高速GPC装置(东曹株式会社制“HLC-8220GPC”)
柱:将东曹株式会社制的下述柱串联连接而使用。
“TSKgel G5000”(7.8mmI.D.×30cm)×1根
“TSKgel G4000”(7.8mmI.D.×30cm)×1根
“TSKgel G3000”(7.8mmI.D.×30cm)×1根
“TSKgel G2000”(7.8mmI.D.×30cm)×1根
检测器:RI(差示折射计)
柱温:40℃
洗脱液:四氢呋喃(THF)
流速:1.0mL/分钟
注入量:100μL(试样浓度0.4质量%的四氢呋喃溶液)
标准试样:使用下述标准聚苯乙烯制作标准曲线。
(标准聚苯乙烯)
东曹株式会社制“TSKgel标准聚苯乙烯A-500”
东曹株式会社制“TSKgel标准聚苯乙烯A-1000”
东曹株式会社制“TSKgel标准聚苯乙烯A-2500”
东曹株式会社制“TSKgel标准聚苯乙烯A-5000”
东曹株式会社制“TSKgel标准聚苯乙烯F-1”
东曹株式会社制“TSKgel标准聚苯乙烯F-2”
东曹株式会社制“TSKgel标准聚苯乙烯F-4”
东曹株式会社制“TSKgel标准聚苯乙烯F-10”
东曹株式会社制“TSKgel标准聚苯乙烯F-20”
东曹株式会社制“TSKgel标准聚苯乙烯F-40”
东曹株式会社制“TSKgel标准聚苯乙烯F-80”
东曹株式会社制“TSKgel标准聚苯乙烯F-128”
东曹株式会社制“TSKgel标准聚苯乙烯F-288”
东曹株式会社制“TSKgel标准聚苯乙烯F-550”
[氨基甲酸酯树脂(X)的平均粒径的测定方法]
对于实施例和比较例中得到的氨基甲酸酯树脂水分散体,使用激光衍射/散射式粒度分布测定装置(株式会社堀场制作所制“LA-910”),使用水作为分散液,测定相对折射率=1.10、粒径基准为面积时的平均粒径。
[实施例2~7、比较例1~6]
如表1~2所示那样变更所使用的聚氨酯乳液(X-1)的种类,除此以外,与实施例1同样地操作,得到加工布,进行泡保持性、手感和剥离强度的评价。
【表1】
【表2】
可知本发明的发泡片如实施例1~7所示,可以稳定地得到氨基甲酸酯树脂的水分散体,并且成膜性优异。
另一方面,比较例1~3是使用了氨基甲酸酯树脂(X)的含有率低于本发明中规定的范围的具有阴离子性基团的氨基甲酸酯树脂的方式,但泡保持性、手感不良。比较例4~6是使用了氨基甲酸酯树脂(X)的含有率低于本发明中规定的范围的具有非离子性基团的氨基甲酸酯树脂的方式,但剥离强度不良。
Claims (8)
1.一种发泡片,其特征在于,是由氨基甲酸酯树脂(X)的水分散体形成的发泡片,
所述水分散体中的氨基甲酸酯树脂(X)的含有率为50质量%~80质量%,且所述水分散体不含有机溶剂。
2.根据权利要求1所述的发泡片,其密度为200kg/m3~1000kg/m3。
3.根据权利要求1或2所述的发泡片,其中,所述氨基甲酸酯树脂(X)以扩链剂(a1)为原料。
4.根据权利要求3所述的发泡片,其中,所述扩链剂(a1)具有氨基。
5.根据权利要求1~4中任一项所述的发泡片,其中,所述氨基甲酸酯树脂(X)具有阴离子性基团和/或非离子性基团。
6.根据权利要求1~5中任一项所述的发泡片,其中,所述氨基甲酸酯树脂(X)的平均粒径为0.01μm~1μm的范围。
7.根据权利要求1~6中任一项所述的发泡片,其中,所述氨基甲酸酯树脂(X)以具有亲水性基团的化合物(a4)为原料,所述化合物(a4)的使用比例在构成氨基甲酸酯树脂(X)的原料的合计质量中为5质量%以下。
8.一种合成皮革,其特征在于,至少具有基材(i)和聚氨酯层(ii),
所述聚氨酯层(ii)由权利要求1~7中任一项所述的发泡片形成。
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JPWO2021084953A1 (ja) | 2021-11-25 |
EP4053198A4 (en) | 2023-11-08 |
EP4053198A1 (en) | 2022-09-07 |
JP6981575B2 (ja) | 2021-12-15 |
KR20220038393A (ko) | 2022-03-28 |
WO2021084953A1 (ja) | 2021-05-06 |
TW202124491A (zh) | 2021-07-01 |
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