CN114616284A - 层叠聚酯膜 - Google Patents
层叠聚酯膜 Download PDFInfo
- Publication number
- CN114616284A CN114616284A CN202080075402.1A CN202080075402A CN114616284A CN 114616284 A CN114616284 A CN 114616284A CN 202080075402 A CN202080075402 A CN 202080075402A CN 114616284 A CN114616284 A CN 114616284A
- Authority
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- China
- Prior art keywords
- mass
- resin
- parts
- polyester film
- crosslinking agent
- Prior art date
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- Granted
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- 239000003431 cross linking reagent Substances 0.000 claims abstract description 66
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 52
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 50
- 239000011247 coating layer Substances 0.000 claims abstract description 45
- 239000000203 mixture Substances 0.000 claims abstract description 40
- 239000002253 acid Substances 0.000 claims abstract description 39
- 150000001875 compounds Chemical class 0.000 claims description 22
- 239000012948 isocyanate Substances 0.000 claims description 22
- 150000002513 isocyanates Chemical group 0.000 claims description 22
- 229920005989 resin Polymers 0.000 abstract description 45
- 239000011347 resin Substances 0.000 abstract description 45
- 239000011248 coating agent Substances 0.000 abstract description 23
- 239000000243 solution Substances 0.000 description 58
- 229920001225 polyester resin Polymers 0.000 description 50
- 239000004645 polyester resin Substances 0.000 description 50
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- 239000010408 film Substances 0.000 description 44
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 39
- -1 polyethylene terephthalate Polymers 0.000 description 36
- 239000000976 ink Substances 0.000 description 35
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- 239000010410 layer Substances 0.000 description 26
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- 239000004417 polycarbonate Substances 0.000 description 15
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- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 10
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 10
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 9
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- 125000001931 aliphatic group Chemical group 0.000 description 8
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 238000009775 high-speed stirring Methods 0.000 description 8
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 8
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 7
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- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 7
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- 238000011282 treatment Methods 0.000 description 7
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000002981 blocking agent Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 5
- 229920002799 BoPET Polymers 0.000 description 5
- 229920001634 Copolyester Polymers 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 239000001361 adipic acid Substances 0.000 description 5
- 235000011037 adipic acid Nutrition 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 4
- 229940035437 1,3-propanediol Drugs 0.000 description 4
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 4
- 229920000298 Cellophane Polymers 0.000 description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000007514 bases Chemical class 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- 238000010494 dissociation reaction Methods 0.000 description 4
- 230000005593 dissociations Effects 0.000 description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 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 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- XKVUYEYANWFIJX-UHFFFAOYSA-N 5-methyl-1h-pyrazole Chemical compound CC1=CC=NN1 XKVUYEYANWFIJX-UHFFFAOYSA-N 0.000 description 3
- 239000004971 Cross linker Substances 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 3
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 description 3
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 230000008034 disappearance Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000010954 inorganic particle Substances 0.000 description 3
- WHIVNJATOVLWBW-SNAWJCMRSA-N methylethyl ketone oxime Chemical compound CC\C(C)=N\O WHIVNJATOVLWBW-SNAWJCMRSA-N 0.000 description 3
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- 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 3
- 238000004383 yellowing Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-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
- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-UHFFFAOYSA-N 0.000 description 2
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- CARJPEPCULYFFP-UHFFFAOYSA-N 5-Sulfo-1,3-benzenedicarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(S(O)(=O)=O)=C1 CARJPEPCULYFFP-UHFFFAOYSA-N 0.000 description 2
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- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
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- 238000007334 copolymerization reaction Methods 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
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- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 2
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 description 2
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- 239000000975 dye Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 2
- 239000012788 optical film Substances 0.000 description 2
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Abstract
本发明的目的在于提供一种层叠聚酯膜，其与UV固化性树脂的粘接性良好、特别是与UV固化性墨等涂布剂的粘接性优异、并且具有长期高水平地保持粘接性的优异性能。一种层叠聚酯膜，其包括：聚酯膜；和形成在聚酯膜的至少一个表面上的涂布层，该涂布层由含有以下的组合物形成：具有羧基并且酸值为30～50mgKOH/g的聚氨酯树脂和具有羧基并且酸值为30～50mgKOH/g的交联剂。
Description
技术领域
本发明涉及层叠聚酯膜。更具体地，本发明涉及高度适用于例如光学、包装和标签等所有领域中的、包含易粘接性涂布层的层叠聚酯膜。
热塑性树脂膜，特别是聚酯膜，在机械性能、电性能、尺寸稳定性、透明性、耐化学性等方面具有优异的性能。因此，这种膜可以例如在磁记录材料；包装材料；太阳能电池应用；用于平板显示器等的防反射膜；扩散片；棱镜片等光学膜；和用于标签印刷的膜等得到广泛的应用。然而，由于聚酯膜在其表面上具有高度取向的结晶，因此聚酯膜在用于这些应用的加工中具有在对各种涂料、树脂和墨的粘接性不良的缺点。
为此，迄今已研究了各种方法以赋予聚酯膜表面粘接性。
例如，作为赋予粘接性的方法，迄今已知有表面活化法，例如包括对基材聚酯膜的表面进行电晕放电处理、紫外线照射处理、等离子体处理等的方法。但是，通过这些处理获得的粘接效果随着时间而降低，因此难以长期维持高水平的粘接性(专利文献(PTL)1)。
因此，经常使用包括将各种树脂施涂至聚酯膜的表面以形成易粘接性涂布层的方法。
迄今为止，已知一种技术，该技术包括使用含有共聚酯树脂或聚氨酯树脂的涂布液或使用含有共聚酯树脂、聚氨酯树脂和交联剂的涂布液形成涂布层以增强与它们的亲和性，从而能够容易地与硬涂层剂和棱镜透镜剂中使用的聚氨酯丙烯酸酯或丙烯酸酯等树脂成分粘接(专利文献(PTL)2和3)。但是，用于标签印刷的UV固化性墨(紫外线固化性墨)除了树脂以外，还含有表现色调的染料或颜料，耐光性比较好的颜料占墨成分的约15～25wt.％。此外，由于要求具有遮盖性的白色墨含有约50wt.％的高比例的白色颜料，传统技术仍然不足以实现对白色墨的良好的粘接性，尤其当白色墨在低剂量的UV照射下固化时难以实现高粘接性。
引文列表
专利文献
PTL 1：JPS58-27724A
PTL 2：JP2000-229355A
PTL 3：JP2009-220376A
发明内容
发明要解决的问题
鉴于现有技术的上述问题做出了本发明。更具体地，本发明的目的在于提供一种与UV固化性树脂、特别是如UV固化性墨等涂布剂的粘接性良好、且在长时间维持高水平的粘接性方面也是优异的层叠聚酯膜。
用于解决问题的方案
具体而言，本发明具有以下特征。
1.一种层叠聚酯膜，其包括：
聚酯膜和，
在所述聚酯膜的至少一个表面上的涂布层，
所述涂布层包括含有以下的组合物：具有羧基且酸值为30～50mgKOH/g的聚氨酯树脂，和具有羧基且酸值为30～50mgKOH/g的交联剂。
2.根据项1所述的层叠聚酯膜，其中所述交联剂为异氰酸酯系化合物。
发明的效果
本发明的层叠聚酯膜对如硬涂层、透镜层和墨等UV固化性树脂的粘接性优异，特别是具有对UV固化性墨的高水平的粘接性。
具体实施方式
聚酯膜基材
可用于形成本发明的聚酯膜基材的聚酯树脂的实例包括聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚2,6-萘二甲酸乙二醇酯、聚对苯二甲酸丙二醇酯等；上述聚酯树脂的二醇成分或二羧酸成分的一部分被共聚成分替代而成的共聚酯树脂。这样的共聚成分的实例包括例如二甘醇、新戊二醇、1,4-环己烷二甲醇、聚亚烷基二醇等二醇成分；例如己二酸、癸二酸、邻苯二甲酸、间苯二甲酸、5-间苯二甲酸钠、2,6-萘二甲酸等二羧酸成分；等等。
优选用于本发明的聚酯膜基材的聚酯树脂主要选自聚对苯二甲酸乙二醇酯、聚对苯二甲酸丙二醇酯、聚对苯二甲酸丁二醇酯和聚2,6-萘二甲酸乙二醇酯。在这些聚酯树脂中，从物性与成本之间的平衡的观点出发，最优选聚对苯二甲酸乙二醇酯。使用这样的聚酯树脂形成的聚酯膜基材优选为双轴拉伸聚酯膜，能够改善耐化学药品性、耐热性、机械强度等。
用于聚酯树脂的生产中的缩聚催化剂没有特别限定。从低成本和优异催化活性的观点出发，优选三氧化二锑。使用锗化合物或钛化合物也是优选的。更优选的缩聚催化剂的实例包括含有铝和/或铝化合物和酚类化合物的催化剂；含有铝和/或铝化合物和磷化合物的催化剂；以及含有磷化合物的铝盐的催化剂。
本发明的聚酯膜基材的层结构没有特别限定，可以是单层聚酯膜，两层的成分不同的具有两层结构的聚酯膜，或者由包括外层和内层的至少三层组成的聚酯膜基材。
涂布层
为了提高对硬涂层的粘接性、对UV固化性墨的粘接性、耐粘连性，本发明的层叠聚酯膜优选通过使用包含具有羧基且酸值为30～50mgKOH/g的聚氨酯树脂和具有羧基且酸值为30～50mgKOH/g的交联剂的组合物在聚酯膜的至少一个表面上形成涂布层。涂布层可以形成在聚酯膜的两个表面上；或者可以仅在聚酯膜的一个表面上形成，并且可以在另一个表面上形成不同类型的树脂涂布层。
本发明的涂布层对例如硬涂层、透镜层、或墨等UV固化性树脂或热固性树脂的粘接性优异，对含有颜料等的墨的粘接性特别优异。推测该效果是由于涂布层的羧基和墨的颜料颗粒之间的相互作用。另外，由于聚氨酯树脂和交联剂均含有一定范围内的量的羧基，因此本发明可以使涂布层本身含有许多羧基，同时抑制由于仅在一种树脂中存在许多羧基而发生的耐水性降低引起的如不良的耐湿热性等缺点。
具有羧基的聚氨酯树脂与具有羧基的交联剂的重量比优选在90/10～10/90的范围内，更优选80/20～20/80，甚至更优选70/30～30/70。如果交联剂的量少，则耐湿热性等耐久性降低。另一方面，如果聚氨酯树脂的量少，则粘接性降低。
下面将详细描述涂布层的各组分。
具有羧基且酸值为30～50mgKOH/g的聚氨酯树脂
具有羧基的聚氨酯树脂是指至少使用多元醇成分和多异氰酸酯成分，根据需要进一步使用扩链剂等合成的聚氨酯树脂；并且在分子或侧链中含有羧基。这里提及的“分子中的羧基”是指羧基存在于聚氨酯树脂的主链或至少一端。这里提及的“侧链中的羧基”是指通过合成或聚合例如上述那些等的至少一种具有三个以上的末端官能团的原料成分而得到的在聚氨酯树脂的支链中引入的羧基。
本发明中具有羧基的聚氨酯树脂通过主要使用含羧基的多元醇成分作为氨基甲酸酯成分而获得。
含羧基的多元醇成分的实例包括相对高分子量的多元醇，例如含羧基的聚亚烷基二醇、含羧基的丙烯酸类多元醇、含羧基的聚烯烃多元醇、含羧基的聚酯多元醇等。实例还包括相对低分子量的多元醇，例如2,2-二羟甲基丙酸、2,2-二羟甲基丁酸、2,2-二羟甲基酪酸和2,2-二羟甲基戊酸。为了引入羧基，特别优选二羟甲基丙酸和二羟甲基丁酸。
具有羧基的聚氨酯树脂的酸值优选为30～50mgKOH/g，更优选为35～45mgKOH/g。当酸值为30mgKOH/g以上时，对UV固化性树脂、特别是UV固化性墨的粘接性增加。另一方面，酸值为50mgKOH/g以下是优选的，因为保持了涂布层的耐水性并且膜不会由于吸湿而倾向于彼此粘附。为了补偿聚氨酯树脂的水溶性或水分散性，可以在本发明的聚氨酯树脂中引入其他亲水性基团，如羟基、醚基、磺酸基、膦酸基、季胺基等，只要性能不劣化即可。
聚氨酯树脂中的羧基可以被碱性化合物中和。可用于中和的碱性化合物包括碱金属如钠和钾，碱土金属如镁和钙，以及有机胺化合物。其中，优选加热时容易从羧基解离的有机胺化合物。有机胺化合物的实例包括氨；C1-20直链或支链伯胺、仲胺或叔胺，例如甲胺、乙胺、丙胺、异丙胺、丁胺、2-乙基己胺、环己胺、二甲胺、二乙胺、二丙胺、二异丙胺、二丁胺、三甲胺、三乙胺、三异丙胺、三丁胺，和乙二胺；环状胺类，例如吗啉、N-烷基吗啉和吡啶；含羟基的胺类，例如单异丙醇胺、甲基乙醇胺、甲基异丙醇胺、二甲基乙醇胺、二异丙醇胺、二乙醇胺、三乙醇胺、二乙基乙醇胺和三乙醇胺；等等。
用于合成和聚合本发明的聚氨酯树脂的其他多元醇成分的优选实例包括聚碳酸酯多元醇。特别优选包括耐热性和耐水解性优异的脂肪族聚碳酸酯多元醇。脂肪族聚碳酸酯多元醇的实例包括脂肪族聚碳酸酯二醇和脂肪族聚碳酸酯三醇。优选地，可以使用脂肪族聚碳酸酯二醇。用于合成和聚合本发明的具有聚碳酸酯结构的聚氨酯树脂的脂肪族聚碳酸酯二醇的实例包括通过使一种或两种以上的二醇与碳酸酯反应而获得的脂肪族聚碳酸酯二醇。二醇的实例包括乙二醇、丙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、3-甲基-1,5-戊二醇、1,6-己二醇、1,9-壬二醇、1,8-壬二醇、新戊二醇、二甘醇、二丙二醇等。碳酸酯的实例包括碳酸二甲酯、碳酸亚乙酯、光气等。
本发明的聚碳酸酯多元醇的数均分子量优选为300～5000，更优选400～4000，最优选为500～3000。鉴于提高墨粘接性，优选数均分子量为300以上。鉴于提高耐粘连性，优选数均分子量为3000以下。
用于合成或聚合本发明的聚氨酯树脂的多异氰酸酯的实例包括具有芳环的脂肪族二异氰酸酯，例如二甲苯二异氰酸酯等；脂环族二异氰酸酯，例如异佛尔酮二异氰酸酯、4,4-二环己基甲烷二异氰酸酯、1,3-双(异氰酸根合甲基)环己烷等；脂肪族二异氰酸酯，例如己二异氰酸酯、2,2,4-三甲基六亚甲基二异氰酸酯等；含有各自均由二异氰酸酯产生的异氰脲酸酯键、缩二脲键或脲基甲酸酯键的改性多异氰酸酯；以及通过将一种以上的二异氰酸酯加成至例如三羟甲基丙烷中而生产的多异氰酸酯。优选使用上述的具有芳环的脂肪族二异氰酸酯、脂环族二异氰酸酯或脂肪族二异氰酸酯，因为没有黄变问题。
扩链剂的实例包括二醇，例如乙二醇、二甘醇、1,4-丁二醇、新戊二醇、1,6-己二醇等；多元醇，例如甘油、三羟甲基丙烷和季戊四醇等；二胺，例如乙二胺、六亚甲基二胺和哌嗪等；氨基醇，例如单乙醇胺和二乙醇胺等；硫二甘醇类，例如硫代二甘醇等；和水。也可以使用具有三个以上的官能团的多元醇、多胺等，只要其量少即可。
本发明的聚氨酯树脂可以在树脂的一端或两端或一个以上的侧链中具有反应性基团，例如封端异氰酸酯，以改善韧性。
交联剂
在本发明中，使用具有羧基且酸值为30～50mgKOH/g的交联剂。与上述聚氨酯树脂的情况一样，交联剂的羧基可以用碱性化合物中和。具有羧基的交联剂的酸值优选为30～50mgKOH/g，更优选为35～45mgKOH/g。酸值为30mgKOH/g以上是优选的，因为改善了对UV固化性树脂、特别是UV固化性墨的粘接性。另一方面，酸值为50mgKOH/g以下是优选的，因为保持了施涂后的涂布层的耐水性，并且由于吸湿而不太可能容易地彼此粘附。为了补偿本发明的交联剂的水溶性或水分散性，可以引入其他亲水性基团，如羟基、醚基、磺酸基、膦酸基、季胺基，只要性能不劣化即可。
具有羧基的交联剂的实例包括在分子中引入一个以上的羧基的噁唑啉系化合物、碳二亚胺系化合物、环氧化合物和异氰酸酯系化合物。羧基也可以预先用碱性化合物中和，以防止与引入分子中的羧基发生分子内或分子间反应。在这些交联剂中，优选容易将羧基引入分子内的异氰酸酯系化合物，特别优选封端异氰酸酯系化合物。
封端剂的实例包括亚硫酸盐化合物如亚硫酸氢钠等；吡唑系化合物如3,5-二甲基吡唑、3-甲基吡唑、4-溴-3,5-二甲基吡唑、4-硝基-3,5-二甲基吡唑等；酚类化合物如苯酚、甲酚等；脂肪族醇化合物如甲醇、乙醇等；活性亚甲基化合物如丙二酸二甲酯、乙酰丙酮等；硫醇系化合物如丁硫醇、十二烷基硫醇等；酸酰胺系化合物如乙酰苯胺、乙酰胺等；内酰胺系化合物如ε-己内酰胺、δ-戊内酰胺等；酸酰亚胺系化合物如琥珀酰亚胺、马来酰亚胺等；肟系化合物如乙醛肟、丙酮肟、甲乙酮肟等；胺系化合物如二苯基苯胺、苯胺、乙烯亚胺等；等等封端剂。
封端异氰酸酯的封端剂的沸点的下限优选为150℃，更优选为160℃，甚至更优选为180℃，特别优选为200℃，最优选为210℃。封端剂的沸点越高，在涂布液施涂后的干燥过程中、还有于在线涂布法的情况下的成膜过程中越能抑制通过加热引起的封端剂的挥发，并且越能抑制涂布表面的微小凹凸的形成，从而改善膜的透明性。尽管封端剂的沸点的上限没有特别限定，但鉴于生产性，300℃左右似乎是上限。由于沸点与分子量有关，因此优选使用具有高分子量的封端剂以提高封端剂的沸点。封端剂的分子量优选为50以上，更优选为60以上，甚至更优选为80以上。
封端剂的解离温度的上限优选为200℃，更优选为180℃，甚至更优选为160℃，特别优选为150℃，最优选为120℃。封端剂在涂布液施涂后的干燥过程或于在线涂布法的情况下的成膜过程中的加热时解离，产生再生的异氰酸酯基。因此，聚氨酯树脂等的交联反应进展从而改善粘接性。如果封端异氰酸酯的解离温度为上述温度以下，则封端剂的解离充分进展，结果粘接性良好、特别是耐湿热性良好。
解离温度为120℃以下、沸点为150℃以上且可用于本发明的封端异氰酸酯的封端剂的实例如上所述包括亚硫酸氢钠、3,5-二甲基吡唑、3-甲基吡唑、丙二酸二甲酯、丙二酸二乙酯、丙酮肟和甲乙酮肟。其中，鉴于耐湿热性和耐黄变性，如3,5-二甲基吡唑、3-甲基吡唑等吡唑系化合物是优选的。
封端异氰酸酯优选具有2个以上官能团。鉴于涂膜的交联性，更优选具有3个以上官能团的封端异氰酸酯。
作为本发明的封端异氰酸酯的前驱体的具有3个以上官能团的多异氰酸酯可以优选由异氰酸酯单体获得。实例包括通过改性例如芳香族二异氰酸酯、脂肪族二异氰酸酯、芳香族脂肪族二异氰酸酯或脂环族二异氰酸酯等具有2个异氰酸酯基的异氰酸酯单体获得的缩二脲、异氰脲酸酯和加合物。
缩二脲是具有通过异氰酸酯单体自缩合形成的缩二脲键的自缩合物。实例包括己二异氰酸酯的缩二脲等。
异氰脲酸酯是异氰酸酯单体的三聚体。实例包括己二异氰酸酯的三聚体、异佛尔酮二异氰酸酯的三聚体、甲苯二异氰酸酯的三聚体等。
加合物是含有三个以上官能团、通过异氰酸酯单体与含有三个以上活性氢官能团的低分子量化合物反应而获得的异氰酸酯系化合物。实例包括通过使三羟甲基丙烷与己二异氰酸酯反应获得的化合物、通过使三羟甲基丙烷与甲苯二异氰酸酯反应获得的化合物、通过使三羟甲基丙烷与亚二甲苯二异氰酸酯反应获得的化合物、通过使三羟甲基丙烷与异佛尔酮二异氰酸酯反应获得的化合物等。
异氰酸酯单体的实例包括芳香族二异氰酸酯，例如2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、4,4'-二苯基甲烷二异氰酸酯、2,4'-二苯基甲烷二异氰酸酯、2,2'-二苯基甲烷二异氰酸酯、1,5-萘二异氰酸酯、1,4-萘二异氰酸酯、苯二异氰酸酯、四甲基亚二甲苯二异氰酸酯、4,4'-二苯醚二异氰酸酯、2-硝基二苯基-4,4'-二异氰酸酯、2,2'-二苯基丙烷-4,4'-二异氰酸酯、3,3'-二甲基二苯基甲烷-4,4'-二异氰酸酯、4,4'-二苯基丙烷二异氰酸酯、3,3'-二甲氧基二苯基-4,4'-二异氰酸酯和二甲苯二异氰酸酯等；脂环族二异氰酸酯，例如异佛尔酮二异氰酸酯、4,4-二环己基甲烷二异氰酸酯、1,3-双(异氰酸根合甲基)环己烷等；和脂肪族二异氰酸酯，例如己二异氰酸酯和2,2,4-三甲基六亚甲基二异氰酸酯等。鉴于透明性、耐黄变性、粘接性和耐湿热性，脂肪族和脂环族二异氰酸酯及其改性物是优选的。
本发明中，一种以上的其他树脂可以与聚氨酯树脂和交联剂一起使用，只要它们不影响性能即可。与聚氨酯树脂一起使用的这种其他树脂的实例包括不含羧基的聚氨酯、聚酯树脂、丙烯酸类树脂、纤维素树脂、聚烯烃树脂、聚缩醛树脂等。在这些树脂中，特别优选聚酯树脂，因为它与聚氨酯树脂一起使用改善了对UV固化性树脂的粘接性。当聚酯树脂与聚氨酯树脂一起使用时，聚酯树脂的含量可以是含羧基的聚氨酯树脂和含羧基的交联剂的组合含量的1.5倍以上。因为聚酯树脂对基材用聚酯树脂的亲和性与含羧基的聚氨酯树脂或含羧基的交联剂相比更好，所以聚酯树脂可以在厚度方向上容易定位于基材侧，增加对基材的粘接性，位于涂布层表面的含羧基的聚氨酯树脂和含羧基的交联剂表现出增加对UV固化性树脂的粘接性的协同效果。
聚酯树脂
在本发明中一起用于形成涂布层的聚酯树脂可以是直链的；然而，优选含有二羧酸和具有支链结构的二元醇(二醇)或具有一个以上醚键的二醇作为成分的聚酯树脂。这里提及的二羧酸的实例主要包括脂肪族二羧酸如己二酸、癸二酸等；芳香族二羧酸，如对苯二甲酸、间苯二甲酸、邻苯二甲酸、2,6-萘二甲酸等。支链二醇是指具有支链烷基的二醇。实例包括2,2-二甲基-1,3-丙二醇、2-甲基-2-乙基-1,3-丙二醇、2-甲基-2-丁基-1,3-丙二醇、2-甲基-2-丙基-1,3-丙二醇、2-甲基-2-异丙基-1,3-丙二醇、2-甲基-2-正己基-1,3-丙二醇、2,2-二乙基-1,3-丙二醇、2-乙基-2-正丁基-1,3-丙二醇、2-乙基-2-正己基-1,3-丙二醇、2,2-二正丁基-1,3-丙二醇、2-正丁基-2-丙基-1,3-丙二醇、2,2-二正己基-1,3-丙二醇等。
此外，含有一个以上醚键的二醇的实例包括如二甘醇、三甘醇、二丙二醇等亚烷基二醇的缩合产物；双酚化合物的环氧乙烷加合物、双酚化合物的环氧丙烷加合物等。分子中的醚键数没有特别限定，但优选为4个以下，更优选为2个以下，因为存在大量醚键会降低聚酯树脂的强度或玻璃化转变温度。
聚酯树脂中，作为上述更优选的实施方案的含有1个以上醚键的支链二醇成分或二元醇成分认为基于全部二醇成分以10mol％以上、更优选20mol％以上的比例存在。10mol％以上的含量是优选的，因为结晶度不会太高并且保持涂布层的粘接性。全部二醇成分中的二醇成分含量的上限优选为80mol％以下，更优选为70质量％以下。二醇成分含量为80mol％以下是优选的，因为作为副产物的低聚物的浓度不太可能增加，这维持了涂布层的透明性。作为上述化合物以外的二醇成分，最优选乙二醇。可以使用丙二醇、丁二醇、己二醇、1,4-环己烷二甲醇等，只要其量少即可。
作为聚酯树脂的构成成分的二羧酸最优选对苯二甲酸或间苯二甲酸。除了上述二羧酸以外，为了赋予共聚酯树脂水分散性，1～10mol％量的5-磺基间苯二甲酸等优选进行共聚。这种化合物的实例包括磺基对苯二甲酸、5-磺基间苯二甲酸、5-磺基间苯二甲酸钠等。
当将涂布层形成用涂布液中的树脂和交联剂的总固体含量定义为100质量％时，聚酯树脂含量为10质量％以上是优选的，因为提供了良好的涂布层和聚酯膜基材之间的粘接性。聚酯树脂含量的上限优选为65质量％以下，更优选为60质量％以下。聚酯树脂含量为70质量％以下是优选的，因为提供了良好的墨加工后的耐热性。
上述聚酯树脂以外的树脂也可以用于涂布层中，只要膜的性能不受损即可。聚酯树脂以外的树脂的典型实例是含羧基的聚氨酯树脂。也可以包括其他树脂，或者可以仅使用含羧基的聚氨酯树脂。这种情况下，当涂布层形成用涂布液中树脂和交联剂的总固体含量为100质量％时，聚酯树脂以外的树脂的含量优选为40质量％以下，更优选为30质量％以下，特别优选为20质量％以下。聚酯树脂和除聚酯树脂以外的树脂的总含量优选为70质量％以下。基于树脂和交联剂的总固体含量，涂布层形成用涂布液中聚氨酯树脂的含量和交联剂的含量各自优选为3质量％以上。
3质量％以上的含量是优选的，因为提供了对UV固化性树脂的高粘接性和对如UV固化性墨等涂布剂的高粘接性的效果。该含量更优选在3.5～90质量％的范围内，更优选为7～80质量％，特别优选为10.5～70质量％。
添加剂
本发明的涂布层可以含有已知的添加剂，例如表面活性剂、抗氧化剂、耐热稳定剂、耐候稳定剂、紫外线吸收剂、有机润滑剂、颜料、染料、有机或无机颗粒、抗静电剂和成核剂，只要不损害本发明的效果。
在本发明的优选实施方案中，将颗粒添加到涂布层中以进一步改善涂布层的耐粘连性。本发明中，涂布层中所含的颗粒的实例包括氧化钛、硫酸钡、碳酸钙、硫酸钙、二氧化硅、氧化铝、滑石、高岭土、粘土、或它们的混合物、或它们与例如磷酸钙、云母、锂蒙脱石、氧化锆、氧化钨、氟化锂和氟化钙等其他一般无机颗粒的组合的无机颗粒；有机聚合物颗粒，例如苯乙烯、丙烯酸类、三聚氰胺、苯并胍胺、硅酮等聚合物颗粒；等等。
涂布层中的颗粒的平均粒径(基于用扫描电子显微镜(SEM)测量的颗粒数的平均粒径，下同)优选为0.04～2.0μm，更优选为0.1～1.0μm。平均粒径为0.04μm以上的惰性颗粒是优选的，因为它们容易在膜表面上形成凹凸，结果例如滑动性、卷绕性等膜的操作性改善，贴合时的加工性良好。另一方面，平均粒径为2.0μm以下的惰性颗粒是优选的，因为颗粒不太可能脱落。基于涂布层的固体成分，涂布层中的颗粒浓度优选为1～20质量％。
颗粒的平均粒径通过包括用扫描型电子显微镜观察层叠聚酯膜的截面中的30个颗粒，并且将颗粒的粒径的平均值定义为平均粒径的方法来测量。
颗粒的形状没有特别限定，只要满足本发明的目的即可，可以使用球状颗粒或具有不规则形状的非球状颗粒。具有不规则形状的颗粒的粒径可以计算为圆当量直径。圆当量直径是通过将观察到的颗粒的面积除以π，计算平方根，并将平方根的值加倍而获得的值。
层叠聚酯膜的生产
以使用聚对苯二甲酸乙二醇酯(以下可以简称为“PET”)膜基材为例，对本发明的层叠聚酯膜的生产方法进行说明。然而，自然地，本发明的方法不限于该示实例。
在PET树脂在真空中充分干燥后，将树脂送入挤出机，将在约280℃下熔融的PET树脂从T模头以片状形式熔融挤出至旋转冷却辊上，然后通过施加静电冷却而使片材固化，从而形成未拉伸PET片材。未拉伸PET片材可以为单层的，或者可以通过共挤出法而为多层的。
将所得的未拉伸PET片材进行单轴拉伸或双轴拉伸以进行结晶取向。例如，在双轴拉伸的情况下，将未拉伸的PET片材用加热至80～120℃的辊沿纵向拉伸2.5～5.0倍，从而获得单轴拉伸PET膜；然后用夹子夹住膜的端部，并将膜引导到加热至80～180℃的热风区，然后沿宽度方向拉伸2.5-5.0倍。在单轴拉伸的情况下，未拉伸PET片材在拉幅机中拉伸2.5-5.0倍。拉伸后，将所得膜引导至热处理区并进行热处理以完成结晶取向。
热处理区的温度的下限优选为170℃，更优选为180℃。热处理区温度为170℃以上是优选的，因为固化充分进展，在液态水的存在下获得良好的耐粘连性，并且干燥不需要花费很长时间。另一方面，热处理区的温度的上限优选为250℃，更优选为240℃。热处理区温度为240℃以下是优选的，因为降低了膜的物性劣化的可能性。
涂布层可以在膜生产之后或在生产过程中形成。特别地，鉴于生产性，优选在膜的生产过程的任意阶段形成涂布层；即，优选通过将涂布液施涂至未拉伸或单轴拉伸的PET膜的至少一个表面上、沿至少一个轴向拉伸并热处理所得膜来形成涂布层。
可以通过使用任何已知方法将涂布液施涂到PET膜上。可用方法的实例包括逆辊涂布、凹版涂布、吻涂、模涂、辊刷涂布、喷涂、气刀涂布、线棒涂布、管刮刀、浸渍涂布、帘式涂布等方法。这些方法可以单独或组合使用以施涂涂布液。
本发明中，涂布层的厚度可以在0.001～2.00μm的范围内适当确定。为了兼顾加工性和粘接性，该厚度优选在0.01～1.00μm的范围内，更优选为0.02～0.80μm，甚至更优选为0.05～0.50μm。涂布层厚度为0.001μm以上由于良好的粘接性而是优选的。涂布层厚度为2.00μm以下是优选的，因为不太可能发生粘连。
本发明的层叠聚酯膜的雾度的上限优选为2.5％，更优选为2.0％，甚至更优选为1.5％，特别优选为1.2％。鉴于透明性，雾度为2.5％以下的层叠聚酯膜是优选的，可以适合用于要求透明性的光学膜。通常优选较低的雾度值。但是，雾度为0.1％以上也是优选的，甚至雾度为0.2％以上也是优选的。
实施例
接下来，以下参照实施例和比较例更详细地描述本发明。然而，本发明不限于以下实施例。下面首先说明本发明中使用的评价方法。
(1)雾度
使用浊度计(NDH5000，由Nippon Denshoku Industries,Co.,Ltd.制造)依照JISK 7136:2000测量所得的层叠聚酯膜的雾度。
(2)酸值
树脂和交联剂的酸值通过JIS K1557-5:2007中描述的滴定法测量。
当测量用胺等中和的羧基时，在通过高温处理除去胺等、或者预先进行盐酸等处理以释放或除去胺等之后，进行测量。当测量交联剂时，预先使如异氰酸酯基等反应性基团与胺等反应，然后进行测量。如果待测量的树脂在用作溶剂的异丙醇中的溶解度不良，则使用N-甲基吡咯烷酮代替异丙醇。在诸如上述那些的任意处理中，完全进行了对照测量。
(3)耐粘连性
将两张相同的膜样品以它们的涂布层表面彼此面对的方式彼此叠置。施加98kPa的载荷以使两张相同的膜样品彼此紧密接触，并在50℃的气氛中放置24小时。然后将两张相同的膜样品彼此分离，并根据以下标准评价分离状态。
〇：这两张可以容易地彼此分离，而不会有一层涂布层任意转移到另一层上。
△：涂布层基本保持；然而，一层涂布层的表面层部分地转移到相对的表面上。
×：这两张以彼此无法分离的方式紧密粘接；或者即使这两张可以彼此分离，膜基材的裂开也会发生。
(4)UV固化性墨粘接性
用印刷机(商品名“RI Tester”，由Akira Seisakusho Co.,Ltd.制造)的两个分滚轮以吸墨管的刻度为4的量在层叠聚酯膜的涂布层上使用UV固化性墨(商品名“BEST CUREUV161 Indigo S”或“BEST CURE UV161 White S”；均由T&K TOKA Co.,Ltd.制造)形成印刷物。随后，使用高压汞灯用100或40mJ/cm2的UV光照射涂有墨层的膜，从而固化UV固化性墨。随后，用间隔为2mm的刀具导轨进行穿过墨层到达膜基材的切口以在墨层表面上形成100个方格的网格。随后，将玻璃纸胶带(由Nichiban Co.,Ltd.制造，No.405，宽度：24mm)以网格形式牢固地粘贴到切割面以确保完全粘合。然后将玻璃纸胶带从墨层叠膜的墨层表面垂直剥离，并且目测计数从墨层叠膜的墨层表面剥离的方格数，根据下式确定墨层与膜基材之间的粘接性。部分剥离的方格也计为剥离。
墨粘接性(％)＝100-(剥离的方格数)
根据以下标准评价墨粘接性。
◎：100％
〇：96～99％
△：80～95％
×：小于80％
评价标准中，◎和〇是可接受的等级。
(5)对硬涂层的粘接性
使用#5线棒将UV固化性硬涂层剂Opstar Z7503(由Arakawa ChemicalIndustries,Ltd.制造)施涂到层叠聚酯膜的涂布层，并在80℃下干燥1分钟。施涂了硬涂层剂的膜使用高压水银灯用100mJ/cm2的紫外线照射，从而获得硬涂层的厚度为4μm的硬涂层膜。
随后，使用间隔为2mm的刀具导轨进行穿过硬涂层到达膜基材的切口以形成100个方格的网格。随后，将玻璃纸胶带(由Nichiban Co.,Ltd.制造，No.405，宽度：24mm)以网格形式牢固地粘贴到切割面以确保完全粘合。然后将玻璃纸胶带从硬涂层层叠膜的硬涂层表面垂直剥离。胶带剥离操作在同一位置进行5次后，目测计数从硬涂层层叠膜的硬涂层表面剥离的方格数，根据下式确定硬涂层与膜基材之间的粘接性。部分剥离的方格也计为剥离。
对硬涂层的粘接性(％)＝100-(剥离的方格数)
根据以下标准评价硬涂层与膜基材之间的粘接性。
◎：100％
〇：96～99％
△：80～95％
×：小于80％
评价标准中，◎和〇是可接受的等级。
(6)耐湿热性
将以与上述(4)和(5)相同的方式制备的UV固化性墨涂布膜(施涂BEST CUREUV161 White后，通过在100mJ/cm2的UV照射固化的产品)和硬涂层涂布膜在80℃和80％RH的环境中在没有其他膜或其他物体与涂布面接触的情况下放置500小时，以涂布面垂直放置。处理后，将膜在23℃和65％RH的环境中在没有其他膜或其他物体与涂布面接触的情况下放置10分钟。经过一段时间后，立即以与上述相同的方式评价涂布面的粘接性。
聚氨酯树脂A-1的聚合
将82.8质量份氢化间亚二甲苯二异氰酸酯、25.0质量份二羟甲基丙酸、21.0质量份1,6-己二醇、和150.0质量份的包含己二酸和1,4-丁二醇且数均分子量为2000的聚酯二醇、以及110质量份作为溶剂的甲乙酮放入装备有搅拌器、蛇形冷凝管、氮气导入管、硅胶干燥管和温度计的四颈烧瓶中。将所得混合物在氮气氛下在75℃下搅拌3小时，并确认已达到预定的胺当量。随后，在将反应混合物的温度降低至40℃之后，添加19.8质量份三乙胺从而获得聚氨酯聚合物溶液。随后，将500g水添加至装备有能够高速搅拌的均质机的反应容器，并且将温度调节至25℃。在将所得混合物通过在2000min-1下搅拌混合的同时，添加聚氨酯聚合物溶液以获得水分散液。然后在减压下除去溶剂甲乙酮。用水调节浓度以制备包含酸值为37.5mgKOH/g的聚氨酯树脂(A-1)的固体含量为35质量％的溶液。
聚氨酯树脂A-2的聚合
将63.0质量份氢化间亚二甲苯二异氰酸酯、21.0质量份二羟甲基丙酸、147.0质量份的数均分子量为2000的聚碳酸酯二醇(源自于1,6-己二醇)、以及110质量份作为溶剂的甲乙酮放入装备有搅拌器、蛇形冷凝管、氮气导入管、硅胶干燥管和温度计的四颈烧瓶中。将所得混合物在氮气氛下在75℃下搅拌3小时，并确认已达到预定的胺当量。随后，在将反应混合物的温度降低至40℃之后，添加16.6质量份三乙胺从而获得聚氨酯聚合物溶液。随后，将500g水添加至装备有能够高速搅拌的均质机的反应容器，并且将温度调节至25℃。在将所得混合物通过在2000min-1下搅拌混合的同时，添加聚氨酯聚合物溶液以获得水分散液。然后在减压下除去溶剂甲乙酮。用水调节浓度以制备包含酸值为36.3mgKOH/g的聚氨酯树脂(A-2)的固体含量为35质量％的溶液。
聚氨酯树脂A-3的聚合
将64.5质量份氢化二苯基甲烷二异氰酸酯、21.5质量份二羟甲基丙酸、11.2质量份新戊二醇、和150.5质量份的数均分子量为2000的聚碳酸酯二醇(源自于1,6-己二醇)、以及110质量份作为溶剂的甲乙酮放入装备有搅拌器、蛇形冷凝管、氮气导入管、硅胶干燥管和温度计的四颈烧瓶中。将所得混合物在氮气氛下在75℃下搅拌3小时，并确认已达到预定的胺当量。随后，在将反应混合物的温度降低至40℃之后，添加17.0质量份三乙胺从而获得聚氨酯聚合物溶液。随后，将500g水添加至装备有能够高速搅拌的均质机的反应容器，并且将温度调节至25℃。在将所得混合物通过在2000min-1下搅拌混合的同时，添加聚氨酯聚合物溶液以获得水分散液。然后在减压下除去溶剂甲乙酮。用水调节浓度以制备包含酸值为36.0mgKOH/g的聚氨酯树脂(A-3)的固体含量为35质量％的溶液。
聚氨酯树脂A-4的聚合
将83.4质量份氢化间亚二甲苯二异氰酸酯、16.9质量份二羟甲基丙酸、28.4质量份1,6-己二醇、和151.0质量份的包含己二酸和1,4-丁二醇且数均分子量为2000的聚酯二醇、以及110质量份作为溶剂的甲乙酮放入装备有搅拌器、蛇形冷凝管、氮气导入管、硅胶干燥管和温度计的四颈烧瓶中。将所得混合物在氮气氛下在75℃下搅拌3小时，并确认已达到预定的胺当量。随后，在将反应混合物的温度降低至40℃之后，添加13.3质量份三乙胺从而获得聚氨酯聚合物溶液。随后，将500g水添加至装备有能够高速搅拌的均质机的反应容器，并且将温度调节至25℃。在将所得混合物通过在2000min-1下搅拌混合的同时，添加聚氨酯聚合物溶液以获得水分散液。然后在减压下除去溶剂甲乙酮。用水调节浓度以制备包含酸值为25.3mgKOH/g的聚氨酯树脂(A-4)的固体含量为35质量％的溶液。
聚氨酯树脂A-5的聚合
将104.9质量份氢化间亚二甲苯二异氰酸酯、41.8质量份二羟甲基丙酸、19.0质量份1,6-己二醇、和152.0质量份的包含己二酸和1,4-丁二醇且数均分子量为2000的聚酯二醇、以及110质量份作为溶剂的甲乙酮放入装备有搅拌器、蛇形冷凝管、氮气导入管、硅胶干燥管和温度计的四颈烧瓶中。将所得混合物在氮气氛下在75℃下搅拌3小时，并确认已达到预定的胺当量。随后，在将反应混合物的温度降低至40℃之后，添加33.1质量份三乙胺从而获得聚氨酯聚合物溶液。随后，将500g水添加至装备有能够高速搅拌的均质机的反应容器，并且将温度调节至25℃。在将所得混合物通过在2000min-1下搅拌混合的同时，添加聚氨酯聚合物溶液以获得水分散液。然后在减压下除去溶剂甲乙酮。用水调节浓度以制备包含酸值为55.0mgKOH/g聚氨酯树脂(A-5)的固体含量为35质量％的溶液。
聚氨酯树脂A-6的聚合
将45.0质量份氢化间亚二甲苯二异氰酸酯、20.0质量份1,6-己二醇、1491.0质量份的数均分子量为2000的聚乙二醇、以及110质量份作为溶剂的甲乙酮放入装备有搅拌器、蛇形冷凝管、氮气导入管、硅胶干燥管和温度计的四颈烧瓶中。将所得混合物在氮气氛下在75℃下搅拌3小时，并确认已达到预定的胺当量。
随后，在将反应混合物的温度降低至40℃之后，获得聚氨酯聚合物溶液。将500g水添加至装备有能够高速搅拌的均质机的反应容器，并且将温度调节至25℃。在将所得混合物通过在2000min-1下搅拌混合的同时，添加聚氨酯聚合物溶液以获得水分散液。
然后在减压下除去溶剂甲乙酮。用水调节浓度以制备包含酸值为0.2mgKOH/g的聚氨酯树脂(A-6)的固体含量为35质量％的溶液。
聚氨酯树脂A-7的聚合
将43.8质量份氢化二苯基甲烷二异氰酸酯、12.9质量份二羟甲基丁酸、和153.4质量份的数均分子量为2000的聚碳酸酯二醇(源自于1,6-己二醇)、以及110质量份作为溶剂的甲乙酮放入装备有搅拌器、蛇形冷凝管、氮气导入管、硅胶干燥管和温度计的四颈烧瓶中。将所得混合物在氮气氛下在75℃下搅拌3小时，并确认已达到预定的胺当量。随后，在将反应混合物的温度降低至40℃之后，添加8.8质量份三乙胺从而获得聚氨酯聚合物溶液。随后，将500g水添加至装备有能够高速搅拌的均质机的反应容器，并且将温度调节至25℃。在将所得混合物通过在2000min-1下搅拌混合的同时，添加聚氨酯聚合物溶液以获得水分散液。然后在减压下除去溶剂甲乙酮。用水调节浓度以制备包含酸值为23.1mgKOH/g的聚氨酯树脂(A-7)的固体含量为35质量％的溶液。
聚氨酯树脂A-8的聚合
将68.0质量份氢化二苯基甲烷二异氰酸酯、19.8质量份二羟甲基丙酸、148.0质量份的数均分子量为2000的聚碳酸酯二醇(源自于1,6-己二醇)、以及110质量份作为溶剂的甲乙酮放入装备有搅拌器、蛇形冷凝管、氮气导入管、硅胶干燥管和温度计的四颈烧瓶中。将所得混合物在氮气氛下在75℃下搅拌2小时，并确认已达到预定的胺当量。随后，添加6.6质量份2-丁酮肟，将反应再搅拌1小时。在将该反应溶液的温度降低至40℃之后，添加15.7质量份三乙胺从而获得聚氨酯聚合物溶液。随后，将500g水添加至装备有能够高速搅拌的均质机的反应容器，并且将温度调节至25℃。在将所得混合物通过在2000min-1下搅拌混合的同时，添加聚氨酯聚合物溶液以获得水分散液。边搅拌边添加1.1质量份的10质量％乙二胺水溶液。然后在减压下除去溶剂甲乙酮。用水调节浓度以制备包含酸值为32.0mgKOH/g的聚氨酯树脂(A-8)的固体含量为35质量％的溶液。
交联剂B-1的合成
将59.5质量份己二异氰酸酯、10.7质量份新戊二醇、11.0质量份二羟甲基丁酸、和20.0质量份作为溶剂的N-甲基吡咯烷酮放入装备有搅拌器、温度计和回流冷凝管的烧瓶中。将所得混合物在氮气氛下在80℃下搅拌3小时，并确认已达到预定的胺当量。随后，将29.9质量份2-丁酮肟滴加至反应溶液，并且将反应混合物在氮气氛下在80℃下保持1小时。然后将反应混合物进行红外光谱测量，并且确认异氰酸酯基吸收峰消失。然后将反应混合物的温度降低至40℃，添加7.9质量份三乙胺。在搅拌1小时之后，添加适当量的水以制备固体含量为40质量％的封端异氰酸酯交联剂(B-1)的溶液。交联剂(B-1)的固体成分的酸值为37.6mgKOH/g。
交联剂B-2的合成
将66.6质量份使用己二异氰酸酯作为原料制备的具有异氰脲酸酯结构的多异氰酸酯系化合物(Duranate TPA，由Asahi Kasei Corporation制造)和17.5质量份N-甲基吡咯烷酮放入装备有搅拌器、温度计和回流冷凝管的烧瓶中，并且滴加21.7质量份3,5-二甲基吡唑。将所得混合物在氮气氛下保持在70℃下1小时。滴加9.0质量份二羟甲基丙酸。在将反应混合物进行红外光谱测量并且确认异氰酸酯基吸收峰消失之后，添加6.3质量份N,N-二甲基乙醇胺。搅拌1小时之后，添加适当量的水以制备固体含量为40质量％的封端异氰酸酯交联剂(B-2)的溶液。交联剂(B-2)的固体成分的酸值为41.2mgKOH/g。
交联剂B-3的合成
将150.0质量份水和250.0质量份甲氧基丙醇放入装备有搅拌器、温度计和回流冷凝管的烧瓶中。将所得混合物在氮气氛下加热至80℃。在将烧瓶中的温度保持在80℃下的同时，在氮气氛下从滴液漏斗中经2小时分别添加包含126.0质量份甲基丙烯酸甲酯、210.0质量份2-异丙烯基-2-噁唑啉和53.0质量份三乙胺甲基丙烯酸酯的单体混合物，以及由18.0质量份作为聚合引发剂的2,2’-偶氮双(2-脒基丙烷)二盐酸盐和和170.0质量份水组成的聚合引发剂溶液。滴加之后，将反应混合物在80℃下搅拌5小时，然后冷却至室温。添加适当量的水以制备固体含量为40质量％的噁唑啉交联剂(B-3)的溶液。交联剂(B-3)的固体成分的酸值为39.8mgKOH/g。
交联剂B-4的制备
将65.0质量份使用己二异氰酸酯作为原料制备的具有异氰脲酸酯结构的多异氰酸酯系化合物(Duranate TPA，由Asahi Kasei Corporation制造)、17.5质量份N-甲基吡咯烷酮、29.2质量份3,5-二甲基吡唑、和21.9质量份数均分子量为500的聚乙二醇单甲基醚放入装备有搅拌器、温度计和回流冷凝管的烧瓶中。将所得混合物在氮气氛下保持在70℃下2小时。然后滴加4.0质量份三羟甲基丙烷。在将反应混合物进行红外光谱测量并且确认异氰酸酯基吸收峰消失之后，添加280.0质量份水。添加适当量的水以制备固体含量为40质量％的封端聚异氰酸酯交联剂(B-4)的溶液。交联剂(B-4)的固体成分的酸值为0.0mgKOH/g。
交联剂B-5的合成
将66.04质量份使用己二异氰酸酯作为原料制备的具有异氰脲酸酯结构的多异氰酸酯系化合物(Duranate TPA，由Asahi Kasei Corporation制造)和17.50质量份N-甲基吡咯烷酮放入装备有搅拌器、温度计和回流冷凝管的烧瓶中，并且滴加25.19质量份3,5-二甲基吡唑。将所得混合物在氮气氛下保持在70℃下1小时。之后，滴加5.27质量份二羟甲基丙酸。在将反应混合物进行红外光谱测量并且确认异氰酸酯基吸收峰消失之后，添加5.59质量份N,N-二甲基乙醇胺和132.5质量份水。添加适当量的水以制备固体含量为40质量％的封端聚异氰酸酯交联剂(B-5)的溶液。交联剂(B-5)的固体成分的酸值为22.8mgKOH/g。
交联剂B-6的合成
将59.5质量份己二异氰酸酯、6.8质量份新戊二醇、16.6质量份二羟甲基丁酸、和20.0质量份作为溶剂的N-甲基吡咯烷酮放入装备有搅拌器、温度计和回流冷凝管的烧瓶中。将所得混合物在氮气氛下在80℃下搅拌3小时，并确认已达到预定的胺当量。随后，向反应混合物中滴加30.3质量份2-丁酮肟，并且将反应混合物在氮气氛下保持在80℃下1小时。然后将反应混合物进行红外光谱测量并且确认异氰酸酯基吸收峰消失。然后将反应混合物的温度降低至40℃，并且添加11.9质量份三乙胺。搅拌1小时之后，添加适当量的水以制备固体含量为40质量％的封端异氰酸酯交联剂(B-6)的溶液。交联剂(B-6)的固体成分的酸值为55.4mgKOH/g。
聚酯树脂C-1的制备
将194.2质量份对苯二甲酸二甲酯、184.5质量份间苯二甲酸二甲酯、14.8质量份5-磺基间苯二甲酸二甲酯钠、233.5质量份二甘醇、136.6质量份乙二醇、和0.2质量份钛酸四正丁酯放入装备有搅拌器、温度计和部分回流冷凝器的不锈钢高压釜中。在160～220℃的温度下进行酯交换反应4小时。随后，升温至255℃，逐渐降低反应体系内的压力。然后，反应在30Pa的减压下进行1小时30分钟，从而获得共聚酯树脂(C-1)。所得的聚酯树脂(C-1)为淡黄色透明的。聚酯树脂(C-1)的比浓粘度测定为0.70dl/g。
此外，将15质量份聚酯树脂(C-1)和15质量份乙二醇正丁基醚放入装备有搅拌器、温度计和回流冷凝器的反应器中。将所得混合物在110℃下加热并搅拌以溶解树脂。树脂完全溶解之后，边搅拌边将70质量份水逐渐添加至聚酯溶液中。添加后，将所得液体边搅拌边冷却至室温。添加适当量的水以制备固体含量为30质量％的聚酯树脂(C-1)的溶液。聚酯树脂(C-1)的固体成分的酸值为0.9mgKOH/g。
聚酯树脂C-2的制备
将194.2质量份对苯二甲酸二甲酯、194.2质量份间苯二甲酸二甲酯、233.5质量份二甘醇、136.6质量份乙二醇、和0.2质量份钛酸四正丁酯放入装备有搅拌器、温度计和部分回流冷凝器的不锈钢高压釜中。在160～220℃的温度下进行酯交换反应4小时。随后，升温至255℃，逐渐降低反应体系内的压力。然后，反应在30Pa的减压下进行1小时。此外，在将氮气导入体系内以释放减压的同时，将体系冷却至200℃。边搅拌边向体系中添加28.0质量份偏苯三酸酐，加成反应再进行2小时，从而获得聚酯树脂(C-2)。所得的聚酯树脂(C-2)为淡黄色透明的。聚酯树脂(C-2)的比浓粘度测定为0.35dl/g。
此外，将15质量份聚酯树脂(C-2)和15质量份四氢呋喃放入装备有搅拌器、温度计和回流冷凝器的反应器中。将所得混合物在70℃下加热并搅拌以溶解树脂。树脂完全溶解之后，边搅拌边将31质量份三乙胺和70质量份水逐渐添加至聚酯溶液中。添加后，降低反应体系中的压力以除去四氢呋喃并将所得混合物冷却至室温。添加适当量的水以制备固体含量为30质量％的聚酯树脂(C-2)的溶液。聚酯树脂(C-2)的固体成分的酸值为37.4mgKOH/g。
丙烯酸类树脂D-1的制备
将40份丙二醇单甲基醚放入装备有搅拌器、温度计和回流冷凝器的烧瓶中。在加热烧瓶以将温度保持在100℃的同时，经3小时滴加60.0质量份丙烯酸正丁酯、42.0质量份甲基丙烯酸甲酯、2.9质量份甲基丙烯酸2-羟乙酯、5.7质量份丙烯酸和5质量份偶氮二异丁腈的混合物。滴加后，将所得混合物在相同温度下熟化2小时。然后，将反应混合物的温度降低至40℃，并且边搅拌边添加8.4质量份三乙胺和165质量份水。再继续搅拌1小时之后，添加适当量的水以制备固体含量为35质量％的丙烯酸类树脂(D-1)的溶液。丙烯酸树脂(D-1)的固体成分的酸值为40.1mgKOH/g。
基材用聚酯树脂E-1的制备
三氧化二锑溶液的制备
将三氧化二锑(由Sigma-Aldrich Japan制造)和乙二醇放入烧瓶中并在150℃下搅拌4小时以溶解三氧化二锑。然后，将所得溶液冷却至室温以制备20g/l的三氧化二锑在乙二醇中的溶液。
基材用聚酯树脂E-1的聚合
将高纯度对苯二甲酸和乙二醇以1:2的摩尔比放入装备有搅拌器的2升不锈钢高压釜中。以相对于酸成分为0.3mol％的量添加三乙胺。在250℃、0.25MPa的压力下从反应体系中蒸馏出水的同时，进行酯化反应，从而获得酯化率约95％的对苯二甲酸双(2-羟乙基)酯和低聚物的混合物(以下简称为BHET混合物)。随后，将作为聚合催化剂的三氧化二锑在乙二醇中的溶液以相对于聚酯的酸成分以锑原子计为0.04mol％的量添加到BHET混合物中。随后，将所得混合物在氮气氛下在常压、250℃下搅拌10分钟。之后，在经60分钟升温至280℃的同时，将反应体系的压力逐渐降低至13.3Pa(0.1托)，进一步在280℃、13.3Pa下进行缩聚反应68分钟，从而获得特性粘度(IV)(溶剂：苯酚/四氯乙烷＝60/40)为0.61dl/g且实质上不含颗粒的聚酯树脂(E-1)。
基材用聚酯树脂E-2的制备
铝化合物溶液的制备例
将20g/l碱式乙酸铝(二乙酸羟基铝；由Sigma-Aldrich Japan制造)的水溶液和等体积(体积比)的乙二醇放入烧瓶中，在室温下搅拌6小时。然后，在70～90℃和减压(133Pa)下搅拌数小时从反应体系中蒸馏出水，制备20g/l的铝化合物在乙二醇中的溶液。
磷化合物溶液的制备例
将作为磷化合物的3,5-二-叔丁基-4-羟基苄基膦酸二乙酯(Irganox 1222，由BASF制造)和乙二醇放入烧瓶中，并在氮气氛下在160℃的液温下边搅拌边加热25小时以制备50g/l的磷化合物在乙二醇中的溶液。
铝化合物溶液和磷化合物溶液的混合物的制备
将上述“铝化合物溶液的制备例”部分中获得的铝化合物在乙二醇中的溶液和上述“磷化合物溶液的制备例”部分中获得的磷化合物在乙二醇中的溶液放入烧瓶中，在室温下混合，以使铝原子：磷原子摩尔比达到1:2，搅拌1天以制备催化剂溶液。
基材用聚酯树脂E-2的聚合
除了使用铝化合物溶液和磷化合物溶液的混合物代替三氧化二锑溶液作为缩聚催化剂，并且相对于聚酯的酸成分，铝含量和磷含量以铝原子和磷原子计分别为0.014mol％和0.028mol％的量添加混合物以外，以与聚酯树脂(E-1)中相同的方式进行聚合；将聚合时间改变为68分钟，从而获得特性粘度(IV)为0.61dl/g且实质上不含颗粒的聚酯树脂(E-2)。
实施例1
(1)涂布液的制备
将以下涂布组分在水和异丙醇的混合溶剂(质量比：80/20)中混合以制备基于固体含量的聚氨酯树脂溶液(A-1)/交联剂(B-1)溶液质量比为70/30的涂布液。
(2)层叠聚酯膜的制备
作为膜材料聚合物，将聚酯树脂(E-1)的树脂丸粒在133Pa的减压下在135℃下干燥6小时。然后将干燥的丸粒送入挤出机并在约280℃下熔融挤出成片材。然后将所得产物在其表面温度保持在20℃的旋转冷却金属辊上快速冷却、粘接和固化，由此获得未拉伸的PET片材。
使用加热辊组和红外线加热器将未拉伸的PET片材加热至100℃，然后使用圆周速度不同的辊组将其沿纵向拉伸3.5倍，由此获得单轴拉伸PET膜。
随后，将涂布液以使得最终(双轴拉伸后)的干燥后的涂布量为0.13g/m2的量施涂在PET膜的一个表面上。涂布液干燥后，在110℃下将膜沿宽度方向拉伸4.0倍，并且在固定膜的宽度方向的情况下在230℃下加热5秒。进一步，将该膜沿宽度方向进行3％的松弛处理，由此获得厚度为100μm的层叠聚酯膜。表1显示了评价结果。
实施例2
除了将聚氨酯树脂改变为聚氨酯树脂(A-2)并且聚氨酯树脂与交联剂之比改变为60/40(质量比)以外，以与实施例1中相同的方式获得层叠聚酯膜。
实施例3
除了将聚氨酯树脂改变为聚氨酯树脂(A-3)并且聚氨酯树脂与交联剂之比改变为50/50(质量比)以外，以与实施例1中相同的方式获得层叠聚酯膜。
实施例4
除了将交联剂改变为交联剂(B-2)并且聚氨酯树脂与交联剂之比改变为60/40(质量比)以外，以与实施例1中相同的方式获得层叠聚酯膜。
实施例5
除了将交联剂改变为交联剂(B-3)并且聚氨酯树脂与交联剂之比改变为60/40(质量比)以外，以与实施例1中相同的方式获得层叠聚酯膜。
实施例6
除了在聚氨酯树脂(A-1)和交联剂(B-1)之外还使用交联剂(B-4)，并且组分的比例改变为(A-1)/(B-1)/(B-4)＝55/35/10(质量比)以外，以与实施例1中相同的方式获得层叠聚酯膜。
实施例7
除了在聚氨酯树脂(A-1)和交联剂(B-1)之外还使用聚酯树脂(C-1)，并且组分的比例改变为(A-1)/(B-1)/(C-1)＝36/24/40(质量比)以外，以与实施例1中相同的方式获得层叠聚酯膜。
实施例8
除了在聚氨酯树脂(A-1)和交联剂(B-1)之外还使用聚酯树脂(C-1)，并且组分的比例改变为(A-1)/(B-1)/(C-1)＝24/16/60(质量比)以外，以与实施例1中相同的方式获得层叠聚酯膜。
实施例9
除了将聚酯树脂(E-2)的树脂丸粒用作膜材料聚合物以外，以与实施例1中相同的方式获得层叠聚酯膜。
实施例10
除了将聚氨酯树脂改变为聚氨酯树脂(A-8)以外，以与实施例1中相同的方式获得层叠聚酯膜。
比较例1
除了仅使用聚氨酯树脂(A-1)而不使用交联剂(B-1)以外，以与实施例1中相同的方式获得层叠聚酯膜。
比较例2
除了仅使用交联剂(B-1)而不使用聚氨酯树脂(A-1)以外，以与实施例1中相同的方式获得层叠聚酯膜。
比较例3
除了将聚氨酯树脂改变为聚氨酯树脂(A-4)以外，以与实施例1中相同的方式获得层叠聚酯膜。
比较例4
除了将聚氨酯树脂改变为聚氨酯树脂(A-5)并且聚氨酯树脂与交联剂之比改变为60/40(质量比)以外，以与实施例1中相同的方式获得层叠聚酯膜。
比较例5
除了将聚氨酯树脂改变为聚氨酯树脂(A-6)并且聚氨酯树脂与交联剂之比改变为50/50(质量比)以外，以与实施例1中相同的方式获得层叠聚酯膜。
比较例6
除了将聚氨酯树脂改变为聚氨酯树脂(A-7)并且将交联剂改变为交联剂(B-5)以外，以与实施例1中相同的方式获得层叠聚酯膜。
比较例7
除了将交联剂改变为交联剂(B-5)并且聚氨酯树脂与交联剂之比改变为75/25(质量比)以外，以与实施例1中相同的方式获得层叠聚酯膜。
比较例8
除了将交联剂改变为交联剂(B-6)以外，以与实施例1中相同的方式获得层叠聚酯膜。
比较例9
除了使用聚氨酯树脂(C-2)代替聚氨酯树脂(A-1)以外，以与实施例1中相同的方式获得层叠聚酯膜。
比较例10
除了使用丙烯酸类树脂(D-1)代替聚氨酯树脂(A-1)以外，以与实施例1中相同的方式获得层叠聚酯膜。
表1总结了实施例和比较例的评价结果。
如表1中所示，实施例中获得的层叠聚酯膜在雾度、耐粘连性、对UV固化性墨的粘接性、对硬涂层的粘接性和耐湿热性方面是令人满意的。相对的，比较例1～10中获得的层叠聚酯膜在上述评价项目的至少一个方面是不令人满意的。
产业上的可利用性
根据本发明，可以提供适合用于在如光学、包装和标签应用等所有领域中的层叠聚酯膜。
Claims (2)
1.一种层叠聚酯膜，其包括：
聚酯膜和，
在所述聚酯膜的至少一个表面上的涂布层，
所述涂布层包括含有以下的组合物：具有羧基且酸值为30～50mgKOH/g的聚氨酯树脂，和具有羧基且酸值为30～50mgKOH/g的交联剂。
2.根据权利要求1所述的层叠聚酯膜，其中所述交联剂为异氰酸酯系化合物。
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- 2020-10-23 CN CN202311417812.1A patent/CN117551297A/zh active Pending
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- 2020-10-23 WO PCT/JP2020/039892 patent/WO2021085327A1/ja unknown
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| WO2021085327A1 (ja) | 2021-05-06 |
| CN117551297A (zh) | 2024-02-13 |
| JP2022089835A (ja) | 2022-06-16 |
| US11932742B2 (en) | 2024-03-19 |
| TW202122274A (zh) | 2021-06-16 |
| KR20220094204A (ko) | 2022-07-05 |
| JP7207589B2 (ja) | 2023-01-18 |
| JP7103507B2 (ja) | 2022-07-20 |
| US20220332910A1 (en) | 2022-10-20 |
| CN114616284B (zh) | 2024-03-19 |
| JPWO2021085327A1 (ja) | 2021-11-25 |
| EP4053196A4 (en) | 2023-11-22 |
| EP4053196A1 (en) | 2022-09-07 |
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