CN107151471B - 硬质涂膜及使用该硬质涂膜的图像显示装置 - Google Patents
硬质涂膜及使用该硬质涂膜的图像显示装置 Download PDFInfo
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- CN107151471B CN107151471B CN201710128897.XA CN201710128897A CN107151471B CN 107151471 B CN107151471 B CN 107151471B CN 201710128897 A CN201710128897 A CN 201710128897A CN 107151471 B CN107151471 B CN 107151471B
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- hard coating
- acrylate
- coating film
- meth
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- 239000011248 coating agent Substances 0.000 title claims abstract description 54
- 238000000576 coating method Methods 0.000 title claims abstract description 54
- 239000000758 substrate Substances 0.000 claims abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 44
- 239000008199 coating composition Substances 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 10
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 3
- 229920001519 homopolymer Polymers 0.000 claims 1
- 238000005452 bending Methods 0.000 abstract description 11
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 24
- -1 ethylene oxide-modified bisphenol a diglycidyl ether Chemical class 0.000 description 20
- 239000003795 chemical substances by application Substances 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 16
- 239000004743 Polypropylene Substances 0.000 description 15
- 229920001155 polypropylene Polymers 0.000 description 15
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 239000002105 nanoparticle Substances 0.000 description 12
- 238000001723 curing Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 239000012963 UV stabilizer Substances 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 5
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
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- 239000006096 absorbing agent Substances 0.000 description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
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- 239000012760 heat stabilizer Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
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- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 4
- 239000003381 stabilizer Substances 0.000 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 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
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- 239000000178 monomer Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 3
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 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
- 150000001412 amines Chemical class 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 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
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- 229910052681 coesite Inorganic materials 0.000 description 2
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- 238000002788 crimping Methods 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
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- 229960000969 phenyl salicylate Drugs 0.000 description 2
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- FHYUCVWDMABHHH-UHFFFAOYSA-N toluene;1,2-xylene Chemical group CC1=CC=CC=C1.CC1=CC=CC=C1C FHYUCVWDMABHHH-UHFFFAOYSA-N 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
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- GFNDFCFPJQPVQL-UHFFFAOYSA-N 1,12-diisocyanatododecane Chemical compound O=C=NCCCCCCCCCCCCN=C=O GFNDFCFPJQPVQL-UHFFFAOYSA-N 0.000 description 1
- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及硬质涂膜,更具体地,涉及在透明基板上的硬质涂膜,其包括具有弹性模量和断裂伸长率在特定范围内的高伸长率低聚物,并且因此可以表现出优异的抗冲击性和抗弯曲性,并且可以使由硬质涂膜的固化收缩引起的卷曲的发生最小化,以及涉及使用该硬质涂膜的图像显示装置。
Description
技术领域
本发明涉及具有优异的抗冲击性和抗弯曲性的硬质涂膜,以及涉及使用该硬质涂膜的图像显示装置。
背景技术
近年来,随着移动装置(例如智能手机和平板电脑)的发展,需要更薄和更轻的显示基板。作为具有优异机械性能的材料的玻璃或钢化玻璃通常用于这些移动装置的显示视窗或前板。然而,玻璃由于其自身重量使得移动装置的重量变重,并且具有由于外部冲击而损坏的问题。
因此,正在研究将塑料树脂作为玻璃的替代品。塑料树脂组合物适合于追求更轻的移动装置的趋势,因为其重量轻并且不太可能破裂。特别地,已经提出了其中支撑基板涂布有硬质涂层的组合物,以实现具有高硬度和耐磨性的组合物。
作为改善硬质涂层的表面硬度的方法,可以考虑增加硬质涂层的厚度的方法。为了确保足够的表面硬度以替代玻璃,必须实现恒定厚度的硬质涂层。
随着硬质涂层的厚度增加,表面硬度会增加。然而,由于硬质涂层的固化收缩,起皱或卷曲增加,并且同时硬质涂层容易破裂或剥离。因此,实际应用该方法并不容易。
近来,已经提出了一些用于实现高硬度的硬质涂膜并同时解决由固化收缩引起的硬质涂层开裂或卷曲的问题的方法。
在第2014-0027022号韩国专利公开中,公开了一种硬质涂布组合物,其包括丙烯酸酯单体和具有在预定范围内的伸长率的可光固化弹性体并因此表现出改善的抗冲击性。然而,上述公开的硬质涂布组合物不能表现出足够的抗弯曲性和抗冲击性以替代显示器的玻璃面板。
在韩国专利公开第2011-0078783号中,公开了一种硬质涂布组合物,其包括5重量%至80重量%的亚烷基二醇基丙烯酸类单体并因此表现出改善的表面硬度和抗冲击性。然而,上述公开的硬质涂布组合物也未表现出足够的抗冲击性以替代显示器的玻璃面板。
[现有技术文献]
[专利文献]
韩国专利公开第2014-0027022号(2014年03月06日,LG Chem Ltd.)
韩国专利公开第2011-0078783号(2011年07月07日,Cheil Industries Inc.)
发明内容
本发明旨在提供能够表现出优异的抗冲击性和抗弯曲性并且使卷曲的发生最小化的硬质涂膜和包括该硬质涂膜的图像显示装置。
为了实现上述目的,本发明提供硬质涂膜,其形成在透明基板上并且包括硬质涂布组合物的固化产物,所述硬质涂布组合物包括弹性模量为10MPa至3000MPa且断裂伸长率为30%至150%的高伸长率低聚物。
另外,为了实现上述目的,本发明提供包括该硬质涂膜的图像显示装置。
根据本发明的硬质涂膜包括具有弹性模量和断裂伸长率在特定范围内的高伸长率低聚物,并且因此可以表现出优异的抗冲击性和抗弯曲性,并且使由硬质涂膜的固化收缩引起的卷曲的发生最小化。
具体实施方式
当一个部分“包括”本发明中的一个要素时,除非另有描述,否则还可以包括另一要素,而不排除该另一要素的存在。
在下文中,将参考示例性实施方式详细描述本发明。
<硬质涂膜>
根据本发明实施方式的硬质涂膜形成在透明基板上并且包括硬质涂布组合物的固化产物,所述硬质涂布组合物包括弹性模量为10MPa至3000MPa和断裂伸长率为30%至150%的高伸长率低聚物。当硬质涂布组合物具有在这些范围内的弹性模量和断裂伸长率时,可以表现出优异的抗弯曲性和抗冲击性并且使卷曲的发生最小化。
硬质涂布组合物的固化产物具有50μm至300μm的厚度。当硬质涂布组合物的固化产物的厚度小于50μm时,抗冲击性会降低。另一方面,当其厚度大于300μm时,抗弯曲性会降低并且会发生卷曲。
高伸长率低聚物
根据本发明的硬质涂膜包括高伸长率低聚物。
高伸长率低聚物包括可光固化(甲基)丙烯酸酯低聚物。
可光固化(甲基)丙烯酸酯低聚物可以包括选自由环氧(甲基)丙烯酸酯、氨基甲酸乙酯(甲基)丙烯酸酯和聚酯(甲基)丙烯酸酯组成的组中的一者或多者。
环氧(甲基)丙烯酸酯可以通过使具有(甲基)丙烯酰基的羧酸与环氧化合物反应而获得。具体地,环氧化合物可以是(甲基)丙烯酸缩水甘油酯、C1至C12直链醇封端的缩水甘油醚、二甘醇二缩水甘油醚、三丙二醇二缩水甘油醚、双酚A二缩水甘油醚、环氧乙烷改性的双酚A二缩水甘油醚、环氧丙烷改性的双酚A二缩水甘油醚、三羟甲基丙烷三缩水甘油醚、季戊四醇四缩水甘油醚、氢化双酚A二缩水甘油醚、丙三醇二缩水甘油醚等。具有(甲基)丙烯酰基的羧酸可以是(甲基)丙烯酸、2-(甲基)丙烯酰氧基乙基琥珀酸、2-(甲基)丙烯酰氧基乙基六氢邻苯二甲酸等。
氨基甲酸乙酯(甲基)丙烯酸酯可以通过在催化剂的存在下使分子中具有羟基的多官能(甲基)丙烯酸酯和具有异氰酸酯基的化合物反应来制备。
分子中具有羟基的(甲基)丙烯酸酯可以是选自由(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸2-羟基异丙酯、(甲基)丙烯酸-4-羟基丁酯、己内酯开环的羟基丙烯酸酯、季戊四醇三(甲基)丙烯酸酯和季戊四醇四-(甲基)丙烯酸酯的混合物、以及二季戊四醇五-(甲基)丙烯酸酯和二季戊四醇六-(甲基)丙烯酸酯的混合物组成的组中的一者或多者。
分子中具有异氰酸酯基的化合物可以是选自由以下组成的组中的一者或多者:1,4-二异氰酸基丁烷、1,6-二异氰酸基己烷、1,8-二异氰酸基辛烷、1,12-二异氰酸基十二烷、1,5-二异氰酸基-2-甲基戊烷、三甲基-1,6-二异氰酸基己烷、1,3-双(异氰酸酯基甲基)环己烷、反式-1,4-环己烷二异氰酸酯、4,4'-亚甲基双(环己基异氰酸酯)、异佛尔酮二异氰酸酯、甲苯-2,4-二异氰酸酯、甲苯-2,6-二异氰酸酯、二甲苯-1,4-二异氰酸酯、四甲基二甲苯-1,3-二异氰酸酯、1-氯甲基-2,4-二异氰酸酯、4,4'-亚甲基双(2,6-二甲基苯基异氰酸酯)、4,4'-氧基双(苯基异氰酸酯)、来自六亚甲基二异氰酸酯的三官能异氰酸酯和三甲基丙醇-甲苯二异氰酸酯加合物。
聚酯(甲基)丙烯酸酯,具体地,可以是二丙烯酸酯(例如乙二醇二(甲基)丙烯酸酯、二甘醇二(甲基)丙烯酸酯、三甘醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、三环癸烷二(甲基)丙烯酸酯、双酚A二(甲基)丙烯酸酯等)、三羟甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、双三羟甲基丙烷四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、三(2-(甲基)丙烯酰氧基乙基)异氰脲酸酯等。
优选组合使用氨基甲酸乙酯(甲基)丙烯酸酯和聚酯(甲基)丙烯酸酯,或者在一个分子中包括聚酯基团和氨基甲酸乙酯基团两者。
特别地,具有线性结构的丙烯酸酯低聚物可以用于形成具有30%或更大的伸长率的硬质涂膜,并且优选使用具有线性结构和优异的柔性的聚酯(甲基)丙烯酸酯。
相对于100重量%的全部硬质涂布组合物,该硬质涂布组合物可以包括1重量%至90重量%,优选5重量%至80重量%的高伸长率低聚物。当高伸长率低聚物的含量小于1重量%时,难以形成涂膜,或者即使形成涂膜,也难以制造具有足够的抗冲击性水平的硬质涂膜。另一方面,当其含量大于90重量%时,由于在硬质涂膜的制造期间的高粘度,涂膜的均匀性会降低。
在本发明的一个示例性实施方式中,硬质涂布组合物还可以包括选自由溶剂、光引发剂和添加剂组成的组中的一者或多者。
溶剂
溶剂是可以溶解或分散上述组合物的材料,并且可以使用而没有限制,只要材料是本领域中已知的硬质涂布组合物的溶剂。
具体地,溶剂可以优选为:醇(例如甲醇、乙醇、异丙醇、丁醇、甲基溶纤剂、乙基溶纤剂等),酮(例如甲基乙基酮、甲基丁基酮、甲基异丁基酮、二乙基酮、二丙基酮、环己酮等),乙酸酯(例如乙酸乙酯、乙酸丙酯、乙酸正丁酯、乙酸叔丁酯、甲基溶纤剂乙酸酯、乙基溶纤剂乙酸酯、丙二醇单甲醚乙酸酯、丙二醇单乙醚乙酸酯、丙二醇单丙醚乙酸酯、甲氧基丁基乙酸酯、甲氧基戊基乙酸酯等),烷烃(例如己烷、庚烷、辛烷等),苯或其衍生物(例如苯、甲苯、二甲苯等),醚(例如二甘醇二甲醚、二甘醇二乙醚、二甘醇二丙醚、二甘醇二丁醚、丙二醇单甲醚等)等。溶剂可以单独使用或以两种或更多种组合使用。
相对于100重量%的全部硬质涂布组合物,该硬质涂布组合物可以包括10重量%至95重量%的溶剂。当溶剂的含量小于10重量%时,不仅由于粘度的增加而可加工性会降低,而且不能充分进行在其上涂布有硬质涂布组合物的透明基板的溶胀。另一方面,当其含量大于95重量%时,干燥工艺会需要较长时间,并且经济可行性会降低。
光引发剂
光引发剂可以使用而没有限制,只要是在本领域中使用的材料,并且可以是选自由羟基酮、氨基酮和夺氢型光引发剂组成的组中的一者或多者。
具体地,光引发剂可以是2-甲基-1-[4-(甲硫基)苯基]-2-吗啉基-1-丙酮、二苯基酮、苄基二甲基缩酮、2-羟基-2-甲基-1-苯基-1-酮、4-羟基环戊基酮、2,2-二甲氧基-2-苯基苯乙酮、蒽醌、芴、三苯胺、咔唑、3-甲基苯乙酮、4-氯苯乙酮、4,4-二甲氧基苯乙酮、4,4-二氨基二苯甲酮、1-羟基环己基苯基酮、二苯甲酮、二苯基(2,4,6-三甲基苯甲酰基)氧化膦等。光引发剂可以单独使用或以两种或更多种组合使用。
相对于100重量%的全部硬质涂布组合物,该硬质涂布组合物可以包括0.1重量%至10重量%,优选1重量%至5重量%的光引发剂。当光引发剂的含量小于0.1重量%时,硬质涂布组合物的固化速度减小,发生不充分的固化,并因此机械性能会降低。另一方面,当光引发剂含量大于10重量%时,涂膜会由于过固化而破裂。
添加剂
添加剂可以包括选自由无机纳米颗粒、流平剂和稳定剂组成的组中的一者或多者。
(1)无机纳米颗粒
可以选择性地添加无机纳米颗粒以提高硬质涂膜的硬度。具体地,当在硬质涂膜组合物中包括无机纳米颗粒时,可以进一步提高机械性能。更具体地,无机纳米颗粒均匀地形成在涂膜中,并因此可以改善机械性能,例如耐磨性、抗划伤性、铅笔硬度等。
无机纳米颗粒可以具有1nm至100nm,特别是1nm至80nm,更特别是5nm至50nm的平均直径。当无机纳米颗粒的平均直径在这些范围内时,可以防止在组合物中发生团聚的现象并因此形成均匀的涂膜并防止涂膜的光学特性和机械性能的降低。
无机纳米颗粒可以包括选自由Al2O3、SiO2、ZnO、ZrO2、BaTiO3、TiO2、Ta2O5、Ti3O5、ITO、IZO、ATO、ZnO-Al、Nb2O3、SnO、MgO及其组合组成的组中的一者或多者,但是本发明不限于此。无机纳米颗粒可以包括本领域中通常使用的金属氧化物。
具体地,无机纳米颗粒可以是Al2O3、SiO2或ZrO2。无机纳米颗粒可以直接制造,或者可以是其中无机纳米颗粒以10重量%至80重量%的浓度分散在有机溶剂中的市售产品。
(2)流平剂
流平剂可以包括选自由硅氧烷基流平剂、氟基流平剂和丙烯酸类流平剂组成的组中的一者或多者。当在硬质涂膜组合物中包括流平剂时,在形成涂膜期间可以提供平滑性和涂布性。
具体地,流平剂可以是:BYK-323、BYK-331、BYK-333、BYK-337、BYK-373、BYK-375、BYK-377或BYK-378,它们均可从BYK Chemie GmbH商购获得;TEGO Glide 410、TEGO Glide411、TEGO Glide 415、TEGO Glide 420、TEGO Glide 432、TEGO Glide 435、TEGO Glide440、TEGO Glide 450、TEGO Glide 455、TEGO Rad 2100、TEGO Rad 2200N、TEGO Rad 2250、TEGO Rad 2300、TEGO Rad 2500,它们均可从Evonik TEGO Chemie GmbH商购获得;FC-4430、FC-4432,它们均可从3M商购获得,诸如此类,但本发明不限于此。可以使用本领域中常用的流平剂。
(3)稳定剂
稳定剂可以包括选自由受阻胺、水杨酸苯酯、二苯甲酮、苯并三唑、镍衍生物、自由基清除剂、多酚、亚磷酸酯和内酯稳定剂组成的组中的一者或多者。
本文中使用的术语“UV稳定剂”是指为了通过阻挡或吸收UV射线来保护粘合剂的目的而添加的添加剂,因为由于连续UV射线暴露引起的分解,涂膜的固化表面变色并且容易破裂。
基于原理,UV稳定剂可以分类为吸收剂、淬灭剂或受阻胺光稳定剂(HALS)。此外,基于化学结构,UV稳定剂可以分类为水杨酸苯酯(吸收剂)、二苯甲酮(吸收剂)、苯并三唑(吸收剂)、镍衍生物(淬灭剂)或自由基清除剂。
然而,本发明不限于此,只要UV稳定剂不显著改变粘合剂的初始颜色即可。
作为商业上可应用的产品的热稳定剂,可以单独或组合使用多酚(主要热稳定剂)和亚磷酸酯和内酯(次要热稳定剂)。UV稳定剂和热稳定剂可以通过在不影响UV固化性能的水平下适当调节其含量来使用。
透明基板
根据本发明的硬质涂膜是通过将上述硬质涂布组合物涂布在透明基板的一个表面上,然后使该组合物固化而形成的。
本文使用的术语“透明性”是指可见光的透射率为70%或大于70%或80%或大于80%。
透明基板可以是具有透明性的任何聚合物膜。
具体地,透明基板可以是由以下聚合物制成的膜:例如具有含环烯烃单体(例如降冰片烯或多环降冰片烯基单体)的环烯烃衍生物,纤维素(例如二乙酰纤维素、三乙酰纤维素、乙酰纤维素丁酸酯、异丁酯纤维素、丙酰纤维素、丁酰纤维素或乙酰丙酰纤维素),乙烯/乙酸乙烯酯共聚物、聚环烯烃、聚酯、聚苯乙烯、聚酰胺、聚醚酰亚胺、聚丙烯酸、聚酰亚胺、聚砜、聚乙烯、聚丙烯、聚甲基戊烯、聚氯乙烯、聚偏氯乙烯、聚乙烯醇、聚乙烯醇缩醛、聚醚酮、聚醚醚酮、聚醚砜、聚甲基丙烯酸甲酯、聚对苯二甲酸乙二酯、聚对苯二甲酸丁二酯、聚萘二甲酸乙二酯、聚碳酸酯、聚氨酯、环氧树脂等,并且也可以是未取向膜或单轴取向膜或双轴取向膜。这些聚合物可以单独使用或以两种或更多种的组合使用。
在上述透明基板中,可以优选使用显示优异的透明性和耐热性的聚酰亚胺膜或单轴或双轴取向聚酯膜,显示优异的透明性和耐热性并且能够支撑大尺寸膜的环烯烃衍生物膜或聚甲基丙烯酸甲酯膜,显示透明性并且不具有光学各向异性的三乙酰纤维素膜或异丁酯纤维素膜。
根据本发明的硬质涂膜可以是用于柔性显示器的膜。具体地,硬质涂膜可以用作显示器(例如LCD、OLED、LED、FED等)的盖板玻璃、使用该显示器的各种移动通信终端、智能电话或平板电脑的触摸面板、电子纸等的功能层或替代品。
本发明提供一种包括该硬质涂膜的视窗。
另外,本发明提供一种包括视窗的柔性图像显示装置。
在下文中,将描述本发明的优选实施方式,以帮助理解本发明。然而,对于本领域技术人员显而易见的是,这里提出的描述仅仅是用于说明的目的的优选实施例,并且不旨在限制或限定本发明的范围。因此,应当理解,在不脱离本发明的范围的情况下,可以对本发明的示例性实施方式进行各种改变和修改,使得本发明覆盖所提供的所有这些改变和修改,并且它们在所附权利要求及其等同物的范围之内。以下,除非另有说明,否则表示实施例和比较实施例中的含量的所有“百分比”和“份”均以重量计。
制备实施例1至7:硬质涂布组合物的制备
制备实施例1
将70重量份的氨基甲酸乙酯丙烯酸酯(UA-122P,从Shin-Nakamura ChemicalCo.,Ltd.商购得到)、25重量份的甲基乙基酮、4.5重量份的光引发剂(1-羟基-环己基-苯基-酮)、和0.5重量份的流平剂(BYK-3570,从BYK Chemie GmbH商购得到)使用搅拌器混合,并使用由聚丙烯(PP)材料制成的过滤器过滤以制备硬质涂布组合物。这里,氨基甲酸乙酯丙烯酸酯的弹性模量为2070MPa,断裂伸长率为58%。
制备实施例2
将70重量份的氨基甲酸乙酯丙烯酸酯(UA-232P,从Shin-Nakamura ChemicalCo.,Ltd.商购得到)、25重量份的甲基乙基酮、4.5重量份的光引发剂(1-羟基-环己基-苯基-酮)、和0.5重量份的流平剂(BYK-3570,从BYK Chemie GmbH商购得到)使用搅拌器混合,并使用由聚丙烯(PP)材料制成的过滤器过滤以制备硬质涂布组合物。这里,氨基甲酸乙酯丙烯酸酯的弹性模量为1320MPa,断裂伸长率为135%。
制备实施例3
将70重量份的氨基甲酸乙酯丙烯酸酯(UA-122P,从Shin-Nakamura ChemicalCo.,Ltd.商购得到)、25重量份的甲基乙基酮、4.5重量份的光引发剂(1-羟基-环己基-苯基-酮)、和0.5重量份的流平剂(BYK-3570,从BYK Chemie GmbH商购得到)使用搅拌器混合,并使用由聚丙烯(PP)材料制成的过滤器过滤以制备硬质涂布组合物。这里,氨基甲酸乙酯丙烯酸酯的弹性模量为2570MPa,断裂伸长率为67%。
制备实施例4
将50重量份的氨基甲酸乙酯丙烯酸酯(UA-122P,从Shin-Nakamura ChemicalCo.,Ltd.商购得到)、20重量份的季戊四醇三丙烯酸酯、25重量份的甲基乙基酮、4.5重量份的光引发剂(1-羟基-环己基-苯基-酮)、和0.5重量份的流平剂(BYK-3570,从BYK ChemieGmbH商购得到)使用搅拌器混合,并使用由聚丙烯(PP)材料制成的过滤器过滤以制备硬质涂布组合物。这里,氨基甲酸乙酯丙烯酸酯和季戊四醇三丙烯酸酯的混合物的弹性模量为3220MPa,断裂伸长率为12%。
制备实施例5
将35重量份的氨基甲酸乙酯丙烯酸酯(UA-122P,从Shin-Nakamura ChemicalCo.,Ltd.商购得到)、35重量份的季戊四醇三丙烯酸酯、25重量份的甲基乙基酮、4.5重量份的光引发剂(1-羟基-环己基-苯基-酮)、和0.5重量份的流平剂(BYK-3570,从BYK ChemieGmbH商购得到)使用搅拌器混合,并使用由聚丙烯(PP)材料制成的过滤器过滤以制备硬质涂布组合物。这里,氨基甲酸乙酯丙烯酸酯和季戊四醇三丙烯酸酯的混合物的弹性模量为3705MPa,断裂伸长率为7%。
制备实施例6
将20重量份的氨基甲酸乙酯丙烯酸酯(UA-122P,从Shin-Nakamura ChemicalCo.,Ltd.商购得到)、50重量份的季戊四醇三丙烯酸酯、25重量份的甲基乙基酮、4.5重量份的光引发剂(1-羟基-环己基-苯基-酮)、和0.5重量份的流平剂(BYK-3570,从BYK ChemieGmbH商购得到)使用搅拌器混合,并使用由聚丙烯(PP)材料制成的过滤器过滤以制备硬质涂布组合物。这里,氨基甲酸乙酯丙烯酸酯和季戊四醇三丙烯酸酯的混合物的弹性模量为4210MPa,断裂伸长率为5%。
制备实施例7
将35重量份的氨基甲酸乙酯丙烯酸酯(UA-122P,从Shin-Nakamura ChemicalCo.,Ltd.商购得到)、35重量份的二季戊四醇六丙烯酸酯、25重量份的甲基乙基酮、4.5重量份的光引发剂(1-羟基-环己基-苯基-酮)、和0.5重量份的流平剂(BYK-3570,从BYK ChemieGmbH商购得到)使用搅拌器混合,并使用由聚丙烯(PP)材料制成的过滤器过滤以制备硬质涂布组合物。这里,氨基甲酸乙酯丙烯酸酯和二季戊四醇六丙烯酸酯的混合物的弹性模量为4570MPa,断裂伸长率为3%。
实施例1至7和比较实施例1至4:硬质涂膜的制造
实施例1
将制备实施例1中制备的硬质涂布组合物以使得固化后的组合物的厚度为200μm的这样一种方式涂布在厚度为80μm的聚酰亚胺膜上。在涂布膜之后,干燥溶剂并且以500mJ/cm2的集成光强度照射UV射线,以使组合物固化,从而制造硬质涂膜。
实施例2
除了使用制备实施例2中制备的硬质涂布组合物外,以与实施例1相同的方式制造硬质涂膜。
实施例3
除了使用制备实施例3中制备的硬质涂布组合物外,以与实施例1相同的方式制造硬质涂膜。
实施例4
除了固化后硬质涂层的厚度为70μm外,以与实施例1相同的方式制造硬质涂膜。
实施例5
除了固化后硬质涂层的厚度为250μm外,以与实施例1相同的方式制造硬质涂膜。
实施例6
除了固化后硬质涂层的厚度为20μm外,以与实施例1相同的方式制造硬质涂膜。
实施例7
除了固化后硬质涂层的厚度为500μm外,以与实施例1相同的方式制造硬质涂膜。
比较实施例1
除了使用制备实施例4中制备的硬质涂布组合物外,以与实施例1相同的方式制造硬质涂膜。
比较实施例2
除了使用制备实施例5中制备的硬质涂布组合物外,以与实施例1相同的方式制造硬质涂膜。
比较实施例3
除了使用制备实施例6中制备的硬质涂布组合物外,以与实施例1相同的方式制造硬质涂膜。
比较实施例4
除了使用制备实施例7中制备的硬质涂布组合物外,以与实施例1相同的方式制造硬质涂膜。
实验实施例
实施例1至7和比较例1至4中制备的硬质涂膜的性质以如下方式测定,其结果示于表1。本发明中使用的测定方法和评价方法如下。
(1)抗弯曲性
将硬质涂膜的硬质涂层朝向内侧,并将硬质涂膜对折以在其表面之间具有6mm的间距。然后,通过肉眼观察和确定该膜再次展开时折叠部分是否发生破裂,其结果示于下表1中。
良好:在折叠部分没有破裂
不合格:在折叠部分破裂
(2)抗冲击性
使用50μm光学透明粘合剂(OCA)(弹性模量为0.08MPa)将硬质涂膜的硬质涂层的相对表面(即透明基板层),粘附到玻璃上。然后,当将钢球从50cm的高度自由地落在硬质涂层的表面上时,测定未破坏硬质涂膜下方玻璃的该钢球的最大重量,其结果示于下表1中。
(3)卷曲
将硬质涂膜切割成10cm×10cm的尺寸,并在25℃和48RH%的条件下保持24小时。然后,评价从底部提起每个边缘的程度,其结果示于下表1中。
◎:四个边缘的平均高度为20mm或以下
Ο:四个边缘的平均高度为50mm或以下
Δ:四个边缘的平均高度大于50mm
X:四个边缘被完全提起,并因此膜以圆柱形形式卷起
[表1]
抗弯曲性 | 抗冲击性 | 卷曲 | |
实施例1 | 良好 | 40g | ◎ |
实施例2 | 良好 | 55g | ◎ |
实施例3 | 良好 | 45g | ◎ |
实施例4 | 良好 | 40g | ◎ |
实施例5 | 良好 | ≥65g | ◎ |
实施例6 | 良好 | 30g | ◎ |
实施例7 | 不合格 | ≥65g | Ο |
比较实施例1 | 良好 | 20g | Ο |
比较实施例2 | 不合格 | 10g | X |
比较实施例3 | 不合格 | 5g | X |
比较实施例4 | 不合格 | 5g | X |
参考表1,可以看出,与弹性模量和断裂伸长率在上述范围之外的根据比较例1至4的硬质涂膜相比,弹性模量和断裂伸长率在上述范围内的根据本发明的实施例1至7的硬质涂膜表现出优异的抗弯曲性、抗冲击性和卷曲发生的降低。
另外,可以看出,与厚度在50μm至300μm范围之外的根据实施例6至7的硬质涂膜相比,在硬质涂布组合物固化后,厚度为50μm至300μm范围内的根据实施例1至5的硬质涂膜显示出更优异的抗弯曲性、抗冲击性和发生卷曲的降低。
Claims (5)
1.一种硬质涂膜,所述硬质涂膜形成在透明基板上并且由一个硬质涂层构成,其中,所述硬质涂层包括硬质涂布组合物的固化产物,所述硬质涂布组合物包括弹性模量为10MPa至1320MPa且断裂伸长率为30%至150%的高伸长率低聚物,
其中,所述高伸长率低聚物仅包括氨基甲酸乙酯(甲基)丙烯酸酯,
其中,相对于100重量%的包括所述高伸长率低聚物的全部的硬质涂布组合物,所述硬质涂布组合物包括70重量%至90重量%的所述高伸长率低聚物,
其中,所述硬质涂布组合物的固化产物中的聚合物为所述高伸长率低聚物的均聚物。
2.根据权利要求1所述的硬质涂膜,其中,所述硬质涂布组合物还包括溶剂、光引发剂和添加剂中的一者或多者。
3.根据权利要求1所述的硬质涂膜,其中,所述硬质涂布组合物的固化产物的厚度为50μm至300μm。
4.一种包含根据权利要求1至3中任一项所述的硬质涂膜的视窗。
5.一种包含根据权利要求4所述的视窗的柔性图像显示装置。
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