CN102905898A - 叠层聚酯膜 - Google Patents
叠层聚酯膜 Download PDFInfo
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- CN102905898A CN102905898A CN2011800255594A CN201180025559A CN102905898A CN 102905898 A CN102905898 A CN 102905898A CN 2011800255594 A CN2011800255594 A CN 2011800255594A CN 201180025559 A CN201180025559 A CN 201180025559A CN 102905898 A CN102905898 A CN 102905898A
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- Prior art keywords
- polyester film
- acid
- film
- coating layer
- methyl
- 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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- 229920006267 polyester film Polymers 0.000 title claims abstract description 70
- 239000011247 coating layer Substances 0.000 claims abstract description 62
- 238000000576 coating method Methods 0.000 claims abstract description 48
- 239000011248 coating agent Substances 0.000 claims abstract description 46
- 239000010410 layer Substances 0.000 claims abstract description 26
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 22
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 22
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 17
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 16
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 16
- 239000012530 fluid Substances 0.000 claims description 29
- 229920005749 polyurethane resin Polymers 0.000 claims description 25
- 229920002799 BoPET Polymers 0.000 claims description 21
- 239000005041 Mylar™ Substances 0.000 claims description 21
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- 239000003431 cross linking reagent Substances 0.000 claims description 8
- 238000010422 painting Methods 0.000 claims description 3
- 239000010408 film Substances 0.000 abstract description 51
- 239000007788 liquid Substances 0.000 abstract description 10
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 4
- 239000012788 optical film Substances 0.000 abstract description 4
- 238000000465 moulding Methods 0.000 abstract description 3
- 239000000470 constituent Substances 0.000 abstract description 2
- 229920001225 polyester resin Polymers 0.000 abstract 1
- 239000004645 polyester resin Substances 0.000 abstract 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 abstract 1
- -1 cyclic imide esters Chemical class 0.000 description 89
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 55
- 239000000203 mixture Substances 0.000 description 44
- 238000000034 method Methods 0.000 description 31
- 239000002245 particle Substances 0.000 description 29
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- 239000000178 monomer Substances 0.000 description 24
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 22
- 229920000642 polymer Polymers 0.000 description 22
- 150000001875 compounds Chemical class 0.000 description 21
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- 239000002346 layers by function Substances 0.000 description 18
- 239000012948 isocyanate Substances 0.000 description 16
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
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- 230000008676 import Effects 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 10
- 239000000463 material Substances 0.000 description 10
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- 239000006097 ultraviolet radiation absorber Substances 0.000 description 9
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 8
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- 229920000877 Melamine resin Polymers 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 6
- 150000002118 epoxides Chemical class 0.000 description 6
- 229940051250 hexylene glycol Drugs 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 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
- 125000005968 oxazolinyl group Chemical group 0.000 description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 6
- 229920000515 polycarbonate Polymers 0.000 description 6
- 239000004417 polycarbonate Substances 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
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- 238000002310 reflectometry Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
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- 239000008187 granular material Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 5
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 5
- 229920005862 polyol Polymers 0.000 description 5
- 150000003077 polyols Chemical class 0.000 description 5
- 239000001103 potassium chloride Substances 0.000 description 5
- 235000011164 potassium chloride Nutrition 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 4
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 239000001361 adipic acid Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 150000002221 fluorine Chemical class 0.000 description 4
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 4
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- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- 239000011976 maleic acid Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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Abstract
本发明提供一种叠层聚酯膜,其能够适用于要求对硬涂层等具有良好视认性和附着性的用途,例如,液晶显示器的构件等各种光学用膜和成型用膜。该叠层聚酯膜在聚酯膜的至少一个面具有由涂布液形成的涂布层,该涂布液包含含萘骨架的聚酯树脂、金属氧化物和丙烯酸树脂和/或聚氨酯树脂。
Description
技术领域
本发明涉及一种叠层聚酯膜,例如涉及液晶显示器、等离子体显示器面板、有机电致发光等需要减轻由外部光线的反射产生的干涉斑的叠层聚酯膜。
背景技术
近年来,聚酯膜多用在各种光学用膜和成型用膜中,用在作为液晶或等离子体显示器等构件的触摸面板、防反射膜、棱镜片、光扩散片、电磁波屏蔽膜或模内转印膜、模内标签膜等的用途中。对于这些构件中使用的基膜(base film),要求优异的透明性、视认性。
为了提高这些膜的防卷曲、抗损伤和表面硬度等性能,大多进行硬涂层加工。另外,作为基材,一般使用透明性、机械特性优异的聚酯膜。为了提高聚酯膜与硬涂层的附着性,一般情况下设置易粘接的涂布层作为中间层。因此,如果不考虑聚酯膜、易粘接的涂布层、硬涂层这3层的折射率,就会产生干涉斑。
如果将有干涉斑的膜用在触摸面板等显示器中,就会成为视认性差的显示器,成为难以使用的产品。因此,要求制定干涉斑的对策。一般认为用于减轻干涉斑的涂布层的折射率,处于基材的聚酯膜折射率和硬涂层的折射率的几何平均值附近,调整为该值附近的折射率较为理想。因为聚酯膜的折射率高,所以一般需要将涂布层的折射率设计得较高。
作为提高涂布层的折射率来改善干涉斑的例子,例如,有组合金属螯合化合物和树脂来提高涂布层中折射率的方法(专利文献1)。该方法由于金属螯合物在水溶液中的不稳定性,所以通过组合会有涂布液稳定性不充分的情况,在进行长时间生产时,有可能造成液体更换作业的增加。另外,因为使用金属螯合物,所以耐湿热性不充分。因此,要求有涂布液的稳定性优异且耐湿热性优异的涂布层。
现有技术文献
专利文献
专利文献1:日本特开2005-97571号公报
发明内容
发明所要解决的课题
本发明是鉴于上述实际情况而完成的,其解决课题在于提供一种能够减轻由外部光线的反射产生的干涉斑,与硬涂层等各种表面功能层的附着性优异的叠层聚酯膜。
用于解决课题的方法
本发明的发明者们鉴于上述实际情况进行了深入研究,结果发现如果使用具有特定构成的叠层聚酯膜,就能够容易解决上述问题,从而完成了本发明。
即,本发明的要点在于一种叠层聚酯膜,其特征在于,在聚酯膜的至少一个面具有由涂布液形成的涂布层,该涂布层包含含萘骨架的聚酯树脂、金属氧化物和丙烯酸树脂和/或聚氨酯树脂。
发明的效果
根据本发明的叠层聚酯膜,就能够提供在叠层硬涂层等各种表面功能层时由外部光线的反射产生的干涉斑少、与各种表面功能层的附着性优异的膜,其工业价值高。
具体实施方式
构成本发明的叠层聚酯膜的聚酯膜,既可以是单层结构,也可以是多层结构,在2层、3层结构以外,只要不超越本发明的要点,还可以是4层或其以上的多层,没有特别限定。
本发明中使用的聚酯既可以是均聚聚酯也可以是共聚聚酯。由均聚聚酯构成时,优选使芳香族二元羧酸和脂肪族二醇缩聚得到的聚酯。作为芳香族二元羧酸,可以列举对苯二甲酸、2,6-萘二甲酸等,作为脂肪族二醇,可以列举乙二醇、一缩二乙二醇、1,4-环己烷二甲醇等。作为代表性的聚酯,可以例示聚对苯二甲酸乙二醇酯等。另一方面,作为共聚聚酯的二元羧酸成分,可以列举间苯二甲酸、邻苯二甲酸、对苯二甲酸、2,6-萘二甲酸、己二酸、癸二酸、羟基羧酸(例如对羟基苯甲酸等)等中的一种或两种以上,作为二元醇成分,可以列举乙二醇、一缩二乙二醇、丙二醇、丁二醇、4-环己烷二甲醇、季戊二醇等中的一种或两种以上。
另外,为了提高膜的耐候性,防止在滤色器等中使用的色素劣化,可以使聚酯膜中含有紫外线吸收剂。紫外线吸收剂是具有紫外线吸收功能的化合物,只要是能够耐受聚酯膜的制造工序中所施加的热的化合物,就没有特别限定。
作为紫外线吸收剂,有有机类紫外线吸收剂和无机类紫外线吸收剂,但从透明性的观点出发,优选有机类紫外线吸收剂。作为有机类紫外线吸收剂,没有特别限定,例如,可以列举环状亚胺酸酯类、苯并三唑类、二苯甲酮类等。从耐久性的观点出发,更优选环状亚胺酸酯类、苯并三唑类。另外,也能够并用2种以上的紫外线吸收剂来使用。
以赋予滑动性和防止在各工序中发生损伤为主要目的,也可以在本发明的膜的聚酯层中配合颗粒。配合的颗粒种类,只要是能够赋予滑动性的颗粒,就没有特别限定,作为具体例子,例如,可以列举二氧化硅、碳酸钙、碳酸镁、碳酸钡、硫酸钙、磷酸钙、磷酸镁、高岭土、氧化铝、氧化钛、有机颗粒等颗粒。另外,在聚酯制造工序中,还能够使用使一部分催化剂等金属化合物沉淀、微分散得到的析出颗粒。
本发明的叠层聚酯膜,因为在各种光学用膜和装饰用膜中使用,所以优选提高透明性和鲜明性。为了提高透明性、鲜明性,优选聚酯膜中的颗粒含量少。由此,优选设为只使膜的表层含有颗粒的多层结构或在聚酯膜中不含颗粒的设计。在从透明性、鲜明性的观点出发而更优选的聚酯膜中不含颗粒的设计的情况下,为了改善膜的滑动性等操作性,优选设计为在涂布层中含有颗粒。
另外,在本发明的聚酯膜中,根据需要能够添加现有公知的抗氧化剂、防静电剂、热稳定剂、润滑剂、染料、颜料等。
本发明的聚酯膜的厚度,只要是作为膜可成膜的范围就没有特别限定,通常为10~300μm的范围,优选为25~250μm的范围。
接着,具体说明本发明的聚酯膜的制造例,但不受以下的制造例的任何限定。即,优选如下方法:使用先前所述的聚酯原料,用冷却辊冷却固化从模头中挤出的熔融片,得到未拉伸片。此时,为了提高片的平面性,优选提高片和旋转冷却鼓的附着性,优选采用静电施加附着法和/或液体涂布附着法。接着,将得到的未拉伸片在双轴方向上拉伸。此时,首先采用辊或拉幅机方式的拉伸机在一个方向上拉伸上述的未拉伸片。拉伸温度通常为70~120℃,优选为80~110℃,拉伸倍率通常为2.5~7倍,优选为3.0~6倍。接着,沿与第一阶段拉伸方向正交的方向进行拉伸,此时,拉伸温度通常为70~170℃,拉伸倍率通常为3.0~7倍,优选为3.5~6倍。然后,继续以180~270℃的温度在紧拉下或30%以内的松弛下进行热处理,得到双轴取向膜。在上述拉伸中,也能够采用以2阶段以上进行一个方向的拉伸的方法。此时,优选以最终在两个方向的拉伸倍率分别为上述范围的方式进行。
另外,在本发明中,关于构成叠层聚酯膜的聚酯膜制造,还能够采用同时双轴拉伸法。同时双轴拉伸法是通常以70~120℃、优选以80~110℃的温度被控制的状态,在机械方向和宽度方向使上述未拉伸片同时拉伸取向的方法,作为拉伸倍率,以面积倍率计为4~50倍,优选为7~35倍,更优选为10~25倍。然后,继续在170~250℃的温度,在紧拉下或30%以内的松弛下进行热处理,得到拉伸取向膜。关于采用上述拉伸方式的同时双轴拉伸装置,可以采用螺旋方式、缩放方式、线性驱动方式等现有公知的拉伸方式。
接着,说明构成本发明的叠层聚酯膜的涂布层的形成。关于涂布层,既可以通过在聚酯膜的拉伸工序中对膜表面进行处理的在线涂布设置,也可以采用在系统外在暂时制造的膜上进行涂布的离线涂布,还可以并用两者。因为能够与制膜的同时进行涂布,所以能够廉价地进行制造,从能够利用拉伸倍率使涂布层的厚度变化方面考虑,优选使用在线涂布。
就在线涂布而言,并不限定于以下的方式,例如,在逐次双轴拉伸中,特别在纵向拉伸结束后的横向拉伸前,能够实施涂布处理。通过在线涂布在聚酯膜上设置涂布层时,能够与制膜的同时进行涂布,并且能够在高温处理涂布层,从而能够制造适合的膜作为聚酯膜。
本发明的叠层聚酯膜,其必要的条件是,在聚酯膜的至少一个面具有由涂布液形成的涂布层,该涂布液包含:含萘骨架的聚酯树脂、金属氧化物和丙烯酸树脂和/或聚氨酯树脂。
本发明中的含萘骨架的聚酯树脂主要是用于调整涂布层折射率以及改善与硬涂层等表面功能层的附着性而使用的树脂。
作为在聚酯树脂中导入萘骨架的方法,例如有在萘环上导入2个或2个以上的作为取代基的羟基作为二元醇成分或多元羟基成分,或导入2个或2个以上的羧酸基作为二元酸成分或多元羧酸成分进行制造的方法。从聚酯树脂稳定性的观点出发,优选在萘环上导入羧酸基作为酸成分。作为导入了羧酸基的萘骨架,作为代表性的化合物,可以列举2,6-萘二甲酸、1,5-萘二甲酸和2,7-萘二甲酸等。其中,特别优选2,6-萘二甲酸。
另外,作为含萘骨架的聚酯树脂的构成成分,也可以并用不具有萘骨架的例如下述那样的多元羧酸和多元羟基化合物。即,作为多元羧酸,能够使用对苯二甲酸、间苯二甲酸、邻苯二甲酸、苯二甲酸、4,4′-二苯基二羧酸、1,4-环己烷二甲酸、2-硫代对苯二甲酸钾、5-硫代间苯二甲酸钠、己二酸、壬二酸、癸二酸、十二烷二羧酸、戊二酸、琥珀酸、偏苯三酸、苯均三酸、苯均四酸、偏苯三酸酐、苯二甲酸酐、对羟基苯甲酸、偏苯三酸一钾盐和它们的酯形成性衍生物等,作为多元羟基化合物,可以列举乙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丙二醇、1,4-丁二醇、1,6-己二醇、2-甲基-1,5-戊二醇、季戊二醇、1,4-环己二醇、对苯二甲醇、双酚A-乙二醇加成物、一缩二乙二醇、三甘醇、聚乙二醇、聚丙二醇、聚丁二醇、聚氧亚丁基二醇、二羟甲基丙酸、丙三醇、三羟甲基丙烷、二羟甲基乙基磺酸钠、二羟甲基丙酸钾等。
本发明中的金属氧化物主要是用于调整涂布层折射率而使用的化合物。特别是因为在涂布层中使用的树脂的折射率低,所以优选使用具有高折射率的金属氧化物,优选使用作为折射率为1.7以上的金属氧化物。作为金属氧化物的具体例子,例如,可以列举氧化锆、氧化钛、氧化锡、氧化钇、氧化锑、氧化铟、氧化锌、氧化锑锡、氧化铟锡等,它们既可以单独使用,也可以使用2种以上。这些金属氧化物中,更优选使用氧化锆或氧化钛,特别从耐候性的观点出发,更优选使用氧化锆。
金属氧化物因为随着使用形态而有附着性和涂布液稳定性下降的担忧,所以优选以颗粒状态使用,另外,从透明性和涂布液稳定性的观点出发,其平均粒径优选为0.001~0.1μm的范围,其中,粒径小的金属氧化物能够在保持透明性的状态下,更容易地进行涂布层折射率的调整,故而优选。
但是,如后所述,在以还要赋予滑动性等操作性的目的使用时,也能够在不损害透明性的范围内,少量使用平均粒径为0.1~1.0μm范围的颗粒。
本发明中的丙烯酸树脂和/或聚氨酯树脂,用于提高在涂布层上形成表面功能层后的附着性。发现了通过组合聚酯树脂和丙烯酸树脂和/或聚氨酯树脂,能够出现各树脂单独所不能达到的附着性。
本发明中的丙烯酸树脂是以丙烯酸类、甲基丙烯酸类的单体为代表的具有碳-碳双键的聚合性单体所构成的聚合物。这些丙烯酸树脂可以是均聚物或共聚物的任意聚合物。另外,还包含这些聚合物与其它聚合物(例如,聚酯、聚氨酯等)的共聚物。例如,为嵌段共聚物、接枝共聚物。或者,也包含在聚酯溶液或在聚酯分散液中聚合具有碳-碳双键的聚合性单体而得到的聚合物(根据情况是聚合物的混合物)。同样,还包含在聚氨酯溶液、在聚氨酯分散液中聚合具有碳-碳双键的聚合性单体而得到的聚合物(根据情况是聚合物的混合物)。还包含同样操作,在其它聚合物溶液或分散液中聚合具有碳-碳双键的聚合性单体而得到的聚合物(根据情况是聚合物的混合物)。另外,为了使附着性进一步提高,也能够含有羟基、氨基。
作为上述具有碳-碳双键的聚合性单体,没有特别限制,作为特别具有代表性的化合物,例如,可以列举丙烯酸、甲基丙烯酸、丁烯酸、衣康酸、富马酸、马来酸、柠康酸那样的各种含羧基单体类及其盐,2-羟乙基(甲基)丙烯酸酯、2-羟丙基(甲基)丙烯酸酯、4-羟丁基(甲基)丙烯酸酯、羟基富马酸单丁酯、羟基衣康酸单丁酯那样各种含羟基单体类,(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸月桂酯那样的各种(甲基)丙烯酸酯类,(甲基)丙烯酰胺、二丙酮丙烯酰胺、N-羟甲基丙烯酰胺或(甲基)丙烯腈等那样的各种含氮化合物,苯乙烯、α-甲基苯乙烯、二乙烯基苯、乙烯基甲苯那样的各种苯乙烯衍生物,丙酸乙烯酯那样的各种乙烯基酯类,γ-甲基丙烯酰氧基丙基三甲氧基硅烷、乙烯基三甲氧基硅烷等那样的各种含硅聚合性单体类,含磷乙烯基系单体类,氯乙烯、偏氯乙烯那样的各种卤化乙烯类,丁二烯那样的各种共轭二烯类。
本发明中的聚氨酯树脂是在分子内具有聚氨酯树脂的高分子化合物。通常,聚氨酯树脂由多元醇与异氰酸酯的反应制成。作为多元醇,可以列举聚碳酸酯多元醇类、聚酯多元醇类、聚醚多元醇类、聚烯烃多元醇类、丙烯酸多元醇类,这些化合物既可以单独使用,也可以使用多种。
聚碳酸酯多元醇类通过脱醇反应从多元醇类和碳酸酯化合物得到。作为多元醇类,可以列举乙二醇、1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,4-环己二醇、1,4-环己烷二甲醇、1,7-庚二醇、1,8-辛二醇、1,9-壬二醇、1,10-癸二醇、季戊二醇、3-甲基-1,5-戊二醇、3,3-二羟甲基庚烷等。作为碳酸酯化合物,可以列举碳酸二甲酯、碳酸二乙酯、碳酸二苯酯、碳酸亚乙酯等,作为从这些反应得到的聚碳酸酯系多元醇类,例如,可以列举聚(1,6-己烯)碳酸酯、聚(3-甲基-1,5-戊烯)碳酸酯等。
作为聚酯多元醇类,可以列举从多元羧酸(丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、癸二酸、富马酸、马来酸、对苯二甲酸、间苯二甲酸等)或它们的酸酐与多元醇(乙二醇、一缩二乙二醇、三甘醇、丙二醇、一缩二丙二醇、三丙二醇、丁二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、2-甲基-1,3-丙二醇、1,5-戊二醇、季戊二醇、1,6-己二醇、3-甲基-1,5-戊二醇、2-甲基-2,4-戊二醇、2-甲基-2-丙基-1,3-丙二醇、1,8-辛二醇、2,2,4-三甲基-1,3-戊二醇、2-乙基-1,3-己二醇、2,5-二甲基-2,5-己二醇、1,9-壬二醇、2-甲基-1,8-辛二醇、2-丁基-2-乙基-1,3-丙二醇、2-丁基-2-己基-1,3-丙二醇、环己二醇、双羟甲基环己烷、二甲醇苯、双羟基乙氧基苯、烷基二醇胺、内酯二醇等)的反应得到的聚酯多元醇。
作为聚醚多元醇类,可以列举聚乙二醇、聚丙二醇、聚亚乙基亚丙基二醇、聚四亚甲基醚二醇、聚六亚甲基醚二醇等。
为了提高与各种表面功能层的附着性,优选在上述多元醇类中使用聚碳酸酯多元醇类和聚醚多元醇类,因为即使是少量也能够提高附着性,所以特别优选使用聚碳酸酯多元醇类。
作为为了得到聚氨酯树脂而使用的聚异氰酸酯化合物,可以例示亚苄基二异氰酸酯、苯二甲基二异氰酸酯、亚甲基二苯基二异氰酸酯、苯二异氰酸酯、萘二异氰酸酯、联甲苯胺二异氰酸酯等芳香族二异氰酸酯,α,α,α′,α′-四甲基苯二甲基二异氰酸酯等具有芳香环的脂肪族二异氰酸酯、亚甲基二异氰酸酯、亚丙基二异氰酸酯、赖氨酸二异氰酸酯、三甲基六亚甲基二异氰酸酯、六亚甲基二异氰酸酯等脂肪族二异氰酸酯,环己烷二异氰酸酯、甲基环己烷二异氰酸酯、异佛尔酮二异氰酸酯、二环己基甲烷二异氰酸酯、异亚丙基二环己基二异氰酸酯等的脂环族二异氰酸酯等。这些聚异氰酸酯化合物既可以单独使用,也可以多种并用。
在合成聚氨酯树脂时也可以使用链延长剂,作为链延长剂,只要是具有2个以上与异氰酸酯基反应的活性基的链延长剂,就没有特别限制,一般而言,主要使用具有2个羟基或氨基的链延长剂。
作为具有2个羟基的链延长剂,例如,能够列举乙二醇、丙二醇、丁二醇等的脂肪族二醇,苯二甲醇、二羟基乙氧基苯等的芳香族二醇,羟基特戊酸新戊二醇酯等称为酯二醇的二醇类。另外,作为具有2个氨基的链延长剂,例如,可以列举甲苯二胺、苯二甲基二胺、二苯基甲烷二胺等的芳香族二胺,乙二胺、丙二胺、己二胺、2,2-二甲基-1,3-丙二胺、2-甲基-1,5-戊二胺、三甲基己二胺、2-丁基-2-乙基-1,5-戊二胺、1,8-辛二胺、1,9-壬二胺、1,10-癸二胺等的脂肪族二胺,1-氨基-3-氨基甲基-3,5,5-三甲基环己烷、二环己基甲烷二胺、异亚丙基环己基-4,4′-二胺、1,4-二氨基环己烷、1,3-二氨基甲基环己烷等的脂环族二胺等。
本发明中的聚氨酯树脂可以以溶剂为介质,但优选为以水为介质。为了使聚氨酯树脂在水中分散或溶解,有使用乳化剂的强制乳化型、在聚氨酯树脂中导入亲水性基团的自乳化型或水溶型等。特别是在聚氨酯树脂骨架中导入离子基而离聚物化的自乳化类型,液体的储存稳定性和得到的涂布层的耐水性、透明性、附着性优异,故而优选。另外,作为导入的离子基,可以列举羧基、磺酸、磷酸、膦酸、季铵盐等各种离子基,优选羧基。作为在聚氨酯树脂中导入羧基的方法,能够在聚合反应的各阶段中采取各种方法。例如,有在合成预聚物时,使用具有羧基的树脂作为共聚成分的方法,和使用具有羧基的成分作为多元醇、聚异氰酸酯或链延长剂等的一个成分的方法。特别优选使用含有羧基的二元醇,根据该成分的加入量来导入所希望量的羧基的方法。例如,能够对于用于聚氨酯树脂聚合的二元醇,使二羟甲基丙酸、二羟甲基丁酸、双-(2-羟乙基)丙酸、双-(2-羟乙基)丁酸等共聚。另外,该羧基优选制成以氨、胺、碱金属类、无机碱类等中和后的盐的形态。特别优选为氨、三甲胺、三乙胺。这样的聚氨酯树脂可以使用在涂布后的干燥工序中中和剂脱离的羧基作为由其它交联剂引起的交联反应位点。由此,在涂布前液体状态的稳定性优异的基础上,能够进一步改善所得到的涂布层的耐久性、耐溶剂性、耐水性、耐粘连性等。
另外,在本发明中,为了提高涂布层强度、附着性、耐湿热特性,优选使用交联剂。作为交联剂,能够使用各种公知的交联剂,例如,可以列举异氰酸酯化合物、三聚氰胺化合物、噁唑啉化合物、环氧化合物、碳化二亚胺化合物等或它们的反应物。
作为异氰酸酯化合物,例如,可以例示亚苄基二异氰酸酯、苯二甲基二异氰酸酯、亚甲基二苯基二异氰酸酯、苯二异氰酸酯、萘二异氰酸酯等的芳香族异氰酸酯,α,α,α′,α′-四甲基亚二甲苯基二异氰酸酯等具有芳香环的脂肪族异氰酸酯,亚甲基二异氰酸酯、亚丙基二异氰酸酯、赖氨酸二异氰酸酯、三甲基六亚甲基二异氰酸酯、六亚甲基二异氰酸酯等的脂肪族异氰酸酯,环己烷二异氰酸酯、甲基环己烷二异氰酸酯、异佛尔酮二异氰酸酯、亚甲基双(4-环己基异氰酸酯)、异亚丙基二环己基二异氰酸酯等的脂环族异氰酸酯等,其中从附着性的观点出发,特别优选亚苄基二异氰酸酯和六亚甲基二异氰酸酯。另外,也可以列举这些异氰酸酯的缩二脲化物、异氰脲酸酯化物、异氰酸酯二聚体化物、碳化二亚胺改性体等的聚合物和衍生物。它们既可以单独使用,也可以多种并用。
以封闭异氰酸酯的状态使用时,作为其封闭剂,例如,可以列举亚硫酸氢盐类、苯酚、邻甲酚、乙基苯酚等的酚类化合物,丙二醇单甲醚、乙二醇、苯甲醇、甲醇、乙醇等的醇类化合物,丙二酸二甲酯、丙二酸二乙酯、乙酰乙酸甲酯、乙酰乙酸乙酯、乙酰丙酮等的活性亚甲基类化合物,丁基硫醇、十二烷基硫醇等的硫醇类化合物,ε-己内酰胺、δ-戊内酰胺等的内酰胺类化合物,二苯基苯胺、苯胺、乙烯亚胺等的胺类化合物,乙酰苯胺、乙酸酰胺的酸酰胺化合物,甲醛、乙醛肟、丙酮肟、甲乙酮肟、环己酮肟等的肟类化合物,这些封闭剂既可以单独也可以并用2种以上。
另外,上述异氰酸酯化合物既可以以单体使用,也可以作为与各种聚合物的混合物或结合物使用。
三聚氰胺化合物是指在化合物中具有三聚氰胺骨架的化合物。例如,能够使用烷醇化三聚氰胺衍生物、使醇与烷醇化三聚氰胺衍生物反应而部分或完全醚化的化合物和它们的混合物。作为在醚化中使用的醇,可以适当地使用甲醇、乙醇、异丙醇、正丁醇、异丁醇等。另外,作为三聚氰胺化合物,既可以是单体或二聚体以上的多聚体中的任意一种,或者也可以使用这些的混合物。另外,既能够使用在一部分三聚氰胺中缩聚尿素等的缩合物,也能够为了提高三聚氰胺化合物反应性而使用催化剂。
噁唑啉化合物是指在分子内具有噁唑啉基的化合物。特别优选含有噁唑啉基的聚合物,能够通过由加聚性含噁唑啉基的单体单独或与其它单体的聚合制成。加聚性含噁唑啉基的单体,能够列举2-乙烯基-2-噁唑啉、2-乙烯基-4-甲基-2-噁唑啉、2-乙烯基-5-甲基-2-噁唑啉、2-异丙烯基-2-噁唑啉、2-异丙烯基-4-甲基-2-噁唑啉、2-异丙烯基-5-乙基-2-噁唑啉等,能够使用它们的1种或2种以上的混合物。其中,2-异丙烯基-2-噁唑啉在工业上也容易购入而适合。其它单体只要是能够与加聚性含噁唑啉基的单体共聚的单体就没有限制,例如能够使用烷基(甲基)丙烯酸酯(作为烷基,为甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、2-乙基己基、环己基)等的(甲基)丙烯酸酯类,丙烯酸、甲基丙烯酸、衣康酸、马来酸、富马酸、丁烯酸、苯乙烯磺酸及其盐(钠盐、钾盐、铵盐、叔胺盐等)等不饱和羧酸类,丙烯腈、甲基丙烯腈等不饱和腈类,(甲基)丙烯酰胺、N-烷基(甲基)丙烯酰胺、N,N-二烷基(甲基)丙烯酰胺(作为烷基,为甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、2-乙基己基、环己基等)等不饱和酰胺类,乙酸乙烯酯、丙酸乙烯酯等乙烯基酯类,甲基乙烯基醚、乙基乙烯基醚等乙烯基醚类,乙烯、丙烯等α-烯烃类,氯乙烯、偏氯乙烯、氟化乙烯等含卤素的α,β-不饱和单体类,苯乙烯、α-甲基苯乙烯等α,β-不饱和芳香族单体等,能够使用它们中的1种或2种以上的单体。
作为环氧化合物,例如,可以列举环氧氯丙烷与乙二醇、聚乙二醇、丙三醇、聚甘油、双酚A等的羟基或氨基的缩合物,有聚环氧化合物、二环氧化合物、一环氧化合物、缩水甘油胺化合物等。作为聚环氧化合物,例如,可以列举山梨糖醇聚缩水甘油醚、聚甘油聚缩水甘油醚、季戊四醇聚缩水甘油醚、二甘油聚缩水甘油醚、三缩水甘油基三(2-羟乙基)异氰酸酯、甘油聚缩水甘油醚、三羟甲基丙烷聚缩水甘油醚等,作为二环氧化合物,例如,可以列举季戊二醇二缩水甘油醚、1,6-己二醇二缩水甘油醚、间苯二酚二缩水甘油醚、乙二醇二缩水甘油醚、聚乙二醇二缩水甘油醚、丙二醇二缩水甘油醚、聚丙二醇二缩水甘油醚、聚四亚甲基二醇二缩水甘油醚等,作为一环氧化合物,例如,可以列举烯丙基缩水甘油醚、2-乙基己基缩水甘油醚、苯基缩水甘油醚等,作为缩水甘油胺化合物,可以列举N,N,N′,N′-四缩水甘油基-间苯二甲基二胺、1,3-双(N,N-二缩水甘油基氨基)环己烷等。
这些交联剂,既可以单独使用,也可以混合多种使用。还可以优选在考虑对于在线涂布的适用等时,具有水溶性或水分散性。
为了改善涂布面状态、减少在涂布面上叠层硬涂层等各种表面功能层时的干涉斑、提高透明性和附着性等,也能够在本发明的叠层聚酯膜中,并用上述以外的各种聚合物。
作为聚合物的具体例子,可以列举不含萘骨架的聚酯树脂、聚亚烷基二醇、聚亚烷基亚胺、甲基纤维素、羟基纤维素、淀粉类等。其中,从改善与硬涂层等表面功能层的附着性的观点出发,优选使用不含萘骨架的聚酯树脂。
另外,本发明以改善涂布层的固着性、润滑性为目的,优选在涂布层中含有上述金属氧化物以外的颗粒。特别是在聚酯膜中不含颗粒的设计时,为了改善膜的滑动性等的操作性,优选设计为在涂布层中含有比上述金属氧化物颗粒的粒径大的颗粒。从膜的透明性的观点出发,以该目的使用的在涂布层中含有的颗粒的平均粒径优选为1.0μm以下的范围,更优选为0.05~0.7μm的范围,特别优选为0.1~0.5μm的范围。作为颗粒的具体例子,可以列举二氧化硅、氧化铝、高岭土、碳酸钙、有机颗粒等,特别从分散性的观点出发,更优选二氧化硅。
在不损害本发明要点的范围,为了提高对膜的润湿性而均匀地涂布涂布液,还能够适量添加公知的阴离子型表面活性剂或非离子型表面活性剂。为了进一步提高对膜的润湿性,更适合使用氟类表面活性剂。
氟类表面活性剂是指具有部分或全部氢原子被氟原子取代的烃链的化合物。另外,使用水类涂布液时,氟类表面活性剂优选具有一定程度的水溶性或水分散性,例如,可以列举在被氟取代的烃链的基础上还具有亲水性基团的化合物。作为亲水性基团,例如,可以列举磺酸、羧酸、磷酸等的胺或金属盐、叔胺的卤化盐、羟基或醚基等。
作为阴离子型氟类表面活性剂,可以列举全氟烷基(C4~C12)磺酸的锂盐、钾盐、钠盐和铵盐、全氟烷基(C7~C20)羧酸的钾盐、钠盐和铵盐、全氟烷基二羧酸钾盐、全氟烷基磷酸盐等。另外,作为非离子型氟类表面活性剂,可以列举全氟辛烷磺酸二乙醇酰胺、N-丙基-N-(2-羟乙基)全氟辛烷磺酸酰胺、全氟烷基聚氧乙烯乙醇、全氟烷基烷氧基化物等。
另外,在不损害本发明要点的范围,根据需要还可以在涂布层中含有消泡剂、增粘剂、有机类润滑剂、防静电剂、紫外线吸收剂、抗氧化剂、发泡剂、染料、颜料等。
含萘骨架的聚酯树脂中萘环的比例,优选为5~80重量%的范围,更优选为10~60重量%的范围。另外,作为相对于涂布液中的全部不挥发成分的比例,涂布液中的含萘骨架的聚酯树脂的比例通常为5~90重量%的范围,优选为10~85重量%的范围,更加优选为15~80重量%的范围。通过在这些范围内使用,就容易调整涂布层折射率,容易减轻形成硬涂层等表面功能层后的干涉斑。其中,萘环的比例例如能够通过用适当的溶剂或温水溶解涂布层进行提取,用色谱分离提取,以NMR或IR解析结构,再用热分解GC-MS(气相色谱-质谱)或光学分析等进行解析而求出。
作为相对于涂布液中全部不挥发成分的比例,涂布液中的金属氧化物的比例通常为3~70重量%的范围,优选为5~50重量%的范围,更加优选为5~40重量%的范围,特别优选为6~30重量%的范围。金属氧化物的量小于3重量%时,由于不能充分提高涂布层的折射率,而有干涉斑不能被减轻的情况,大于70重量%时,有涂布层的透明性恶化的情况或附着性下降的情况。
作为相对于涂布液中全部不挥发成分的比例,涂布液中的丙烯酸树脂和/或聚氨酯树脂的比例通常为1~50重量%的范围,更优选为5~40重量%的范围,更加优选为10~30重量%的范围。小于1重量%时,有与硬涂层等的表面功能层的附着性下降的可能性,大于50重量%时,由于涂布层的折射率变低,由硬涂层等的表面功能层形成后的干涉斑,而有视认性不良的情况。
作为相对于涂布液中全部不挥发成分的比例,涂布液中的交联剂的比例优选为50重量%以下,更优选为5~30重量%的范围。大于50重量%时,会有涂布层的折射率调整变得困难的情况或涂布面状态恶化的情况。
在本发明中,能够在涂布层中含有的、用于改善膜的滑动性等操作性而使用的颗粒比例,作为相对于涂布液中全部不挥发成分的比例,通常为0.1~5重量%的范围,优选为0.3~3重量%的范围,更优选为0.4~2重量%的范围。少数情况下,需要涂布层中含有的金属氧化物颗粒的效果或通过使膜中含有颗粒来改善操作性,而另一方面,大多情况下,膜的透明性会恶化。
在本发明的聚酯膜中,还可以在与设有上述涂布层的面相反侧的面设置涂布层。例如,在形成硬涂层等表面功能层的相反侧形成微透镜层、棱镜层、防粘连层、光扩散层、硬涂层、粘接层、印刷层等功能层时,能够改善与该功能层的附着性。作为在相反侧的面形成的涂布层的成分,能够使用现有公知的成分。例如,可以列举聚酯树脂、丙烯酸树脂、聚氨酯树脂等粘合剂聚合物,噁唑啉化合物、环氧化合物、三聚氰酰胺化合物、异氰酸酯化合物等交联剂等,既可以单独使用这些材料,也可以并用多种。另外,也可以是含有上述那样含萘骨架的聚酯树脂、金属氧化物和丙烯酸树脂和/或聚氨酯树脂的涂布层(在聚酯膜两面为相同的涂布层)。
涂布层中的成分的分析,例如,可以由TOF-SIMS、ESCA、荧光X射线等的分析进行。
采用在线涂布设置涂布层时,优选以如下要领制造叠层聚酯膜:将上述一系列化合物制成水溶液或水分散体,在聚酯膜上涂布以固体成分浓度0.1~50重量%左右为大致标准配制的涂布液。另外,在不损害本发明要点的范围,以改善对水的分散性、改善成膜性等为目的,也可以在涂布液中含有少量的有机溶剂。有机溶剂既可以仅为1种,也可以适当地使用2种以上。
关于本发明的叠层聚酯膜,在聚酯膜上设置的涂布层膜厚通常为0.04~0.20μm的范围,优选为0.07~0.15μm的范围。当膜厚偏离上述范围时,由于将表面功能层叠层后的干涉斑的影响,会有视认性恶化的情况。
在本发明中,设置涂布层的方法能够使用逆向凹版涂布、直接凹版涂布、辊涂、刚模涂布、棒涂、幕式淋涂等现有公知的涂敷方式。
在本发明中,关于在聚酯膜上形成涂布层时的干燥和固化条件没有特别限定,例如,在采用离线涂布设置涂布层时,通常以80~200℃、3~40秒,优选以100~180℃、3~40秒作为大致标准进行热处理即可。
另一方面,在采用在线涂布设置涂布层时,通常以70~280℃、3~200秒作为大致标准进行热处理即可。
另外,无论离线涂布或在线涂布,根据需要都可以并用热处理和紫外线照射等活性能量线照射。对于构成本发明的叠层聚酯膜的聚酯膜,也可以预先实施电晕处理、等离子体处理等表面处理。
本发明中的涂布层是为了抑制产生干涉斑而进行了折射率调整的层,其折射率设计在基材的聚酯膜和硬涂层等表面功能层的几何平均值附近。涂布层的折射率和涂布层的反射率具有密切关系。就本发明的绝对反射率而言,绘制横轴表示波长、纵轴表示反射率的图,优选反射率的极小值在波长400~800nm的范围为1个,该极小值优选为4.0%以上。在本发明的绝对反射率的范围中,该极小值如果在相同波长处出现,则极小值的反射率在折射率高时为高的值,在折射率低时为低的值。
本发明中的绝对反射率,优选在波长400~800nm的范围存在1个极小值,更优选在波长500~700nm的范围存在1个极小值。另外,该极小值的值优选在4.0~6.5%的范围,更优选在4.5~6.2%的范围。在波长400~800nm范围内的极小值不是1个时,另外,极小值的绝对反射率偏离上述值时,会有形成硬涂层等表面功能层后产生干涉斑、膜的视认性下降的情况。
在本发明的聚酯膜中,一般在涂布层上设置硬涂层等表面功能层。作为用于硬涂层的材料没有特别限定,例如,可以列举单官能(甲基)丙烯酸酯、多官能(甲基)丙烯酸酯、四乙氧基硅烷等反应性硅化合物等的固化物。其中,从兼顾生产率和硬度的观点出发,特别优选为包含紫外线固化性的多官能(甲基)丙烯酸酯组合物的聚合固化物。
作为包含紫外线固化性的多官能(甲基)丙烯酸酯的组合物。没有特别限定。例如,能够使用混合1种以上公知的紫外线固化性多官能(甲基)丙烯酸酯而成的组合物、作为紫外线固化性硬涂层材料所市售的组合物、或在这些的基础上在不损害本实施方式目的的范围另外添加其它成分而成的组合物。
作为紫外线固化性的多官能(甲基)丙烯酸酯没有特别限定,例如,可以列举二季戊四醇六(甲基)丙烯酸酯、四羟甲基甲烷四(甲基)丙烯酸酯、四羟甲基甲烷三(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,6-双(3-丙烯酰氧基-2-羟基丙基氧代)己烷等多官能醇的(甲基)丙烯酸衍生物或聚乙二醇二(甲基)丙烯酸酯,还有聚氨酯(甲基)丙烯酸酯等。
在包含紫外线固化性的多官能(甲基)丙烯酸酯的组合物中所包含的其它成分没有特别限定。例如,可以列举无机或有机的微粒、聚合引发剂、阻聚剂、抗氧化剂、防静电剂、分散剂、表面活性剂、光稳定剂和流平剂等。另外,在湿式涂布法中在成膜后使其干燥时,能够添加任意量的溶剂。
硬涂层的形成方法,在使用有机材料时可采用辊涂法、刚模涂布法等一般的湿式涂布法。对所形成的硬涂层,根据需要能够实施加热和紫外线、电子射线等活性能量线照射,进行固化反应。
实施例
下面,利用实施例进一步详细地说明本发明,但本发明只要不超越其要点,就不受以下的实施例限定。另外,在本发明中使用的测定法和评价方法如下。
(1)聚酯的特征粘度的测定方法:
精确称量1g在聚酯中除去非相溶的其它聚合物成分和颜料的聚酯,加入100ml的苯酚/四氯乙烷=50/50(重量比)的混合溶剂,使其溶解,在30℃进行测定。
(2)平均粒径的测定方法:
使用TEM(日立制H-7650,加速电压100V)观察涂布层,以10个颗粒的粒径平均值作为平均粒径。
(3)涂布层膜厚的测定方法:
将涂布层表面以RuO4进行染色,并包埋在环氧树脂中。然后,将由超薄切片法制成的切片以RuO4进行染色,使用TEM(日立制H-7650,加速电压100V)测定涂布层剖面。
(4)聚酯膜的从涂布层表面的绝对反射率的评价方法:
在聚酯膜的测定背面预先贴合黑胶带(NICHIBAN株式会社制聚氯乙烯胶带VT-50),使用分光光度计(日本分光株式会社生产,紫外可见分光光度计V-570和自动绝对反射率测定装置AM-500N)、以同步模式、入射角5°、N偏光、响应Fast、数据采集区间隔1.0nm、带宽10nm、扫描速度1000m/min测定涂布层面在波长范围300~800nm的绝对反射率,评价在该极小值的波长(底波波长(bottom wavelength))和反射率。
(5)干涉斑的评价方法:
在聚酯膜的涂布层侧,以干燥膜厚为5μm的方式涂布72重量份二季戊四醇六丙烯酸酯、18重量份1,6-己二醇二丙烯酸酯、10重量份五氧化二锑、1重量份光聚合引发剂(商品名:IRGACURE 184,汽巴精化生产)、200重量份甲乙酮的混合涂布液,照射紫外线使其固化,形成硬涂层。对得到的膜,在3波长光区域型荧光灯下以目测观察干涉斑,将未能确认干涉斑的膜评价为◎,将可确认淡且稀疏的干涉斑的膜评价为○,将能够确认淡而呈线状的干涉斑的膜评价为△,将可确认明显干涉斑的膜评价为×。
(6)附着性的评价方法:
为了进行更严格的附着性评价,以从上述(5)的评价中使用的硬涂层液中除去了五氧化二锑的材料进行研究。即,以干燥膜厚为5μm的方式涂布80重量份二季戊四醇六丙烯酸酯、20重量份1,6-己二醇二丙烯酸酯、5重量份光聚合引发剂(商品名:IRGACURE 184,汽巴精化生产)、200重量份甲乙酮的混合涂布液,照射紫外线使其固化,形成硬涂层。对得到的膜,在60℃、90%RH的环境下放置100小时后,进行10×10的交叉切割(cross cut),在其上贴附18mm宽的胶带(NICHIBAN株式会社生产的CELLOTAPE(注册商标)、CT-18),观察以180度的剥离角度迅速地剥离后的剥离面,剥离面积如果不足3%则评价为◎,如果为3%以上、小于10%则评价为○,如果为10%以上不足50%则评价为△,如果为50%以上则评价为×。
在实施例和比较例中使用的聚酯是如以下操作而准备的聚酯。
<聚酯(A)的制造方法>
以100重量份对苯二甲酸二甲酯和60重量份乙二醇为起始原料,作为催化剂在反应器中加入0.09重量份四水合乙酸镁,将反应开始温度设为150℃,伴随甲醇的蒸馏除去使反应温度缓慢上升,3小时后达到230℃。4小时后,使酯交换反应实质性地结束。在该反应混合物中添加0.04重量份磷酸三乙酯后,加入0.04重量份三氧化二锑,进行4小时缩聚反应。即,将温度从230℃缓慢升温到280℃。另一方面,压力由常压缓慢下降,最后达到0.3mmHg。反应开始后,由反应槽搅拌动力的变化,在相当于特征粘度0.63的时刻停止反应,在氮加压下使聚合物排出,得到的聚酯(A)的特征粘度为0.63。
<聚酯(B)的制造方法>
在聚酯(A)的制造方法中,添加0.04重量份磷酸三乙酯后,加入0.2重量份平均粒径为1.6μm的分散乙二醇中的二氧化硅颗粒、0.04重量份三氧化二锑,在相当于特征粘度0.65的时刻停止缩聚反应,除此以外,使用与聚酯(A)的制造方法同样的方法得到聚酯(B)。得到的聚酯(B)的特征粘度为0.65。
构成涂布层的化合物例子如下所示。
(化合物例)
含萘骨架的聚酯树脂:(ⅠA)
以下述组成共聚的聚酯树脂的水分散体
单体组成:(酸成分)2,6-萘二甲酸/5-硫代间苯二甲酸钠//(二元醇成分)乙二醇/一缩二乙二醇=92/8//80/20(mol%)
·含萘骨架的聚酯树脂:(ⅠB)
以下述组成共聚的聚酯树脂的水分散体
单体组成:(酸成分)2,6-萘二甲酸/对苯二甲酸/5-硫代间苯二甲酸钠//(二元醇成分)乙二醇/一缩二乙二醇=78/15/7//90/10(mol%)
·金属氧化物:(ⅡA)平均粒径70nm的氧化锆颗粒
·金属氧化物:(ⅡB)平均粒径15nm的氧化锆颗粒
·金属氧化物:(ⅡC)平均粒径15nm的氧化钛颗粒
·丙烯酸树脂:(ⅢA)以下述组成聚合的丙烯酸树脂的水分散体
丙烯酸乙酯/丙烯酸正丁酯/甲基丙烯酸甲酯/N-羟甲基丙烯酰胺/丙烯酸=65/21/10/2/2(重量%)的乳化聚合物(乳化剂:阴离子型表面活性剂)
·丙烯酸树脂:(ⅢB)以下述组成聚合的丙烯酸树脂的水分散体
丙烯酸乙酯/甲基丙烯酸甲酯/2-羟乙基甲基丙烯酸酯/N-羟甲基丙烯酰胺/丙烯酸=65/28/3/2/2(重量%)的乳化聚合物(乳化剂:阴离子型表面活性剂)
·聚氨酯树脂:(ⅢC)
以三乙胺中和由400份由1,6-己二醇和碳酸二乙酯构成的数均分子量2000的聚碳酸酯多元醇、10.4份季戊二醇、58.4份异佛尔酮二异氰酸酯、74.3份二羟甲基丁酸构成的预聚物,以异佛尔酮二胺将其链延长而得到的聚氨酯树脂的水分散体。
·聚氨酯树脂:(ⅢD)
作为羧酸水分散型聚酯聚氨酯树脂的Hydran AP-40(DIC株式会社生产)。
·异氰酸酯化合物:(ⅣA)
在甲乙酮溶剂中,在100重量份己二酸/间苯二甲酸//1,6-己二醇=50/50//100(mol%)的聚酯多元醇(平均分子量1700)、9重量份1,4-丁二醇、8重量份三羟甲基丙烷中添加80重量份亚苄基二异氰酸酯,进行反应后,添加12重量份二羟甲基丙酸、16重量份聚乙二醇(平均分子量600)、胺催化剂,以75℃进行反应。接着,在55℃添加16重量份甲乙酮肟,制成含有封闭化异氰酸酯基的聚氨酯预聚物。再混合7.2份三乙胺、450重量份水,添加2.9重量份三亚乙基四胺,使其反应,除去甲乙酮溶剂而得到的封闭化异氰酸酯化合物。
·异氰酸酯化合物:(ⅣB)
在200重量份双酚A的2摩尔环氧乙烷加成物与马来酸的聚酯(分子量2000)中,添加33.6重量份六亚甲基二异氰酸酯,以100℃反应2小时。接着,将系统温度暂时降低到50℃,添加73重量份30%亚硫酸氢钠水溶液,以45℃搅拌60分钟后,以718重量份的水稀释的封闭化异氰酸酯化合物。
·噁唑啉化合物:(ⅣC)
具有噁唑啉基和聚亚烷基氧化物链的丙烯酸聚合物EpocrosWS-500(日本触媒生产)。
·六甲氧基甲基三聚氰胺:(ⅣD)
·环氧化合物:(ⅣE)作为聚甘油聚缩水甘油醚的DENACOLEX-521(Nagase Chemtex生产)。
·聚酯树脂:(Ⅴ)
以下述组成共聚的聚酯树脂的水分散体
单体组成:(酸成分)对苯二甲酸/间苯二甲酸/5-硫代间苯二甲酸钠//(二元醇成分)乙二醇/1,4-丁二醇/一缩二乙二醇=56/40/4//70/20/10(mol%)
·颗粒:(ⅥA)平均粒径0.45μm的二氧化硅颗粒
·颗粒:(ⅥB)平均粒径0.30μm的二氧化硅颗粒
·颗粒:(ⅥC)平均粒径0.16μm的二氧化硅颗粒
实施例1:
将聚酯(A)供给挤出机,以285℃熔融后,在设定为40℃的冷却辊上挤出,使其冷却固化,得到未拉伸片。接着,利用辊转速差,以膜温度85℃、在纵向拉伸3.4倍后,在该纵向拉伸膜的两面涂布下述表1所示的涂布液1,导入拉幅机,在横向以120℃拉伸4.0倍,以225℃进行热处理后,在横向松弛2%,得到具有膜厚(干燥后)为0.09μm的涂布层的厚度125μm的聚酯膜。测定得到的聚酯膜的绝对反射率,极小值为580nm,其反射率为4.7%。在叠层硬涂层后的膜中无明显的干涉斑,另外,附着性也良好。在下述表5中表示该膜的特性。
实施例2~23、26~48:
除了在实施例1中,将涂布剂组成变更为下述表1~4所示的涂布剂组成以外,与实施例1同样制造,得到聚酯膜。制成的叠层聚酯膜如表5或表6所示是具有高反射率、干涉斑水平良好、附着性也良好的膜。
实施例24:
将分别以90%、10%的比例混合聚酯(A)、(B)得到的混合原料作为最外层(表层)的原料,以聚酯(A)作为中间层的原料,分别供给2台挤出机,分别在285℃熔融后,在设定为40℃的冷却辊上,以2种3层(表层/中间层/表层=1∶18∶1的排出量)的层结构共同挤出,使其冷却固化,得到未拉伸片。接着,利用辊转速差,以膜温度85℃,在纵向拉伸3.4倍后,在该纵向拉伸膜的两面涂布下述表1所示的涂布液10,导入拉幅机,在横向以120℃拉伸4.0倍,以225℃进行热处理后,在横向松弛2%,得到具有膜厚(干燥后)为0.09μm涂布层的厚度125μm的聚酯膜。测定得到的聚酯膜的绝对反射率,极小值为580nm,其反射率为4.7%。在叠层硬涂层后的膜中无明显的干涉斑,另外,附着性也良好。在下述表3中表示该膜的特性。
实施例25、49、50:
在实施例24中,将涂布剂组成变更为表2~4所示的涂布剂组成以外,与实施例24同样操作制造,得到聚酯膜。制成的叠层聚酯膜如表5或表6所示是具有高反射率、干涉斑水平良好、附着性也良好的膜。
比较例1~7:
在实施例1中,将涂布剂组成变更为表2或表4所示的涂布剂组成以外,与实施例1同样制造,得到聚酯膜。评价制成的叠层聚酯膜,如表5或表6所示,可见能够观察到明显干涉斑的情况、附着性差的情况。
[表1]
[表2]
[表3]
[表4]
[表5]
[表6]
工业上的可利用性
本发明的膜例如能够在作为液晶或等离子体显示器等构件的各种光学用膜和成型用膜等中,重视与硬涂层等表面功能层的附着性和视认性的用途中合适地利用。
Claims (6)
1.一种叠层聚酯膜,其特征在于:
在聚酯膜的至少一个面具有由涂布液形成的涂布层,该涂布液包含含萘骨架的聚酯树脂、金属氧化物和丙烯酸树脂和/或聚氨酯树脂。
2.如权利要求1所述的叠层聚酯膜,其特征在于:
涂布层的膜厚为0.04~0.20μm。
3.如权利要求1或2所述的叠层聚酯膜,其特征在于:
以相对于涂布液中的全部不挥发成分的比例计,涂布液中的含萘骨架的聚酯树脂的比例为5~90重量%,金属氧化物的比例为3~70重量%,丙烯酸树脂和/或聚氨酯树脂的比例为1~50重量%。
4.如权利要求1~3中任一项所述的叠层聚酯膜,其特征在于:
金属氧化物为氧化锆。
5.如权利要求1或2所述的叠层聚酯膜,其特征在于:
涂布液中含有交联剂。
6.如权利要求1~3中任一项所述的叠层聚酯膜,其特征在于:
涂布层表面的绝对反射率在波长400~800nm的范围具有1个极小值,该极小值的绝对反射率为4.0%以上。
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EP (1) | EP2578399B1 (zh) |
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