JP5691261B2 - Photocurable adhesive for polarizing plate formation and polarizing plate - Google Patents
Photocurable adhesive for polarizing plate formation and polarizing plate Download PDFInfo
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- JP5691261B2 JP5691261B2 JP2010144355A JP2010144355A JP5691261B2 JP 5691261 B2 JP5691261 B2 JP 5691261B2 JP 2010144355 A JP2010144355 A JP 2010144355A JP 2010144355 A JP2010144355 A JP 2010144355A JP 5691261 B2 JP5691261 B2 JP 5691261B2
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- 239000000853 adhesive Substances 0.000 title claims description 93
- 230000001070 adhesive effect Effects 0.000 title claims description 84
- 230000015572 biosynthetic process Effects 0.000 title 1
- -1 glycidyl compound Chemical class 0.000 claims description 64
- 230000001681 protective effect Effects 0.000 claims description 44
- 239000012790 adhesive layer Substances 0.000 claims description 43
- 150000001875 compounds Chemical class 0.000 claims description 41
- 125000002723 alicyclic group Chemical group 0.000 claims description 39
- 239000004593 Epoxy Substances 0.000 claims description 38
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 35
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 34
- 125000002091 cationic group Chemical group 0.000 claims description 20
- 125000003700 epoxy group Chemical group 0.000 claims description 19
- 239000003960 organic solvent Substances 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 7
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000008378 aryl ethers Chemical class 0.000 claims description 2
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 claims 1
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- 229920002284 Cellulose triacetate Polymers 0.000 description 9
- 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 9
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- 239000000463 material Substances 0.000 description 3
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- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 2
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- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 2
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- 239000003504 photosensitizing agent Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
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- WKBPZYKAUNRMKP-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)pentyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(CCC)CN1C=NC=N1 WKBPZYKAUNRMKP-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-UHFFFAOYSA-N 0.000 description 1
- LMMGAGCAEGFLMD-UHFFFAOYSA-N 2-(2-methyloxiran-2-yl)ethanol Chemical compound OCCC1(C)CO1 LMMGAGCAEGFLMD-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- WAPRZVXVTPSWEB-UHFFFAOYSA-N 2-[(2-butan-2-ylphenoxy)methyl]oxirane Chemical compound CCC(C)C1=CC=CC=C1OCC1OC1 WAPRZVXVTPSWEB-UHFFFAOYSA-N 0.000 description 1
- BIDWUUDRRVHZLQ-UHFFFAOYSA-N 3-ethyl-3-(2-ethylhexoxymethyl)oxetane Chemical compound CCCCC(CC)COCC1(CC)COC1 BIDWUUDRRVHZLQ-UHFFFAOYSA-N 0.000 description 1
- JUXZNIDKDPLYBY-UHFFFAOYSA-N 3-ethyl-3-(phenoxymethyl)oxetane Chemical compound C=1C=CC=CC=1OCC1(CC)COC1 JUXZNIDKDPLYBY-UHFFFAOYSA-N 0.000 description 1
- LMIOYAVXLAOXJI-UHFFFAOYSA-N 3-ethyl-3-[[4-[(3-ethyloxetan-3-yl)methoxymethyl]phenyl]methoxymethyl]oxetane Chemical compound C=1C=C(COCC2(CC)COC2)C=CC=1COCC1(CC)COC1 LMIOYAVXLAOXJI-UHFFFAOYSA-N 0.000 description 1
- IICCLYANAQEHCI-UHFFFAOYSA-N 4,5,6,7-tetrachloro-3',6'-dihydroxy-2',4',5',7'-tetraiodospiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 IICCLYANAQEHCI-UHFFFAOYSA-N 0.000 description 1
- RGVISJDZLDHPQU-UHFFFAOYSA-N 4-(3-methyloxiran-2-yl)butan-1-ol Chemical compound CC1OC1CCCCO RGVISJDZLDHPQU-UHFFFAOYSA-N 0.000 description 1
- KMHQJKFCDQXYLS-UHFFFAOYSA-N 6-(oxiran-2-yl)hexan-1-ol Chemical compound OCCCCCCC1CO1 KMHQJKFCDQXYLS-UHFFFAOYSA-N 0.000 description 1
- NHJIDZUQMHKGRE-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-yl 2-(7-oxabicyclo[4.1.0]heptan-4-yl)acetate Chemical compound C1CC2OC2CC1OC(=O)CC1CC2OC2CC1 NHJIDZUQMHKGRE-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229940081735 acetylcellulose Drugs 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
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- 101150059062 apln gene Proteins 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- DJUWPHRCMMMSCV-UHFFFAOYSA-N bis(7-oxabicyclo[4.1.0]heptan-4-ylmethyl) hexanedioate Chemical compound C1CC2OC2CC1COC(=O)CCCCC(=O)OCC1CC2OC2CC1 DJUWPHRCMMMSCV-UHFFFAOYSA-N 0.000 description 1
- LMMDJMWIHPEQSJ-UHFFFAOYSA-N bis[(3-methyl-7-oxabicyclo[4.1.0]heptan-4-yl)methyl] hexanedioate Chemical compound C1C2OC2CC(C)C1COC(=O)CCCCC(=O)OCC1CC2OC2CC1C LMMDJMWIHPEQSJ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
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- DNWBGZGLCKETOT-UHFFFAOYSA-N cyclohexane;1,3-dioxane Chemical compound C1CCCCC1.C1COCOC1 DNWBGZGLCKETOT-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
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- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
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- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- KEDGSDIAPIAOGT-UHFFFAOYSA-N triethoxy-[3-[(3-ethyloxetan-2-yl)methoxy]propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1OCC1CC KEDGSDIAPIAOGT-UHFFFAOYSA-N 0.000 description 1
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Images
Description
本発明は、液晶表示装置等に用いられる偏光板及び該偏光板形成用の光硬化性接着剤に関するものである The present invention relates to a polarizing plate used in a liquid crystal display device and the like, and a photocurable adhesive for forming the polarizing plate.
時計、携帯電話、個人用の携帯情報端末（ＰＤＡ）、ノートパソコン、パソコン用モニタ、ＤＶＤプレーヤー、ＴＶなどでは液晶表示装置が急激に市場展開している。液晶表示装置は、液晶のスイッチングによる偏光状態を可視化させたものであり、その表示原理から、偏光板が用いられる。特に、ＴＶ等の用途では、ますます高輝度、高コントラスト、広い視野角が求められ、偏光板においてもますます高透過率、高偏光度、高い色再現性などが求められている。 Liquid crystal display devices are rapidly developing in watches, mobile phones, personal digital assistants (PDAs), notebook computers, personal computer monitors, DVD players, TVs, and the like. The liquid crystal display device visualizes the polarization state by switching of the liquid crystal, and a polarizing plate is used from the display principle. In particular, in applications such as TV, higher brightness, higher contrast, and wider viewing angle are required, and polarizing plates are also required to have higher transmittance, higher degree of polarization, and higher color reproducibility.
液晶表示関連分野などに用いられる偏光板は、ポリビニルアルコール（ＰＶＡ）系偏光フィルムの両面にトリアセチルセルロース（ＴＡＣ）系フィルムを水系接着剤で貼り合せるか、又は片面に保護フィルムもしくは光学補償フィルムとしてポリエステル系樹脂、ポリカーボネート系樹脂、アクリル系樹脂、非結晶性ポリオレフィン系樹脂やシクロオレフィン系樹脂を、もう片面にＴＡＣ系フィルムを水系接着剤で貼り合せて製造されるのが一般的である。 A polarizing plate used in a liquid crystal display-related field or the like is obtained by bonding a triacetyl cellulose (TAC) film on both sides of a polyvinyl alcohol (PVA) polarizing film with a water-based adhesive, or as a protective film or an optical compensation film on one side. In general, the polyester resin, the polycarbonate resin, the acrylic resin, the amorphous polyolefin resin, or the cycloolefin resin is bonded to the other surface of the TAC film with a water-based adhesive.
ＴＡＣ系フィルムは、透湿度が高いことから、水系接着剤を使用し、水分を揮発させることなくそのままＰＶＡ系偏光子フィルムに重ねた状態で、水を乾燥させつつ、接着できる。 Since the TAC-based film has high moisture permeability, it can be adhered to the PVA-based polarizer film using a water-based adhesive and without being evaporated, while drying water.
一方、ポリエステル系樹脂、ポリカーボネート系樹脂、アクリル系樹脂、非結晶性ポリオレフィン系樹脂やシクロオレフィン系樹脂は、ＴＡＣよりも疎水性であることや、透湿度が低いため、ＰＶＡ系偏光子フィルムに重ねる前に水を十分乾燥する必要があるが、水が残り易く、水が残ると、接着強度不足や外観不良などの問題があった。 On the other hand, polyester resins, polycarbonate resins, acrylic resins, non-crystalline polyolefin resins and cycloolefin resins are more hydrophobic than TAC and have low moisture permeability, so they are layered on PVA polarizer films. Although it is necessary to dry the water sufficiently in advance, there are problems such as insufficient adhesion strength and poor appearance when the water remains easily.
上記のような理由から、ＰＶＡ系偏光子フィルムと透湿度が低い保護フィルムとを貼り合せる接着剤として、水系接着剤の代わりに紫外線硬化型接着剤を使用することが提案されている。 For the reasons described above, it has been proposed to use an ultraviolet curable adhesive instead of a water-based adhesive as an adhesive for bonding a PVA polarizer film and a protective film having low moisture permeability.
偏光板を工業的に生産する場合、偏光子の両面に保護フィルムを貼り合わせた長尺の積層体をロール状に巻き取る。その後、ロール状の積層体を巻き戻し、積層体液晶セルのガラス板に偏光板を固定するための粘着剤層が偏光板の一方の面に設けられたり、各種ディスプレイに応じた大きさに裁断されたり等の種々の加工が加えられる。
偏光板がロール状態で保管される時間は様々であるが、保管時に、巻き癖が発生すると、上記したその後の種々の加工の工程における生産性が著しく低下するため、巻き癖の少ない偏光板が求められる。
When producing a polarizing plate industrially, the long laminated body which bonded the protective film on both surfaces of the polarizer is wound up in roll shape. After that, the roll-shaped laminate is rewound, and an adhesive layer for fixing the polarizing plate to the glass plate of the laminated liquid crystal cell is provided on one surface of the polarizing plate, or cut to a size corresponding to various displays. Various kinds of processing such as being done are added.
The time for which the polarizing plate is stored in a roll state varies, but when curling occurs during storage, the productivity in the subsequent various processing steps described above is significantly reduced, so that there is a polarizing plate with little curling. Desired.
特開２００８−６３３９７号公報（特許文献１）には、多官能の脂肪族エポキシ化合物を主成分とする比較的低粘度の接着剤が開示されており、加熱または活性エネルギー線の照射によるカチオン重合による接着法が提案されている。
特許文献１記載の接着剤を用いると、長尺の硬化物を巻取りロール状にした場合、脂肪族エポキシ化合物は硬化性が良くないので、保管時に暗反応が進行し、巻き癖がつきやすいという問題があった。
Japanese Patent Application Laid-Open No. 2008-63397 (Patent Document 1) discloses a relatively low-viscosity adhesive mainly composed of a polyfunctional aliphatic epoxy compound, and cationic polymerization by heating or irradiation with active energy rays. The adhesion method by is proposed.
When the adhesive described in Patent Document 1 is used, when a long cured product is formed into a winding roll shape, the aliphatic epoxy compound is not curable, so a dark reaction proceeds during storage, and curling is likely to occur. There was a problem.
ところで、ＰＶＡ系偏光子と保護フィルムを貼り合わせる接着剤層の厚みは、光の透過率を上げるためや、コストを下げるためにできるだけ薄いことが求められる。具体的には接着剤層は、０．１〜６μｍの厚みで平滑であることが求められる。
このような薄膜の接着剤層を工業的に設けるには、光学接着剤を塗工する際マイクログラビアコーターを用いることが好ましい。小径グラビアコーターは、より細かい凹版を用いることによって薄膜を形成できる。しかし、接着剤の粘度が高いと、可能な限り細かい凹版（例えば５００線／インチ）を用いても、０．１〜６μｍの厚みの接着剤層を形成できない。
従って、０．１〜６μｍの厚みの接着剤層を形成するためには接着剤の粘度を１５０ｍＰａ・ｓ以下にする必要がある。
By the way, the thickness of the adhesive layer that bonds the PVA polarizer and the protective film is required to be as thin as possible in order to increase the light transmittance and to reduce the cost. Specifically, the adhesive layer is required to be smooth with a thickness of 0.1 to 6 μm.
In order to industrially provide such a thin adhesive layer, it is preferable to use a micro gravure coater when applying the optical adhesive. The small-diameter gravure coater can form a thin film by using a finer intaglio. However, when the viscosity of the adhesive is high, an adhesive layer having a thickness of 0.1 to 6 μm cannot be formed even when using an intaglio as fine as possible (for example, 500 lines / inch).
Therefore, in order to form an adhesive layer having a thickness of 0.1 to 6 μm, the viscosity of the adhesive needs to be 150 mPa · s or less.
特開２００４−２４５９２５（特許文献２）には、芳香環を含まないエポキシ樹脂として水素化（水添ともいう）ビスフェノール型エポキシ樹脂を主成分とする接着剤が開示されており、加熱または活性エネルギー線の照射によるカチオン重合による接着法が提案されている。
しかし、特許文献２記載の接着剤は極めて高粘度であり、塗工性に難があった。さらに、水素化（水添ともいう）ビスフェノール型エポキシ樹脂は硬化性が良くないので、保管時に暗反応が進行し、巻き癖がつきやすいという問題もあった。
JP-A-2004-245925 (Patent Document 2) discloses an adhesive mainly composed of a hydrogenated (also referred to as hydrogenated) bisphenol type epoxy resin as an epoxy resin that does not contain an aromatic ring. An adhesion method by cationic polymerization by irradiation of rays has been proposed.
However, the adhesive described in Patent Document 2 has a very high viscosity and has difficulty in coating properties. Furthermore, since hydrogenated (also referred to as hydrogenated) bisphenol-type epoxy resin is not curable, there is a problem that a dark reaction proceeds during storage, and curling tends to occur.
特開２００８−２５７１９９号公報（特許文献３）には、分子内に１個以上の脂環式エポキシ基を有する多官能のエポキシ樹脂と、分子内に脂環式エポキシ基を有さない多官能のエポキシ樹脂を含む接着剤が開示されている。
一般的に脂環式エポキシ樹脂は、光硬化性が良い反面、粘度が２００ｍＰａ・ｓ以上と高い。
一方、脂環式エポキシ基を有しない多官能エポキシ樹脂は、光硬化性は低いが１００ｍＰａ・ｓ以下という低粘度のものがある。
そのため薄膜塗工をするために接着剤粘度を下げようとすると、脂環式エポキシ基を有しない多官能エポキシ樹脂含有量を増やさざるを得ない。しかし、その結果、硬化性が低下し、密着性不良や湿熱暴露するとＰＶＡ系偏光子と保護フィルムの間で剥離が発生する。さらには、脂環式エポキシ基を有しない多官能エポキシ樹脂を増やすと、硬化物中に未反応のエポキシ基が残存するため、長尺の硬化物を巻取りロール状にした場合、保管時に暗反応が進行し、巻き癖がつきやすいという問題があった。
そこで、硬化性を維持しようとすると、脂環式エポキシ樹脂を増やさざるを得なくなる。しかし、この場合、接着剤粘度が上がり、その結果薄膜塗工ができなくなる。
JP 2008-257199 A (Patent Document 3) discloses a polyfunctional epoxy resin having one or more alicyclic epoxy groups in a molecule and a polyfunctional having no alicyclic epoxy groups in the molecule. An adhesive containing the epoxy resin is disclosed.
In general, alicyclic epoxy resins have good photocurability, but have a high viscosity of 200 mPa · s or more.
On the other hand, some polyfunctional epoxy resins not having an alicyclic epoxy group have a low viscosity of 100 mPa · s or less, although the photocurability is low.
Therefore, if it is going to reduce the adhesive viscosity for thin film coating, the content of polyfunctional epoxy resin having no alicyclic epoxy group must be increased. However, as a result, curability is lowered, and peeling occurs between the PVA polarizer and the protective film when exposed to poor adhesion or exposed to wet heat. Furthermore, increasing the number of polyfunctional epoxy resins not having an alicyclic epoxy group leaves unreacted epoxy groups in the cured product. There was a problem that the reaction progressed and the curl was easy to stick.
Then, if it is going to maintain sclerosis | hardenability, an alicyclic epoxy resin must be increased. However, in this case, the viscosity of the adhesive increases, and as a result, thin film coating cannot be performed.
なお、接着剤の粘度を低下させるために、有機溶剤を用いて希釈するという方法がある。しかし、有機溶剤を用いると、塗工設備を防爆仕様にしたり、特別な溶剤回収装置を設置したりしなければならなくなる。
そこで、偏光板形成用の光硬化性接着剤には、実質的に有機溶剤を含有しない状態で低粘度であることが求められる。
In order to reduce the viscosity of the adhesive, there is a method of diluting with an organic solvent. However, if an organic solvent is used, it is necessary to make the coating equipment explosion-proof or install a special solvent recovery device.
Therefore, a photocurable adhesive for forming a polarizing plate is required to have a low viscosity in a state that does not substantially contain an organic solvent.
本発明は、ポリビニルアルコール系偏光子と保護フィルムとを簡便かつ強固に接着できる有機溶剤を実質的に含まず、低粘度で薄膜塗工性に優れる光硬化型接着剤、及びそれを用いて、従来の偏光板に比して打抜き加工性、湿熱耐性及び巻き癖に優れた偏光板を提供することを目的とする。 The present invention substantially does not contain an organic solvent capable of easily and firmly bonding a polyvinyl alcohol polarizer and a protective film, and uses a photocurable adhesive having a low viscosity and excellent thin film coatability, and using it, An object of the present invention is to provide a polarizing plate excellent in punching processability, wet heat resistance and curling habit as compared with a conventional polarizing plate.
本発明者らは前記課題を解決すべく鋭意検討を重ねた結果、以下に示す活性エネルギー線硬化型接着性組成物により前記目標達成できることを見出し、本発明を完成するに至った。
すなわち、本発明は、ポリビニルアルコール系偏光子の両面が、光硬化性接着剤を硬化してなる接着層を介して保護フィルムでそれぞれ被覆されてなる偏光板であって、
前記光硬化性接着剤が、
多官能脂環式エポキシ化合物（Ａ）と単官能グリシジル化合物（Ｂ）とを含むカチオン重合性成分及び光重合開始剤を含有する光硬化性接着剤であって、
前記カチオン重合性成分１００重量％中に、前記多官能脂環式エポキシ化合物（Ａ）を５０重量％以上含み、
前記カチオン重合性成分１００重量部中に、前記単官能グリシジル化合物（Ｂ）由来のエポキシ基を０．０１〜０．２個含み、
実質的に有機溶剤を含有せず、粘度が１０〜１５０ｍＰａ・ｓである、ことを特徴とする光硬化性接着剤に関する。
As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned target can be achieved by the active energy ray-curable adhesive composition shown below, and have completed the present invention.
That is, the present invention is a polarizing plate in which both sides of a polyvinyl alcohol polarizer are respectively covered with a protective film via an adhesive layer formed by curing a photocurable adhesive,
The photo-curable adhesive is
A photocurable adhesive comprising a cationic polymerizable component comprising a polyfunctional alicyclic epoxy compound (A) and a monofunctional glycidyl compound (B) and a photopolymerization initiator,
The polyfunctional alicyclic epoxy compound (A) is contained in 50% by weight or more in 100% by weight of the cationic polymerizable component,
In 100 parts by weight of the cationic polymerizable component, 0.01 to 0.2 epoxy groups derived from the monofunctional glycidyl compound (B) are included,
It is related with the photocurable adhesive agent characterized by not containing an organic solvent substantially and having a viscosity of 10-150 mPa * s.
また、本発明は、ポリビニルアルコール系偏光子の両面が、光硬化性接着剤を硬化してなる接着層を介して保護フィルムでそれぞれ被覆されてなる偏光板であって、
前記光硬化性接着剤が、
多官能脂環式エポキシ化合物（Ａ）と単官能グリシジル化合物（Ｂ）とを含むカチオン重合性成分及び光重合開始剤を含有する光硬化性接着剤であって、
前記カチオン重合性成分１００重量％中に、前記多官能脂環式エポキシ化合物（Ａ）を５０重量％以上含み、
前記カチオン重合性成分１００重量部中に、前記単官能グリシジル化合物（Ｂ）由来のエポキシ基を０．０１〜０．２個含み、
実質的に有機溶剤を含有せず、粘度が１０〜１５０ｍＰａ・ｓである、ことを特徴とする偏光板に関する。
Moreover, the present invention is a polarizing plate in which both sides of a polyvinyl alcohol polarizer are respectively covered with a protective film via an adhesive layer formed by curing a photocurable adhesive,
The photo-curable adhesive is
A photocurable adhesive comprising a cationic polymerizable component comprising a polyfunctional alicyclic epoxy compound (A) and a monofunctional glycidyl compound (B) and a photopolymerization initiator,
The polyfunctional alicyclic epoxy compound (A) is contained in 50% by weight or more in 100% by weight of the cationic polymerizable component,
In 100 parts by weight of the cationic polymerizable component, 0.01 to 0.2 epoxy groups derived from the monofunctional glycidyl compound (B) are included,
It is related with the polarizing plate characterized by not containing an organic solvent substantially and having a viscosity of 10-150 mPa * s.
本発明により、ポリビニルアルコール系偏光子と保護フィルムとを簡便かつ強固に接着できる光硬化型接着剤であって、実質的に有機溶剤を含まず、低粘度で薄膜塗工性に優れる光硬化型接着剤、及びそれを用いて、従来の偏光板に比して打抜き加工性、湿熱耐性及び巻き癖に優れた偏光板を提供することを目的とする。 According to the present invention, a photocurable adhesive capable of easily and firmly bonding a polyvinyl alcohol polarizer and a protective film, which is substantially free of organic solvent, has a low viscosity, and is excellent in thin film coatability. It aims at providing the polarizing plate which was excellent in punching workability, wet heat resistance, and curling wrinkles compared with the conventional polarizing plate using an adhesive agent and it.
本発明の偏光板を構成する接着層について説明する。
接着層は、光硬化性接着剤を硬化してなるものである。
本発明の光硬化性接着剤は、多官能脂環式エポキシ化合物（Ａ）と単官能グリシジル化合物（Ｂ）とを含むカチオン重合性成分及び光重合開始剤を含有する光硬化性接着剤であって、
前記カチオン重合性成分１００重量％中に、前記多官能脂環式エポキシ化合物（Ａ）を５０重量％以上含み、
前記カチオン重合性成分１００重量％中に、前記単官能グリシジル化合物（Ｂ）由来のエポキシ基を０．０１〜０．２個含有する。
The adhesive layer constituting the polarizing plate of the present invention will be described.
The adhesive layer is formed by curing a photocurable adhesive.
The photocurable adhesive of the present invention is a photocurable adhesive containing a cationic polymerizable component containing a polyfunctional alicyclic epoxy compound (A) and a monofunctional glycidyl compound (B) and a photopolymerization initiator. And
The polyfunctional alicyclic epoxy compound (A) is contained in 50% by weight or more in 100% by weight of the cationic polymerizable component,
0.01 to 0.2 epoxy groups derived from the monofunctional glycidyl compound (B) are contained in 100% by weight of the cationic polymerizable component.
多官能脂環式エポキシ化合物（Ａ）とは脂環構造に直接結合したエポキシ基を２個以上有するエポキシ化合物で、例えば、
３，４−エポキシシクロヘキシルメチル−３，４−エポキシシクロヘキサンカルボキシレート、２−（３，４−エポキシシクロヘキシル−５，５−スピロ−３，４−エポキシ）シクロヘキサン−メタ−ジオキサン、ビス（３，４−エポキシシクロヘキシルメチル）アジペート、ビス（３，４−エポキシ−６−メチルシクロヘキシルメチル）アジペートなどが挙げられる。
本発明における光硬化性接着剤は、これらの材料を適宜組み合わせて使うことができる。
The polyfunctional alicyclic epoxy compound (A) is an epoxy compound having two or more epoxy groups directly bonded to the alicyclic structure.
3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4 -Epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate and the like.
The photocurable adhesive in the present invention can be used by appropriately combining these materials.
本発明の光硬化性接着剤は、多官能脂環式エポキシ化合物（Ａ）と単官能グリシジル化合物（Ｂ）とを合計１００重量％とした場合、前記カチオン重合性成分１００重量％中に、前記多官能脂環式エポキシ化合物（Ａ）を５０重量％以上含む。前記多官能脂環式エポキシ化合物（Ａ）は、５０重量％〜９５重量％であることが好ましく、５５重量％〜８５重量％であることがより好ましい。
多官能脂環式エポキシ化合物（Ａ）が５０重量％よりも少ないと、接着力を確保できないばかりでなく、打抜き加工性が悪くなってしまう。一方、多官能脂環式エポキシ化合物（Ａ）が多くなりすぎると、光硬化性接着剤が高粘度となり、薄膜塗工性が確保できない。
なお、多官能脂環式エポキシ化合物（Ａ）としては、粘度が２０００ｍＰａ・ｓ以上のものが多く、１５０〜１０００ｍＰａ・ｓのものが多い。
When the polyfunctional alicyclic epoxy compound (A) and the monofunctional glycidyl compound (B) are 100% by weight in total, the photocurable adhesive of the present invention contains 100% by weight of the cationic polymerizable component, 50 weight% or more of polyfunctional alicyclic epoxy compounds (A) are included. The polyfunctional alicyclic epoxy compound (A) is preferably 50% by weight to 95% by weight, and more preferably 55% by weight to 85% by weight.
When the polyfunctional alicyclic epoxy compound (A) is less than 50% by weight, not only the adhesive strength cannot be secured but also the punching processability is deteriorated. On the other hand, when the polyfunctional alicyclic epoxy compound (A) is too much, the photocurable adhesive has a high viscosity and the thin film coatability cannot be ensured.
In addition, as a polyfunctional alicyclic epoxy compound (A), there are many things with a viscosity of 2000 mPa * s or more, and there are many things of 150-1000 mPa * s.
単官能グリシジル化合物（Ｂ）とは、次式（１）に示すグリシジル基を1個有する化合物である。 The monofunctional glycidyl compound (B) is a compound having one glycidyl group represented by the following formula (1).
例えば、脂肪族アルコールのグリシジルエーテルやフェノール性水酸基含有化合物のグリシジルエーテル、グリコール化合物のグリシジルエーテル、アルキルカルボン酸のグリシジルエステル、芳香環含有カルボン酸のグリシジルエステルなどが挙げられる。
具体例としては、アリルグリシジルエーテル、ブチルグリシジルエーテル、Ｏ‐ｓｅｃ‐ブチルフェニルグリシジルエーテル、２エチルヘキシルグリシジルエーテル、Ｃ１２〜１３混合アルキルグリシジルエーテル、フェニルグリシジルエーテル、３‐メチル‐３，４‐エポキシブタン‐１‐オール、５，６‐エポキシ‐１‐ヘプタノール、７，８‐エポキシ‐１‐オクタノール、などが挙げられる。
本発明における光硬化性接着剤は、これらの材料を適宜組み合わせて使うことができる。
なお、単官能エポキシ化合物（Ｂ）としては、粘度が２０ｍＰａ・ｓ以下のものが好ましく、１〜１０ｍＰａ・ｓのものが好ましい。
Examples include glycidyl ethers of aliphatic alcohols, glycidyl ethers of phenolic hydroxyl group-containing compounds, glycidyl ethers of glycol compounds, glycidyl esters of alkyl carboxylic acids, glycidyl esters of carboxylic acid containing aromatic rings, and the like.
Specific examples include allyl glycidyl ether, butyl glycidyl ether, O-sec-butylphenyl glycidyl ether, 2-ethylhexyl glycidyl ether, C 12 ~ 13 mixed alkyl glycidyl ether, phenyl glycidyl ether, 3-methyl-3,4-epoxy butane -1-ol, 5,6-epoxy-1-heptanol, 7,8-epoxy-1-octanol, and the like.
The photocurable adhesive in the present invention can be used by appropriately combining these materials.
In addition, as a monofunctional epoxy compound (B), a viscosity is 20 mPa * s or less, and a thing of 1-10 mPa * s is preferable.
一般に、光カチオン重合反応は水酸基による反応阻害を受けると考えられている。したがって、本発明では前記単官能グリシジル化合物（Ｂ）のうち、水酸基を有さないものを使用することが好ましい。 In general, it is considered that the photocationic polymerization reaction is inhibited by a hydroxyl group. Therefore, in the present invention, it is preferable to use a monofunctional glycidyl compound (B) that does not have a hydroxyl group.
また、エポキシ当量が大きくなると粘度が大きくなる傾向にあるので、単官能グリシジル化合物（Ｂ）としては、エポキシ当量が１００〜３００（ｇ／ｅｑ）程度のものが好ましい。
単官能グリシジル化合物（Ｂ）は、カチオン重合性成分１００重量部中に、単官能グリシジル化合物（Ｂ）由来のエポキシ基が０．０１〜０．２個となる範囲で含まれ、エポキシ基が０．０５〜０．２個となる範囲で含まれることが好ましい。
単官能グリシジル化合物（Ｂ）由来のエポキシ基が０．０１個未満、即ち、単官能グリシジル化合物（Ｂ）がほとんど含まれていないと、粘度低下効果がほとんど期待できない。一方、単官能グリシジル化合物（Ｂ）由来のエポキシ基が０．２個よりも多い、即ち、単官能グリシジル化合物（Ｂ）の含有量が多すぎると、硬化性が低下し、巻き癖を満足できない。
Moreover, since the viscosity tends to increase as the epoxy equivalent increases, the monofunctional glycidyl compound (B) preferably has an epoxy equivalent of about 100 to 300 (g / eq).
The monofunctional glycidyl compound (B) is contained in an amount of 0.01 to 0.2 epoxy groups derived from the monofunctional glycidyl compound (B) in 100 parts by weight of the cationic polymerizable component, and the epoxy group is 0. It is preferably included in the range of 0.05 to 0.2.
When the number of epoxy groups derived from the monofunctional glycidyl compound (B) is less than 0.01, that is, when the monofunctional glycidyl compound (B) is hardly contained, the effect of reducing the viscosity can hardly be expected. On the other hand, if there are more than 0.2 epoxy groups derived from the monofunctional glycidyl compound (B), that is, if the content of the monofunctional glycidyl compound (B) is too large, curability is lowered and curling habits cannot be satisfied. .
光硬化性接着剤は、上記単官能グリシジル化合物（Ｂ）に加え、脂環式以外の多官能グリシジル化合物（Ｄ）を、必要に応じて、本発明の効果を阻害しない範囲内で含むことができる。換言すると、脂肪族エポキシ化合物を併用することもできるが、その場合は、主剤（１００重量％とする）中に３０重量％未満程度、好ましくは５重量％未満程度に抑える必要がある。
なお、脂環式以外の多官能グリシジル化合物（Ｄ）の中には、多官能脂環式エポキシ化合物（Ａ）に比して比較的低粘度のものもある。しかし、前記単官能グリシジル化合物（Ｂ）の代わりに前記多官能グリシジル化合物（Ｄ）を、前記多官能グリシジル化合物（Ｄ）エポキシ基が０．０１〜０．２個となる範囲で用いても、粘度低下が不十分で薄膜塗工性が確保できなかったり、硬化性が低下し、巻き癖が大きくなったりする。
In addition to the monofunctional glycidyl compound (B), the photocurable adhesive may contain a polyfunctional glycidyl compound (D) other than the alicyclic type as long as it does not inhibit the effects of the present invention. it can. In other words, an aliphatic epoxy compound can be used in combination, but in that case, it is necessary to suppress it to less than 30% by weight, preferably less than 5% by weight in the main agent (100% by weight).
In addition, some polyfunctional glycidyl compounds (D) other than alicyclic compounds have relatively low viscosities as compared with polyfunctional alicyclic epoxy compounds (A). However, instead of the monofunctional glycidyl compound (B), the polyfunctional glycidyl compound (D) may be used in the range where the polyfunctional glycidyl compound (D) epoxy group is 0.01 to 0.2, Insufficient decrease in viscosity cannot ensure thin film coatability, curability decreases, and curl becomes large.
本発明における光硬化性接着剤は、多官能脂環式エポキシ化合物（Ａ）と単官能グリシジル化合物（Ｂ）に加え、粘度調整や硬化性を上げるためオキセタン化合物（Ｃ）を含むことができる。オキセタン化合物（Ｃ）は、分子内に４員環エーテル、すなわちオキセタン環を有する化合物である。オキセタン化合物（Ｃ）としては、粘度が３００ｍＰａ・ｓ以下のものが好ましく、１〜２００ｍＰａ・ｓのものが好ましい。
本発明に用いるオキセタン化合物（Ｃ）としては、例えば、
３-エチル‐３‐ヒドロキシメチルオキセタン、１，４‐ビス[（３‐エチル‐３‐オキセタニル）メトキシメチル]ベンゼン、３-エチル‐３‐（フェノキシメチル）オキセタン、ジ（１‐エチル‐３‐オキセタニル）メチルエーテル、３-エチル‐３‐（２‐エチルヘキシロキシメチル）オキセタン、フェノールノボラックオキセタン、３‐エチル‐｛（３‐トリエトキシシリルプロポキシ）メチル｝オキセタン、などが挙げられる。
なお、オキセタン化合物（Ｃ）が水酸基を有していたとしても、オキセタンによる硬化性促進効果の方が顕著なので、単官能グリシジル化合物（Ｂ）とは異なり反応阻害の影響は極めて小さい。
In addition to the polyfunctional alicyclic epoxy compound (A) and the monofunctional glycidyl compound (B), the photocurable adhesive in the present invention can contain an oxetane compound (C) in order to increase viscosity adjustment and curability. The oxetane compound (C) is a compound having a 4-membered ring ether, that is, an oxetane ring in the molecule. The oxetane compound (C) preferably has a viscosity of 300 mPa · s or less, more preferably 1 to 200 mPa · s.
As the oxetane compound (C) used in the present invention, for example,
3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, 3-ethyl-3- (phenoxymethyl) oxetane, di (1-ethyl-3- Oxetanyl) methyl ether, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, phenol novolac oxetane, 3-ethyl-{(3-triethoxysilylpropoxy) methyl} oxetane, and the like.
In addition, even if the oxetane compound (C) has a hydroxyl group, the effect of reaction inhibition is extremely small unlike the monofunctional glycidyl compound (B) because the effect of promoting hardening by oxetane is more remarkable.
前記オキセタン化合物（Ｃ）を用いる場合には、カチオン重合性成分１００重量％中に、１〜４０重量％含むことが好ましく、３〜３５重量％であることがより好ましい。 When using the said oxetane compound (C), it is preferable to contain 1-40 weight% in 100 weight% of cationically polymerizable components, and it is more preferable that it is 3-35 weight%.
本発明における光硬化性接着剤は、光カチオン重合開始剤（Ｅ）を含む。
光カチオン重合開始剤（Ｅ）としては、例えばＵＶＡＣＵＲＥ１５９０（ダイセル・サイテック製）、ＣＰＩ−１１０Ｐ（サンアプロ製）、などのスルホニウム塩やＩＲＧＡＣＵＲＥ２５０（チバ・スペシャルティ・ケミカルズ製）、ＷＰＩ−１１３（和光純薬製）、Ｒｐ−２０７４（ローディア・ジャパン製）等のヨードニウム塩が挙げられるが、これらに限定されるものではない。
光カチオン重合開始剤（Ｅ）の配合割合は、カチオン重合性成分、即ち、オキセタン化合物（Ｃ）を用いない場合には、多官能脂環式エポキシ化合物（Ａ）と単官能グリシジル化合物（Ｂ）との合計１００重量部に対して、オキセタン化合物（Ｃ）を用いる場合には、多官能脂環式エポキシ化合物（Ａ）と単官能グリシジル化合物（Ｂ）及びオキセタン化合物（Ｃ）の合計１００重量部に対して、０．５〜２０重量部であり、０．５〜１０重量部であることが好ましい。
The photocurable adhesive in the present invention contains a photocationic polymerization initiator (E).
Examples of the cationic photopolymerization initiator (E) include sulfonium salts such as UVACURE1590 (manufactured by Daicel Cytec) and CPI-110P (manufactured by San Apro), IRGACURE250 (manufactured by Ciba Specialty Chemicals), and WPI-113 (Wako Pure Chemical Industries). And iodonium salts such as Rp-2074 (manufactured by Rhodia Japan), but are not limited thereto.
The proportion of the photocationic polymerization initiator (E) is such that when the cationic polymerizable component, that is, the oxetane compound (C) is not used, the polyfunctional alicyclic epoxy compound (A) and the monofunctional glycidyl compound (B). When the oxetane compound (C) is used with respect to a total of 100 parts by weight, the total of 100 parts by weight of the polyfunctional alicyclic epoxy compound (A), the monofunctional glycidyl compound (B) and the oxetane compound (C) Is 0.5 to 20 parts by weight, and preferably 0.5 to 10 parts by weight.
更に、本発明においては上記光カチオン重合開始剤（Ｅ）の性能を向上させるために、光増感剤（Ｆ）を併用しても良い。光増感剤としては、アントラセン系やベンゾフェノン系、チオキサントン系やペリレン、フェノチアジン、ローズベンガル等が挙げられる。 Furthermore, in this invention, in order to improve the performance of the said photocationic polymerization initiator (E), you may use a photosensitizer (F) together. Examples of the photosensitizer include anthracene series, benzophenone series, thioxanthone series, perylene, phenothiazine, and rose bengal.
光硬化性接着剤は、上記カチオン重合性成分及び重合開始剤に加え、重合禁止剤、重合開始助剤、紫外線吸収剤、可塑剤、着色剤、酸化防止剤、消泡剤、可塑剤等の各種の公知の添加剤を、必要に応じて、本発明の効果を阻害しない範囲内で含むことができる。 In addition to the cationic polymerizable component and the polymerization initiator, the photocurable adhesive includes a polymerization inhibitor, a polymerization initiation assistant, an ultraviolet absorber, a plasticizer, a colorant, an antioxidant, an antifoaming agent, a plasticizer, and the like. Various known additives can be included within the range that does not impair the effects of the present invention, if necessary.
本発明における光硬化性接着剤は、実質的に有機溶剤を含まず、粘度は１０〜１５０ｍＰａ・ｓであることが重要であり、好ましくは１５〜１３０ｍＰａ・ｓであり、２０〜９０ｍＰａ・ｓであることがより好ましい。粘度が１５０ｍＰａ・ｓより高いと保護フィルムに塗工した場合、０．１〜６μｍの薄膜塗工ができず、透過率等の光学的特性が悪化してしまう。一方、粘度が１ｍＰａ・ｓより低いと接着剤層の膜厚制御が困難になる。 It is important that the photocurable adhesive in the present invention contains substantially no organic solvent and has a viscosity of 10 to 150 mPa · s, preferably 15 to 130 mPa · s, and 20 to 90 mPa · s. More preferably. When the viscosity is higher than 150 mPa · s, a thin film having a thickness of 0.1 to 6 μm cannot be applied to the protective film, and optical characteristics such as transmittance are deteriorated. On the other hand, when the viscosity is lower than 1 mPa · s, it is difficult to control the thickness of the adhesive layer.
なお、前記の光硬化性接着剤の粘度は、以下のようにして求められる値である。 光硬化性接着剤１．２ｍｌを測定用試料とし、Ｅ型粘度計を用いて、回転速度１００〜０．５ｒｐｍ、２５℃で測定した。 In addition, the viscosity of the said photocurable adhesive is a value calculated | required as follows. 1.2 ml of photocurable adhesive was used as a measurement sample, and measurement was performed using an E-type viscometer at a rotation speed of 100 to 0.5 rpm and 25 ° C.
本発明の光硬化性接着剤は、実質的に有機溶剤を含まない。有機溶剤を全く含まないほうが好ましいが、光重合開始剤はカチオン重合性成分に難溶性のことが多い。そのため光重合開始剤を溶解するための有機溶剤は含んでもよい。光硬化性接着剤中の有機溶剤の含有量は５重量％以内である。 The photocurable adhesive of the present invention contains substantially no organic solvent. Although it is preferable that no organic solvent is contained, the photopolymerization initiator is often poorly soluble in the cationic polymerizable component. Therefore, an organic solvent for dissolving the photopolymerization initiator may be included. The content of the organic solvent in the photocurable adhesive is within 5% by weight.
光硬化性接着剤を硬化してなる接着層の厚みは０．１〜６μｍが好ましく、０．５〜４μｍがより好ましい。０．１μｍよりも薄くなると接着力が低くなる。６μｍよりも厚くなると光の透過率等の光学特性が悪化する。 0.1-6 micrometers is preferable and, as for the thickness of the contact bonding layer formed by hardening | curing a photocurable adhesive agent, 0.5-4 micrometers is more preferable. When it becomes thinner than 0.1 μm, the adhesive strength is lowered. If it is thicker than 6 μm, optical characteristics such as light transmittance deteriorate.
光硬化性接着剤の塗布方法としては、特に限定されないが、例えばダイコート法、ロールコート法、グラビアコート法、小径グラビアコート法、スピンコート法などが挙げられ、薄膜塗工の点からグラビアコート法が好ましい。更に、グラビアコート法の中でも小径グラビアコート法が好ましい。 The method for applying the photocurable adhesive is not particularly limited, and examples thereof include a die coating method, a roll coating method, a gravure coating method, a small-diameter gravure coating method, a spin coating method, and the gravure coating method from the viewpoint of thin film coating. Is preferred. Further, among the gravure coating methods, the small diameter gravure coating method is preferable.
本発明の光硬化性接着剤は実質的に有機溶剤を含有していないため、塗工膜厚が硬化後の膜厚になる。
接着層の膜厚を制御する方法として、機械的方法としては、
・グラビア方式：使用する版のセル（凹部）容積を小さくする、
・ダイコート方式:塗工機のヘッド部（接着剤の塗出部）と基材フィルムのギャップを狭くする、
・スピンコート方式：回転数を上げる、
等の方法が挙げられるが、いずれの方式も塗工膜厚と接着剤粘度は密接な関係があり、０．１〜６μｍのような薄膜を得るためには接着剤の粘度が１５０ｍＰａ・ｓ以下である必要がある。接着剤の粘度が１５０ｍＰａ・ｓより高くなるとどのような機械的方法を施しても膜厚は６μｍより厚くなる。
Since the photocurable adhesive of the present invention contains substantially no organic solvent, the coating film thickness becomes the film thickness after curing.
As a method of controlling the film thickness of the adhesive layer, as a mechanical method,
-Gravure method: reduce the volume of the plate cell (concave) used,
・ Die coating method: Narrow the gap between the coating machine head (adhesive coating) and the base film.
・ Spin coating method: Increase the number of revolutions,
In any method, there is a close relationship between the coating film thickness and the adhesive viscosity, and in order to obtain a thin film of 0.1 to 6 μm, the adhesive viscosity is 150 mPa · s or less. Need to be. When the viscosity of the adhesive is higher than 150 mPa · s, the film thickness becomes thicker than 6 μm regardless of any mechanical method.
［偏光子］
本発明の偏光板に用いられるポリビニルアルコール系偏光子について説明する。
偏光子を形成するポリビニルアルコール系樹脂としては、ポリビニルアルコール、エチレン・ビニルアルコール共重合体などが挙げられるが、耐水性の点から、エチレン・ビニルアルコール共重合体が好ましい。ポリビニルアルコールとしては、酢酸基が数十％残存している部分ケン化ポリビニルアルコールや、酢酸基が残存しない完全ケン化ポリビニルアルコールや、水酸基が変性された変性ポリビニルアルコールなどが挙げられるが、特に限定されるものではない。ポリビニルアルコール系樹脂は、１種単独で使用することも、あるいは２種以上を併用することもできる。
[Polarizer]
The polyvinyl alcohol-type polarizer used for the polarizing plate of this invention is demonstrated.
Examples of the polyvinyl alcohol-based resin that forms the polarizer include polyvinyl alcohol and ethylene / vinyl alcohol copolymer. From the viewpoint of water resistance, an ethylene / vinyl alcohol copolymer is preferable. Examples of polyvinyl alcohol include partially saponified polyvinyl alcohol in which several tens of percent of acetate groups remain, fully saponified polyvinyl alcohol in which acetate groups do not remain, and modified polyvinyl alcohol in which hydroxyl groups have been modified. Is not to be done. A polyvinyl alcohol-type resin can be used individually by 1 type, or can also use 2 or more types together.
上記ポリビニルアルコールの具体例としては、（株）クラレ製のＲＳポリマーであるＲＳ−１１０（ケン化度＝９９％、重合度＝１，０００）、同社製のクラレポバールＬＭ−２０ＳＯ（ケン化度＝４０％、重合度＝２，０００）、日本合成化学工業（株）製のゴーセノールＮＭ−１４（ケン化度＝９９％、重合度＝１．４００）などが挙げられる。ポリビニルアルコールは、例えば、酢酸ビニル、プロピオン酸ビニル、ピバリン酸ビニル等の脂肪酸ビニルエステルの重合体を、アルカリ触媒等を用いてケン化して得られる。 Specific examples of the polyvinyl alcohol include RS-110 (degree of saponification = 99%, degree of polymerization = 1,000) manufactured by Kuraray Co., Ltd., and Kuraray Poval LM-20SO (degree of saponification) manufactured by the same company. = 40%, polymerization degree = 2,000), Gohsenol NM-14 manufactured by Nippon Synthetic Chemical Industry Co., Ltd. (degree of saponification = 99%, polymerization degree = 1.400), and the like. Polyvinyl alcohol is obtained, for example, by saponifying a polymer of a fatty acid vinyl ester such as vinyl acetate, vinyl propionate or vinyl pivalate using an alkali catalyst or the like.
上記エチレン・ビニルアルコール共重合体は、エチレンと酢酸ビニルとの共重合体のケン化物、すなわち、エチレン−酢酸ビニルランダム共重合体をケン化して得られるものであり、酢酸基が数十モル％残存している部分ケン化物から、酢酸基が数モル％しか残存していないかまたは酢酸基が残存しない完全ケン化物まで含み、特に限定されない。 The ethylene-vinyl alcohol copolymer is obtained by saponifying a copolymer of ethylene and vinyl acetate, that is, an ethylene-vinyl acetate random copolymer, and has an acetate group of several tens mol%. The remaining saponified product is not particularly limited, and includes a partially saponified product in which only a few mol% of acetic acid groups remain or no acetic acid group remains.
偏光子は、上述のポリビニルアルコール系樹脂をキャスティング成形法等の方法によって、成形することにより得られる。前記偏光子は、ホウ酸等による架橋や、延伸をされたものであってもよい。偏光子の形状としては、特に限定されないが、例えば、フィルム等が挙げられる。なお、本明細書において、「フィルム」の語は、厚みが小さいもの（厚みが１ｍｍ未満のもの）の他、厚手のシート（例えば、厚みが１〜５ｍｍのもの）も含むものとする。偏光子の厚さは、特に限定されないが、例えば、１０〜４０μｍ程度が好ましい。 The polarizer is obtained by molding the polyvinyl alcohol-based resin described above by a method such as a casting molding method. The polarizer may be cross-linked or stretched with boric acid or the like. Although it does not specifically limit as a shape of a polarizer, For example, a film etc. are mentioned. In this specification, the term “film” includes not only a sheet having a small thickness (thickness of less than 1 mm) but also a thick sheet (for example, having a thickness of 1 to 5 mm). Although the thickness of a polarizer is not specifically limited, For example, about 10-40 micrometers is preferable.
[保護フィルム]
本発明の偏光板に用いられる保護フィルムについて説明する。
保護フィルムは特に限定されず、具体的には、現在偏光板の保護フィルムとして最も広く用いられているトリアセチルセルロース等のアセチルセルロース系樹脂フィルムや、トリアセチルセルロースよりも透湿度の低い透明樹脂フィルムを用いることができる。
トリアセチルセルロースよりも透湿度の低い保護フィルムを構成する材料としては、例えば透明性、機械的強度、熱安定性、水分遮断性、等方性などに優れる熱可塑性樹脂が用いられる。このような熱可塑性樹脂の具体例としては、シクロオレフィン系樹脂、アクリル系樹脂が挙げられる。
[Protective film]
The protective film used for the polarizing plate of this invention is demonstrated.
The protective film is not particularly limited, and specifically, acetylcellulose-based resin films such as triacetylcellulose, which are currently most widely used as protective films for polarizing plates, and transparent resin films having lower moisture permeability than triacetylcellulose. Can be used.
As a material constituting the protective film having a moisture permeability lower than that of triacetyl cellulose, for example, a thermoplastic resin excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like is used. Specific examples of such thermoplastic resins include cycloolefin resins and acrylic resins.
シクロオレフィン系樹脂は、環状オレフィンを重合単位として重合される樹脂の総称である。具体例としては、環状オレフィンの開環（共）重合体、環状オレフィンの付加重合体、環状オレフィンとエチレン、プロピレン等のα−オレフィンとその共重合体（代表的にはランダム共重合体）、及び、これらを不飽和カルボン酸やその誘導体で変性したグラフト重合体、ならびに、それらの水素化物などが挙げられ、ノルボルネン系樹脂が好ましい。ノルボルネン系樹脂フィルムは、特開２００５−１６４６３２号公報、特開２００６−２０１７３６号公報、特開２００８−２３３２７９号公報等に記載された公知の方法により得ることができる。 The cycloolefin-based resin is a general term for resins that are polymerized using a cyclic olefin as a polymerization unit. Specific examples include ring-opening (co) polymers of cyclic olefins, addition polymers of cyclic olefins, cyclic olefins and α-olefins such as ethylene and propylene (typically random copolymers), And the graft polymer which modified these with unsaturated carboxylic acid or its derivative (s), those hydrides, etc. are mentioned, Norbornene-type resin is preferable. The norbornene resin film can be obtained by a known method described in JP-A No. 2005-164632, JP-A No. 2006-201736, JP-A No. 2008-233279, and the like.
シクロオレフィン系樹脂としては、種々の製品が市販されている。具体例としては、日本ゼオン株式会社製の商品名「ゼオノア」、ＪＳＲ株式会社製の商品名「アートン」、ＴＩＣＯＮＡ社製の商品名「トーパス」、三井化学株式会社製の商品名「ＡＰＥＬ」が挙げられる。 Various products are commercially available as cycloolefin resins. Specific examples include the product name “ZEONOR” manufactured by ZEON CORPORATION, the product name “ARTON” manufactured by JSR Corporation, the product name “TOPAS” manufactured by TICONA, and the product name “APEL” manufactured by Mitsui Chemicals, Inc. Can be mentioned.
保護フィルムの厚さは、適宜に決定しうるが、一般には強度や取扱性等の作業性、薄層性などの点より１〜５００μｍ程度である。特に１〜３００μｍが好ましく、５〜２００μｍがより好ましい。透明保護フィルムは、５〜１５０μｍの場合に特に好適である。
なお、偏光子の両側に保護フィルムを設ける場合、その表裏で同じポリマー材料からなる保護フィルムを用いてもよく、異なるポリマー材料等からなる保護フィルムを用いてもよい。
Although the thickness of a protective film can be determined suitably, generally it is about 1-500 micrometers from points, such as workability | operativity, such as intensity | strength and handleability, and thin layer property. 1-300 micrometers is especially preferable, and 5-200 micrometers is more preferable. The transparent protective film is particularly suitable when the thickness is 5 to 150 μm.
In addition, when providing a protective film in the both sides of a polarizer, the protective film which consists of the same polymer material may be used by the front and back, and the protective film which consists of a different polymer material etc. may be used.
本発明の偏光板は、以下のようにして得ることができる。
（Ｉ）第１の保護フィルム（１）の一方の面に、光硬化性接着剤を塗工し、第１の硬化性接着剤層（２’）を形成し、
第２の保護フィルム（５）の一方の面に、光硬化性接着剤を塗工し、第２の硬化性接着剤層（４’）を形成し、
次いで、ポリビニルアルコール系偏光子（３）の各面に、第１の硬化性接着剤層（２’）及び第２の硬化性接着剤層（４’）を、同時に／または順番に重ね合わせた後、活性エネルギー線を照射し、第１の硬化性接着剤層（２’）及び第２の硬化性接着剤層（４’）を硬化することによって製造する方法。
（II）ポリビニルアルコール系偏光子（３）の一方の面に、光硬化性接着剤を塗工し、第１の硬化性接着剤層（２’）を形成し、形成された第１の硬化性接着剤層（２’）の表面を第１の保護フィルム（１）で覆い、次いでポリビニルアルコール系偏光子（３）の他方の面に、光硬化性接着剤を塗工し、第２の硬化性接着剤層（４’）を形成し、形成された第２の硬化性接着剤層（４’）の表面を第２の保護フィルム（２）で覆い、活性エネルギー線を照射し、第１の硬化性接着剤層（２’）及び第２の硬化性接着剤層（４’）を硬化することによって製造する方法。
（III）第１の保護フィルム（１）とポリビニルアルコール系偏光子（３）との間、および第２の保護フィルム（５）とポリビニルアルコール系偏光子（３）との間に、それぞれ接着剤を垂らした後、ロールの間を通過させ各層間に接着剤を広げる。次に活性エネルギー線を照射し、接着剤を硬化させることによって製造する方法。
The polarizing plate of the present invention can be obtained as follows.
(I) A photocurable adhesive is applied to one surface of the first protective film (1) to form a first curable adhesive layer (2 ′),
On one surface of the second protective film (5), a photocurable adhesive is applied to form a second curable adhesive layer (4 ′),
Next, the first curable adhesive layer (2 ′) and the second curable adhesive layer (4 ′) were simultaneously and / or sequentially overlapped on each surface of the polyvinyl alcohol polarizer (3). Then, the method of manufacturing by irradiating an active energy ray and hardening | curing a 1st curable adhesive layer (2 ') and a 2nd curable adhesive layer (4').
(II) A photocurable adhesive is applied to one surface of the polyvinyl alcohol-based polarizer (3) to form a first curable adhesive layer (2 ′), and the first curing formed The surface of the adhesive adhesive layer (2 ′) is covered with the first protective film (1), and then the other surface of the polyvinyl alcohol polarizer (3) is coated with a photocurable adhesive, A curable adhesive layer (4 ′) is formed, the surface of the formed second curable adhesive layer (4 ′) is covered with a second protective film (2), irradiated with active energy rays, A method for producing a curable adhesive layer (2 ') and a second curable adhesive layer (4') by curing.
(III) Adhesives between the first protective film (1) and the polyvinyl alcohol polarizer (3), and between the second protective film (5) and the polyvinyl alcohol polarizer (3), respectively. , And then pass between the rolls to spread the adhesive between each layer. Next, the manufacturing method is performed by irradiating active energy rays and curing the adhesive.
偏光板の製造方法（Ｉ）について、図２に基づいて、工程ごとに説明する。
［工程（ａ）］
工程（ａ）は、図２の（ａ）に示されるように、保護フィルム（１）及び（５）のそれぞれ片面に、接着剤層形成用の光硬化性接着剤を塗布し、必要に応じて乾燥等を行って、硬化性接着剤層（２’）、（４’）を具備する積層体（１’）、（５’）を得る工程である。
The manufacturing method (I) of a polarizing plate is demonstrated for every process based on FIG.
[Step (a)]
In step (a), as shown in FIG. 2 (a), a photocurable adhesive for forming an adhesive layer is applied to one side of each of the protective films (1) and (5). And drying, etc. to obtain laminates (1 ′) and (5 ′) having curable adhesive layers (2 ′) and (4 ′).
［工程（ｂ）］
工程（ｂ）は、図２の（ｂ）に示されるように、ポリビニルアルコール系偏光子（３）の一方の面（図では上面）に、保護フィルム（１）と硬化性接着剤層（２’）とを具備する積層体（１’）を、
ポリビニルアルコール系偏光子（３）の他方の面（図では下面）に、保護フィルム（５）と硬化性接着剤層（４’）とを具備する積層体（５’）を、それぞれ重ね合わせる工程である。
[Step (b)]
In step (b), as shown in FIG. 2 (b), the protective film (1) and the curable adhesive layer (2) are formed on one surface (upper surface in the figure) of the polyvinyl alcohol polarizer (3). A laminate (1 ') comprising:
A step of superimposing a laminate (5 ′) comprising a protective film (5) and a curable adhesive layer (4 ′) on the other surface (lower surface in the figure) of the polyvinyl alcohol polarizer (3). It is.
［工程（ｃ）］
工程（ｃ）は、図２の（ｃ）に示されるように、活性エネルギー線（６）を照射することにより、保護フィルム（１）、（５）とポリビニルアルコール系偏光子（３）とに挟まれた硬化性接着剤層（２’）、（４’）を硬化させ、接着剤層（２），（４）を形成させる工程である。
図では、保護フィルム（５）の側から活性エネルギー線（６）を照射する場合を示すが、保護フィルム（１）の側から活性エネルギー線（６）を照射してもよいし、両側から同時に、または順次活性エネルギー線（６）を照射してもよい。
活性エネルギー線の照射量は、特に限定されるものではないが、波長２００〜４５０ｎｍ、照度１〜５００ｍＷ／ｃｍ2の光を、照射量が１０〜１０００ｍＪ／ｃｍ2となるように照射して露光することが好ましい。照射する活性エネルギー線の種類としては、可視光、紫外線、赤外線、Ｘ線、α線、β線、γ線等を用いることができるが、特に紫外線が好ましい。光の照射装置としては、例えば、高圧水銀ランプ、低圧水銀ランプ、メタルハライドランプ、エキシマランプ等を用いることが好ましい。
活性エネルギー線（６）照射後、室温で１週間程度エージングすることもできる。
工程（ｃ）を経ることにより、硬化性接着剤層（２’）、（４’）を硬化させて接着剤層（２），（４）とし、偏光子（３）と保護フィルム（１）及び（５）とが接着剤層（２），（４）を介して接着されてなる偏光板が完成する（図１、図２中の（ｄ）参照）。
[Step (c)]
In the step (c), as shown in FIG. 2 (c), the active energy rays (6) are irradiated to the protective films (1) and (5) and the polyvinyl alcohol polarizer (3). This is a step of curing the sandwiched curable adhesive layers (2 ′) and (4 ′) to form adhesive layers (2) and (4).
Although the figure shows the case where the active energy ray (6) is irradiated from the protective film (5) side, the active energy ray (6) may be irradiated from the protective film (1) side or simultaneously from both sides. Alternatively, the active energy ray (6) may be sequentially irradiated.
The irradiation amount of the active energy ray is not particularly limited, but exposure is performed by irradiating light having a wavelength of 200 to 450 nm and an illuminance of 1 to 500 mW / cm 2 so that the irradiation amount is 10 to 1000 mJ / cm 2. It is preferable to do. Visible light, ultraviolet rays, infrared rays, X-rays, α rays, β rays, γ rays and the like can be used as the type of active energy rays to be irradiated, and ultraviolet rays are particularly preferable. As the light irradiation device, for example, a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, an excimer lamp, or the like is preferably used.
After irradiation with the active energy ray (6), it can be aged at room temperature for about one week.
Through the step (c), the curable adhesive layers (2 ′) and (4 ′) are cured to form adhesive layers (2) and (4), and the polarizer (3) and the protective film (1). And (5) are bonded through the adhesive layers (2) and (4) to complete a polarizing plate (see (d) in FIGS. 1 and 2).
［ポリビニルアルコール系偏光子］の製造例
ホウ酸２０重量部、ヨウ素０．２重量部、ヨウ化カリウム０．５重量部を水４８０重量部に溶解させて染色液を調整した。この染色液にＰＶＡフィルム（ビニロンフィルム＃４０、アイセロ社製）を、３０秒浸漬した後、フィルムを一方向に２倍に延伸し、乾燥させて、膜厚３０μｍのＰＶＡ偏光子を得た。
Production Example of [Polyvinyl Alcohol Polarizer] A dyeing solution was prepared by dissolving 20 parts by weight of boric acid, 0.2 parts by weight of iodine, and 0.5 parts by weight of potassium iodide in 480 parts by weight of water. A PVA film (Vinylon film # 40, manufactured by Aicello) was immersed in this dyeing solution for 30 seconds, and then the film was stretched twice in one direction and dried to obtain a PVA polarizer having a thickness of 30 μm.
［実施例１〜１３、比較例１〜８］
保護フィルム（１）として、日本ゼオン社製の紫外線吸収剤を含有しないシクロオレフィンフィルム、ゼオノアフィルム「ＺＦ−１４」（１００μｍ）を用い、保護フィルム（５）として、富士ＴＡＣ（株）製の紫外線吸収剤含有トリアセチルセルロース系フィルム：商品名「フジタック」：８０μｍ」を使用し、それぞれその表面に６０Ｗ・ｍｉｎ／ｍ２の放電量でコロナ処理を行い、表面処理後１時間以内に、表１に示す光硬化性接着剤をワイヤーバーコーター＃３を用いて塗工し、硬化性接着剤層（２’）、（４’）を形成し、前記硬化性接着剤層（２’）と（４’）との間に上記のＰＶＡ偏光子を挟み、保護フィルム（１）／硬化性接着剤層（２’）／ＰＶＡ系偏光子／硬化性接着剤層（４’）／保護フィルム（５）からなる積層体を得た。
保護フィルム（１）がブリキ板に接するように、この積層体の四方をセロハンテープで固定し、ブリキ板に固定した。
ＵＶ照射装置（東芝社製 高圧水銀灯）で最大照度４００ｍＷ／ｃｍ2、積算光量７００ｍＪ／ｃｍ２の紫外線を保護フィルム（１）側から照射して、偏光板を作製した。
各接着剤層の厚みは、４μｍとした。
[Examples 1 to 13, Comparative Examples 1 to 8]
As a protective film (1), a cycloolefin film and ZEONOR film “ZF-14” (100 μm) containing no UV absorber manufactured by Nippon Zeon Co., Ltd. are used, and as a protective film (5), UV light manufactured by Fuji TAC Co., Ltd. is used. Absorbent-containing triacetylcellulose-based film: trade name “Fujitac”: 80 μm, and each surface was subjected to corona treatment with a discharge amount of 60 W · min / m 2 within 1 hour after the surface treatment. Is applied using a wire bar coater # 3 to form curable adhesive layers (2 ′) and (4 ′), and the curable adhesive layers (2 ′) and ( 4 ′), and the protective film (1) / curable adhesive layer (2 ′) / PVA polarizer / curable adhesive layer (4 ′) / protective film (5 Was obtained.
Four sides of this laminate were fixed with cellophane tape so that the protective film (1) was in contact with the tin plate, and was fixed to the tin plate.
A polarizing plate was produced by irradiating ultraviolet rays having a maximum illuminance of 400 mW / cm 2 and an integrated light quantity of 700 mJ / cm 2 from the protective film (1) side with a UV irradiation apparatus (high pressure mercury lamp manufactured by Toshiba Corporation).
The thickness of each adhesive layer was 4 μm.
＜粘度＞
各光硬化性接着剤１．２ｍｌを測定用試料とし、Ｅ型粘度計を用いて、回転速度１００〜０．５ｒｐｍ、２５℃で測定した。
<Viscosity>
1.2 ml of each photocurable adhesive was used as a measurement sample, and measurement was performed using an E-type viscometer at a rotation speed of 100 to 0.5 rpm and 25 ° C.
＜薄膜塗工性＞
光硬化性接着剤を小径グラビアコーター（版：５５０線／インチ、ピラミッド型彫刻版）を用いて５０μｍポリエステルフィルムに塗工した後、ＵＶ照射装置（東芝社製 高圧水銀灯）で最大照度５００ｍＷ／ｃｍ2、積算光量８００ｍＪ／ｃｍ２の紫外線を照射し接着剤を硬化させた。膜厚計を用いて接着剤層の膜厚を測定し以下に示す基準で評価した。
２μｍ未満：◎
２μｍ以上〜４μｍ未満：○
４μｍ以上〜６μｍ未満：△
６μｍ以上：×
<Thin film coatability>
A photocurable adhesive is applied to a 50 μm polyester film using a small-diameter gravure coater (plate: 550 lines / inch, pyramid-type engraving plate), and then the maximum illumination is 500 mW / cm with a UV irradiation device (high pressure mercury lamp manufactured by Toshiba Corporation) 2. The adhesive was cured by irradiating with an ultraviolet ray having an integrated light amount of 800 mJ / cm 2 . The film thickness of the adhesive layer was measured using a film thickness meter and evaluated according to the following criteria.
<2 μm: ◎
2 μm or more and less than 4 μm: ○
4 μm or more to less than 6 μm: Δ
6 μm or more: ×
＜剥離強度＞
接着力は、ＪＩＳ Ｋ６ ８５４−４ 接着剤−剥離接着強さ試験方法−第４部：浮動ローラー法に準拠して測定した。
即ち、得られた偏光板を、２５ｍｍ×１５０ｍｍのサイズにカッターを用いて裁断してサンプルとした。サンプルを両面粘着テープ（東洋インキ製造株式会社製ＤＦ８７１２Ｓ）により金属板上に貼り付けた。サンプル（偏光板）には、保護フィルムと偏光子の間に予め剥離のキッカケを設けておき、２３℃、５０％ＲＨ環境下で、ピール速度：３００ｍｍ／ｍｉｎにて測定した。表中の接着力は、
剥離不可：○
５．０（Ｎ／２５ｍｍ）以上〜２０（Ｎ／２５ｍｍ）未満：△
５．０（Ｎ／２５ｍｍ）未満：×
<Peel strength>
The adhesive strength was measured in accordance with JIS K6 854-4 Adhesive-Peel Adhesion Strength Test Method-Part 4: Floating Roller Method.
That is, the obtained polarizing plate was cut into a size of 25 mm × 150 mm using a cutter to obtain a sample. The sample was affixed on the metal plate with a double-sided adhesive tape (DF8712S manufactured by Toyo Ink Manufacturing Co., Ltd.). The sample (polarizing plate) was peeled off in advance between the protective film and the polarizer, and measured at a peel rate of 300 mm / min in an environment of 23 ° C. and 50% RH. The adhesive strength in the table is
No peeling: ○
5.0 (N / 25 mm) or more to less than 20 (N / 25 mm): Δ
Less than 5.0 (N / 25mm): ×
＜打ち抜き加工性＞
ダンベル社製の１００ｍｍ×１００ｍｍの刃を用い、作製した偏光板を保護フィルム（１）側から打ち抜いた。
打ち抜いた偏光板の、周辺の剥離距離を定規で測定した。
剥離距離１ｍｍ以下：○
１〜３ｍｍ：△
３ｍｍ以上：×
<Punching workability>
The produced polarizing plate was punched out from the protective film (1) side using a 100 mm × 100 mm blade manufactured by Dumbbell.
The peripheral peeling distance of the punched polarizing plate was measured with a ruler.
Peeling distance 1 mm or less: ○
1-3mm: △
3 mm or more: ×
＜巻き癖＞
紫外線照射直後の偏光板を、３００ｍｍ×１００ｍｍのサイズに切断し、直径３インチ（即ち、外周約２４０ｍｍ）の巻き芯に、３００ｍｍの長辺が円周に沿うように巻きつけ、巻き芯を天地方向にし、約２３℃で２４ｈ静置した。偏光板を巻き芯から外し直ちに約２３℃の環境下でカールした半径を測定した。
カールなし：◎
半径１００ｍｍ以上：○
半径９０ｃｍ〜１００ｍｍ：△
半径９０ｍｍ以下：×
<Coiled>
The polarizing plate immediately after the ultraviolet irradiation is cut into a size of 300 mm × 100 mm, wound around a winding core having a diameter of 3 inches (that is, an outer circumference of about 240 mm) so that the long side of 300 mm is along the circumference, and the winding core is top and bottom. And left at about 23 ° C. for 24 hours. The polarizing plate was removed from the winding core, and the curled radius was immediately measured in an environment of about 23 ° C.
No curling: ◎
Radius 100mm or more: ○
Radius 90cm-100mm: △
Radius 90mm or less: ×
表１に示すように、いずれの実施例でも、薄膜塗工性、接着力、打ち抜き加工性、及び巻き癖に優れた偏光板を形成することができた。
実施例１〜９はいずれも、多官能脂環式エポキシ化合物（Ａ）と単官能グリシジル化合物（Ｂ）の光硬化性接着剤を用いる場合であり、単官能グリシジル化合物（Ｂ）が多いほど、接着剤の粘度が低くなり薄膜塗工性に優れている。
As shown in Table 1, in any of the examples, a polarizing plate excellent in thin film coating property, adhesive strength, punching workability, and curl can be formed.
Each of Examples 1 to 9 is a case of using a photocurable adhesive of a polyfunctional alicyclic epoxy compound (A) and a monofunctional glycidyl compound (B), and the more monofunctional glycidyl compound (B), The viscosity of the adhesive is lowered and the thin film coating property is excellent.
また、実施例１０〜１２はオキセタン化合物（Ｃ）を含む光硬化性接着剤を用いる場合であり、オキセタン化合物（Ｃ）を含まない実施例２に比して、光硬化性接着剤が低粘度になるので、薄膜塗工性に優れている。さらに、実施例１３のように、増感剤を含んでも良い。 Moreover, Examples 10-12 are the cases where the photocurable adhesive agent containing an oxetane compound (C) is used, and compared with Example 2 which does not contain an oxetane compound (C), a photocurable adhesive agent has a low viscosity. Therefore, it is excellent in thin film coatability. Further, as in Example 13, a sensitizer may be included.
一方、単官能グリシジル化合物（Ｂ）を含有しない光硬化性接着剤を用いる比較例１は、接着剤の粘度が高く薄膜塗工性が悪いばかりでなく、硬化した接着層が固くなりすぎるためか、打ち抜き加工性が不良である。
また、多官能脂環式エポキシ化合物（Ａ）を含有しない光硬化性接着剤を用いる比較例２は、接着力が小さいばかりでなく、打ち抜き加工性も良くない。単官能グリシジル化合物（Ｂ）は、硬化性が極めて悪いため、単独では硬化していないと考えられる。但し、未硬化ゆえ巻き癖は生じなかった。
On the other hand, in Comparative Example 1 using a photo-curable adhesive that does not contain a monofunctional glycidyl compound (B), not only is the viscosity of the adhesive high and the thin film coating property is poor, but also the cured adhesive layer becomes too hard? The punching workability is poor.
Moreover, the comparative example 2 using the photocurable adhesive agent which does not contain a polyfunctional alicyclic epoxy compound (A) not only has small adhesive force, but punching workability is also not good. Since the monofunctional glycidyl compound (B) has extremely poor curability, it is considered that it is not cured alone. However, no curling occurred because it was not cured.
比較例３は、多官能脂環式エポキシ化合物（Ａ）と単官能グリシジル化合物（Ｂ）とを含む場合であるが、光硬化性接着剤の粘度が２００ｃｐｓと高いため、薄膜塗工性が不良である。 Comparative Example 3 is a case containing a polyfunctional alicyclic epoxy compound (A) and a monofunctional glycidyl compound (B), but the thin film coatability is poor because the viscosity of the photocurable adhesive is as high as 200 cps. It is.
さらに、多官能脂環式エポキシ化合物（Ａ）と単官能グリシジル化合物（Ｂ）とを含むが、比較例４は単官能グリシジル化合物（Ｂ）の含有量が多く、単官能グリシジル化合物由来のエポキシ基個数が０．２より多い場合であり、接着力が小さく、巻き癖も不良だった。 Furthermore, although it contains a polyfunctional alicyclic epoxy compound (A) and a monofunctional glycidyl compound (B), Comparative Example 4 has a large content of the monofunctional glycidyl compound (B), and an epoxy group derived from the monofunctional glycidyl compound. When the number was greater than 0.2, the adhesive strength was small and the curl was poor.
比較例５及び６は、いずれも多官能脂環式エポキシ化合物（Ａ）及び単官能グリシジル化合物（Ｂ）を含まない場合であり、比較例５は脂環式以外のエポキシ化合物（Ｄ）のみの場合であり、巻き癖が不良であるばかりでなく、接着剤の粘度が高いため薄膜塗工性が不良だった。一方、比較例６は脂環式以外のエポキシ化合物（Ｄ）の他にオキセタン化合物（Ｃ）を併用することにより、接着剤の粘度を低下させることはできるが、硬化性の良くない脂環式以外のエポキシ化合物（Ｄ）を多量に含んでいるので、巻き癖が不良だった。 Comparative Examples 5 and 6 are cases in which neither the polyfunctional alicyclic epoxy compound (A) nor the monofunctional glycidyl compound (B) is contained, and Comparative Example 5 includes only the epoxy compound (D) other than the alicyclic type. This is not only the case where the curl is poor, but also the thin film coatability is poor due to the high viscosity of the adhesive. On the other hand, Comparative Example 6 can reduce the viscosity of the adhesive by using the oxetane compound (C) in addition to the epoxy compound (D) other than the alicyclic compound, but the alicyclic compound having poor curability. Since the epoxy compound (D) other than the above was contained in a large amount, the curl was poor.
比較例７、８は、いずれも多官能脂環式エポキシ樹脂（Ａ）に対し、単官能グリシジル化合物（Ｂ）の代わりに脂環式以外の多官能エポキシ樹脂（Ｄ）を組み合わせる場合である。比較例７は多官能エポキシ樹脂（Ｄ）の量が少ないので粘度が高く、薄膜塗工性が不良である。比較例８は比較例７よりも多官能エポキシ樹脂（Ｄ）の量が多いので、粘度が低く薄膜塗工性は良好であるが、その反面、硬化性の良くない脂環式以外のエポキシ化合物（Ｄ）が増えたので、巻き癖が不良である。 Comparative Examples 7 and 8 are cases where a polyfunctional epoxy resin (D) other than an alicyclic compound is combined with the polyfunctional alicyclic epoxy resin (A) instead of the monofunctional glycidyl compound (B). In Comparative Example 7, since the amount of the polyfunctional epoxy resin (D) is small, the viscosity is high and the thin film coating property is poor. Comparative Example 8 has a higher amount of polyfunctional epoxy resin (D) than Comparative Example 7, so that the viscosity is low and the thin film coating property is good. Since (D) has increased, the curl is poor.
比較例９は、多官能脂環式エポキシ樹脂（Ａ）に対し、単官能グリシジル化合物（Ｂ）の代わりに脂環式以外の多官能エポキシ樹脂（Ｄ）およびオキセタン化合物（Ｃ）を組み合わせた場合であり、多官能脂環式エポキシ樹脂（Ａ）の量を減らしたので、比較例８よりもさらに低粘度化するが、巻き癖が不良である。 In Comparative Example 9, a polyfunctional epoxy resin (D) other than an alicyclic compound and an oxetane compound (C) are combined with the polyfunctional alicyclic epoxy resin (A) instead of the monofunctional glycidyl compound (B). Since the amount of the polyfunctional alicyclic epoxy resin (A) is reduced, the viscosity is further reduced as compared with Comparative Example 8, but the curl is poor.
比較例１０は単官能グリシジル化合物（Ｂ）の代わりにエポキシ基を有しない化合物を含む場合であり、硬化性不良により接着力、加工性が不良である。 The comparative example 10 is a case where the compound which does not have an epoxy group is included instead of a monofunctional glycidyl compound (B), and adhesive force and workability are bad by sclerosis | hardenability defect.
・ 保護フィルム
（１’）保護フィルム（１）と硬化性組成物からなる層（２’）との積層体
（２）第一の接着剤層
（２’）硬化性組成物からなる層
・ ポリビニルアルコール系偏光子
・ 第二の接着剤層
（４’）硬化性組成物からなる層
・ 保護フィルム
（５’）保護フィルム（５）と硬化性組成物からなる層（４’）との積層体
（６）活性エネルギー線
-Protective film (1 ') Laminate of protective film (1) and layer (2') made of curable composition (2) First adhesive layer (2 ') Layer made of curable composition-Polyvinyl Alcohol-based polarizer-Second adhesive layer (4 ') Layer composed of curable composition-Protective film (5') Laminate of protective film (5) and layer composed of curable composition (4 ') (6) Active energy ray
Claims (6)
前記カチオン重合性成分１００重量％中に、前記多官能脂環式エポキシ化合物（Ａ）を５０重量％以上含み、
前記カチオン重合性成分１００重量部中に、前記単官能グリシジル化合物（Ｂ）由来のエポキシ基を０．０１〜０．２個含み、
実質的に有機溶剤を含有せず、粘度が１０〜１５０ｍＰａ・ｓである、ことを特徴とする光硬化性接着剤。
ただし、（１）、（２）である。
（１）多官能脂環式エポキシ化合物（Ａ）が、脂環構造に直接結合したエポキシ基を２個以上有するエポキシ化合物である。
（２）単官能グリシジル化合物（Ｂ）が、式（１）に示すグリシジル基を１個有する化合物である。
式（１）
The polyfunctional alicyclic epoxy compound (A) is contained in 50% by weight or more in 100% by weight of the cationic polymerizable component,
In 100 parts by weight of the cationic polymerizable component, 0.01 to 0.2 epoxy groups derived from the monofunctional glycidyl compound (B) are included,
A photocurable adhesive characterized by containing substantially no organic solvent and a viscosity of 10 to 150 mPa · s.
However, (1) and (2).
(1) The polyfunctional alicyclic epoxy compound (A) is an epoxy compound having two or more epoxy groups bonded directly to the alicyclic structure.
(2) The monofunctional glycidyl compound (B) is a compound having one glycidyl group represented by the formula (1).
Formula (1)
前記光硬化性接着剤が、請求項１〜５いずれか記載の光硬化性接着剤であることを特徴とする偏光板。 Both surfaces of the polyvinyl alcohol-based polarizer are polarizing plates each covered with a protective film via an adhesive layer formed by curing a photocurable adhesive,
The said photocurable adhesive agent is a photocurable adhesive agent in any one of Claims 1-5, The polarizing plate characterized by the above-mentioned.
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| JP5677883B2 (en) * | 2011-03-29 | 2015-02-25 | 住友化学株式会社 | Photo-curable adhesive, polarizing plate and laminated optical member |
| JP5919574B2 (en) * | 2011-10-24 | 2016-05-18 | パナソニックＩｐマネジメント株式会社 | UV curable resin composition, optical component adhesive, and organic EL device sealing material |
| JP5988649B2 (en) * | 2012-03-29 | 2016-09-07 | 住友化学株式会社 | Manufacturing method of polarizing plate |
| JP2014137477A (en) * | 2013-01-17 | 2014-07-28 | Sumitomo Chemical Co Ltd | Polarizing plate |
| JP2014215472A (en) * | 2013-04-25 | 2014-11-17 | 株式会社ダイセル | Adhesive for manufacturing polarizing plate and polarizing plate |
| CN104937005B (en) * | 2013-07-09 | 2017-09-05 | 株式会社艾迪科 | cationically polymerizable composition |
| KR101614211B1 (en) | 2013-09-30 | 2016-04-20 | 주식회사 엘지화학 | Method for Maunfacturing a Single-faced Thin Polarizing Plate |
| JP2015094823A (en) * | 2013-11-11 | 2015-05-18 | コニカミノルタ株式会社 | Polarizing plate with cellulose ester film |
| WO2016052244A1 (en) | 2014-09-29 | 2016-04-07 | 株式会社Adeka | Photocurable adhesive, and polarizing plate, laminated optical member, and liquid crystal display device using same |
| JP6857839B2 (en) * | 2016-09-13 | 2021-04-14 | パナソニックＩｐマネジメント株式会社 | Portable information terminal |
| JP2018159911A (en) * | 2017-01-27 | 2018-10-11 | 住友化学株式会社 | Polarizing plate and image display device |
| TWI821172B (en) * | 2017-02-13 | 2023-11-11 | 日商三菱化學股份有限公司 | Adhesive composition for polarizing plates, adhesives for polarizing plates and polarizing plates utilizing the same |
| JP6518303B2 (en) * | 2017-09-27 | 2019-05-22 | 日東電工株式会社 | Method of manufacturing polarizing film |
| JP6947870B2 (en) * | 2018-11-12 | 2021-10-13 | 日東電工株式会社 | Method of manufacturing polarizing film |
| JP6689349B2 (en) * | 2018-11-12 | 2020-04-28 | 日東電工株式会社 | Polarizing film manufacturing method |
| JP7224729B2 (en) | 2019-04-25 | 2023-02-20 | 日東電工株式会社 | LAMINATED POLARIZED FILM MANUFACTURING METHOD AND LAMINATED POLARIZED FILM MANUFACTURING APPARATUS |
| JP2020204700A (en) | 2019-06-17 | 2020-12-24 | 日東電工株式会社 | Method for manufacturing laminated polarization film and device for manufacturing laminated polarization film |
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| JPH04178454A (en) * | 1990-11-09 | 1992-06-25 | Mitsubishi Petrochem Co Ltd | Ultraviolet-curing resin composition |
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| JP5448024B2 (en) * | 2007-03-15 | 2014-03-19 | 住友化学株式会社 | Photocurable adhesive, polarizing plate using the photocurable adhesive, method for producing the same, optical member, and liquid crystal display device |
| JP5266935B2 (en) * | 2008-07-29 | 2013-08-21 | Ｄｉｃ株式会社 | Cationic polymerizable adhesive for bonding polarizer and protective film and polarizing plate obtained using the same |
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