JP6920483B2 - Adhesive layer and adhesive film - Google Patents
Adhesive layer and adhesive film Download PDFInfo
- Publication number
- JP6920483B2 JP6920483B2 JP2020000437A JP2020000437A JP6920483B2 JP 6920483 B2 JP6920483 B2 JP 6920483B2 JP 2020000437 A JP2020000437 A JP 2020000437A JP 2020000437 A JP2020000437 A JP 2020000437A JP 6920483 B2 JP6920483 B2 JP 6920483B2
- Authority
- JP
- Japan
- Prior art keywords
- pressure
- sensitive adhesive
- adhesive layer
- meth
- weight
- 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.)
- Active
Links
- 239000012790 adhesive layer Substances 0.000 title claims description 33
- 239000002313 adhesive film Substances 0.000 title description 28
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 158
- 239000010410 layer Substances 0.000 claims description 102
- 239000000178 monomer Substances 0.000 claims description 97
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 85
- 239000010408 film Substances 0.000 claims description 71
- 239000000203 mixture Substances 0.000 claims description 44
- 239000000853 adhesive Substances 0.000 claims description 32
- 230000001070 adhesive effect Effects 0.000 claims description 32
- 229920002554 vinyl polymer Polymers 0.000 claims description 32
- 239000012788 optical film Substances 0.000 claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 22
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- 125000003118 aryl group Chemical group 0.000 claims description 17
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 17
- 229920001577 copolymer Polymers 0.000 claims description 14
- 239000003431 cross linking reagent Substances 0.000 claims description 11
- 238000004132 cross linking Methods 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 8
- 229920000058 polyacrylate Polymers 0.000 claims description 6
- 238000010030 laminating Methods 0.000 claims description 3
- -1 acrylamide compound Chemical class 0.000 description 40
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 28
- 230000003287 optical effect Effects 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 229920006243 acrylic copolymer Polymers 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 3
- 150000003926 acrylamides Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- PWMLMBQHHBLIQM-UHFFFAOYSA-N 1-(3-prop-2-enoyloxypropyl)cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1(CCCOC(=O)C=C)C(O)=O PWMLMBQHHBLIQM-UHFFFAOYSA-N 0.000 description 1
- 125000005978 1-naphthyloxy group Chemical group 0.000 description 1
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- IEQWWMKDFZUMMU-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethyl)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)CCOC(=O)C=C IEQWWMKDFZUMMU-UHFFFAOYSA-N 0.000 description 1
- YDRQKFSCVSLQKI-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethyl)cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1(CCOC(=O)C=C)C(O)=O YDRQKFSCVSLQKI-UHFFFAOYSA-N 0.000 description 1
- UXTGJIIBLZIQPK-UHFFFAOYSA-N 3-(2-prop-2-enoyloxyethyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(CCOC(=O)C=C)=C1C(O)=O UXTGJIIBLZIQPK-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- OCIFJWVZZUDMRL-UHFFFAOYSA-N 6-hydroxyhexyl prop-2-enoate Chemical compound OCCCCCCOC(=O)C=C OCIFJWVZZUDMRL-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 101100433727 Caenorhabditis elegans got-1.2 gene Proteins 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Chemical class 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 125000003368 amide group Chemical class 0.000 description 1
- 125000003277 amino group Chemical class 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
Description
本発明は、光学部材の層間の貼合などに用いられる厚さ１μｍ〜２０μｍの薄膜にも拘わらず、高粘着力、高密着性の性能を有する粘着剤層、及びそれを用いた粘着フィルムに関する。 The present invention relates to an adhesive layer having high adhesive strength and high adhesiveness despite being a thin film having a thickness of 1 μm to 20 μm used for bonding layers of optical members, and an adhesive film using the same. ..
粘着剤層を介して偏光板、位相差板などの光学部材を液晶セルなどの被着体に貼合するため、種々の粘着フィルムが提案されている（例えば特許文献１〜２参照）。
特許文献１には、ブチルアクリレートなどを主成分のモノマーとし、アクリルアミド化合物などを含有する光学用粘着剤組成物が記載されている。
特許文献２には、炭素数４〜８のアルキル基を有する（メタ）アクリレートを主成分のモノマーとし、カルボキシル基含有モノマー、及び窒素含有ビニルモノマーを含有する光学用粘着剤組成物が記載されている。
また、粘着剤層の屈折率を高めるために、種々の工夫をした粘着フィルムが提案されている（例えば特許文献３〜８参照）。
特許文献３には、芳香族環を有し、屈折率１．５１〜１．７５のタッキファイヤーを含有する光学用粘着剤組成物が記載されている。
特許文献４には、芳香族環を含有するアクリル酸変性モノマーの共重合性ポリマーを含む粘着剤組成物を含有する粘着シートが記載されている。
特許文献５には、芳香族環を有する粘着付与樹脂と、芳香族リン酸エステル系可塑剤を含有する光学用粘着剤組成物が記載されている。
特許文献６には、アクリル系樹脂と、エチレン性不飽和基を１つ含有する芳香族化合物を含有する粘着剤組成物が硬化されてなる粘着剤が記載されている。
特許文献７には、芳香族モノマーを含有するアクリル系の粘着剤を介して、位相差フィルム及び複屈折板を互いに固着してなる光学部品が記載されている。
特許文献８には、芳香族ジイソシアネートと、芳香族ポリエステルジオールを反応させてなるウレタン樹脂を含む粘着剤組成物が記載されている。
Various pressure-sensitive adhesive films have been proposed for bonding optical members such as polarizing plates and retardation plates to adherends such as liquid crystal cells via a pressure-sensitive adhesive layer (see, for example, Patent Documents 1 and 2).
Patent Document 1 describes an optical pressure-sensitive adhesive composition containing butyl acrylate or the like as a main component and an acrylamide compound or the like as a main component.
Patent Document 2 describes an optical pressure-sensitive adhesive composition containing a (meth) acrylate having an alkyl group having 4 to 8 carbon atoms as a main component, a carboxyl group-containing monomer, and a nitrogen-containing vinyl monomer. There is.
Further, in order to increase the refractive index of the pressure-sensitive adhesive layer, variously devised pressure-sensitive adhesive films have been proposed (see, for example, Patent Documents 3 to 8).
Patent Document 3 describes an optical pressure-sensitive adhesive composition having an aromatic ring and containing a tack fire having a refractive index of 1.51 to 1.75.
Patent Document 4 describes a pressure-sensitive adhesive sheet containing a pressure-sensitive adhesive composition containing a copolymerization polymer of an acrylic acid-modified monomer containing an aromatic ring.
Patent Document 5 describes an optical pressure-sensitive adhesive composition containing a pressure-sensitive adhesive resin having an aromatic ring and an aromatic phosphoric acid ester-based plasticizer.
Patent Document 6 describes a pressure-sensitive adhesive obtained by curing a pressure-sensitive adhesive composition containing an acrylic resin and an aromatic compound containing one ethylenically unsaturated group.
Patent Document 7 describes an optical component in which a retardation film and a birefringent plate are fixed to each other via an acrylic pressure-sensitive adhesive containing an aromatic monomer.
Patent Document 8 describes a pressure-sensitive adhesive composition containing a urethane resin obtained by reacting an aromatic diisocyanate with an aromatic polyester diol.
近年において、光学部材の層間を貼合するのに用いる粘着フィルムに対して要求されている事項は、光学部材の薄膜化を図るために、粘着剤層の厚さを２０μｍ以下に薄くした粘着フィルムとすることである。
一般に、粘着剤層の粘着力は、粘着剤層の厚さに略比例していることから、粘着剤層の厚さを薄くすると、それに伴って粘着力が低下してしまう。
In recent years, what has been required for an adhesive film used for bonding layers of optical members is an adhesive film in which the thickness of the adhesive layer is reduced to 20 μm or less in order to reduce the thickness of the optical member. Is to be.
In general, the adhesive strength of the pressure-sensitive adhesive layer is substantially proportional to the thickness of the pressure-sensitive adhesive layer. Therefore, if the thickness of the pressure-sensitive adhesive layer is reduced, the adhesive strength is reduced accordingly.
しかし、近年求められている粘着フィルムは、粘着剤層の厚さを薄くしても、従来の粘着フィルム（粘着剤層の厚さが約３０μｍと厚い）と同等の粘着力を有しており、且つ、高温・高湿度の雰囲気下に長時間放置した後の耐久性についても、従来の粘着フィルムと同等以上の性能を有することが求められている。
また、粘着剤層の厚さを薄くできること、及び、エージング処理（恒温で養生を行うこと）を施す必要がない粘着剤層を形成できることから、粘着フィルムの基材を省いた粘着剤層のみからなる、「離型フィルム／粘着剤層／離型フィルム」の部材構成をした、ＮＣＦ（Ｎｏｎ Ｃａｒｒｉｅｒ Ｆｉｌｍ）の形態とすることが求められている。
However, the pressure-sensitive adhesive film that has been demanded in recent years has the same adhesive strength as the conventional pressure-sensitive adhesive film (the thickness of the pressure-sensitive adhesive layer is as thick as about 30 μm) even if the thickness of the pressure-sensitive adhesive layer is reduced. Moreover, it is required to have the same or higher performance as the conventional adhesive film in terms of durability after being left in an atmosphere of high temperature and high humidity for a long time.
Further, since the thickness of the pressure-sensitive adhesive layer can be reduced and the pressure-sensitive adhesive layer that does not need to be subjected to aging treatment (curing at a constant temperature) can be formed, only the pressure-sensitive adhesive layer without the base material of the pressure-sensitive adhesive film can be used. It is required to form an NCF (Non Carrier Film) having a member structure of "release film / adhesive layer / release film".
また、従来の粘着フィルムでは、被着体に粘着フィルムを貼り合せた後に、エージング処理が施されるために、被着体と粘着剤層との密着性の向上を図ることができた。
しかしながら、ＮＣＦの形態をした粘着フィルムは、すでに粘着剤層のエージングを終了させていることから、被着体と粘着剤層との密着力が不足する。そのため、被着体の表面に対して、コロナ処理などの表面処理をする必要があるという問題があった。
これらの要求事項および問題を克服した粘着フィルムが、必要とされている。
Further, in the conventional pressure-sensitive adhesive film, since the pressure-sensitive adhesive film is attached to the adherend and then subjected to an aging treatment, the adhesion between the adherend and the pressure-sensitive adhesive layer can be improved.
However, since the pressure-sensitive adhesive film in the form of NCF has already completed the aging of the pressure-sensitive adhesive layer, the adhesive force between the adherend and the pressure-sensitive adhesive layer is insufficient. Therefore, there is a problem that the surface of the adherend needs to be subjected to surface treatment such as corona treatment.
An adhesive film that overcomes these requirements and problems is needed.
本発明は、上記事情に鑑みてなされたものであり、厚さ１μｍ〜２０μｍの薄膜にも拘わらず、高粘着力、高密着性の性能を有する粘着剤層、及びそれを用いた粘着フィルムを提供することを課題とする。 The present invention has been made in view of the above circumstances, and a pressure-sensitive adhesive layer having high adhesive strength and high adhesion performance despite a thin film having a thickness of 1 μm to 20 μm, and a pressure-sensitive adhesive film using the same. The challenge is to provide.
上記の課題を解決するため、本発明は、アクリル系ポリマーからなる粘着剤組成物を架橋してなる粘着剤層において、アルキル基の炭素数がＣ１〜Ｃ１４のアルキル（メタ）アクリレートモノマーの少なくとも１種以上を合せた７０〜９５重量部と、芳香族基を含有する（メタ）アクリレートモノマーの少なくとも１種以上を合せた５〜３０重量部との合計１００重量部を主成分の（メタ）アクリレートモノマーとし、他の共重合性モノマーとして、共重合可能な窒素含有ビニルモノマーの少なくとも１種以上を含有させて、共重合及び架橋させることにより、強靭な粘着力と高密着性の性能を有する粘着剤層とすることを技術思想としている。
また、上記の課題を解決するため、本発明は、アクリル系ポリマーと、（Ｄ）架橋剤とを含有する粘着剤組成物を架橋してなる粘着剤層において、前記アクリル系ポリマーが、（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４のアルキル（メタ）アクリレートモノマーの少なくとも１種以上を合せた７０〜９５重量部と、芳香族基を含有する（メタ）アクリレートモノマーの少なくとも１種以上を合せた５〜３０重量部との合計１００重量部に対して、（Ｂ）ヒドロキシル基を含有しない窒素含有ビニルモノマーの少なくとも１種以上を５〜５０重量部と、（Ｃ）カルボキシル基を含有する共重合性ビニルモノマーの少なくとも１種以上を０．１〜２重量部、及び／又は、ヒドロキシル基を含有する共重合性ビニルモノマーの少なくとも１種以上を０．１〜５重量部と、を共重合させた重量平均分子量２０万〜２００万の共重合体からなり、前記粘着剤組成物が、前記（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４のアルキル（メタ）アクリレートモノマーの少なくとも１種以上を合せた７０〜９５重量部と、芳香族基を含有する（メタ）アクリレートモノマーの少なくとも１種以上を合せた５〜３０重量部との合計１００重量部に対して、前記（Ｄ）架橋剤を０．０１〜５重量部の割合で含有してなり、前記粘着剤層の厚さが１μｍ〜２０μｍであり、前記粘着剤層の屈折率が１．４７〜１．５０であり、被着体に、前記粘着剤層を貼り合せる前に、エージング処理が施されており、被着体に、前記粘着剤層を貼り合せた後には、エージング処理を施す必要がないことを特徴とする粘着剤層を提供する。
In order to solve the above problems, the present invention presents the present invention in a pressure-sensitive adhesive layer obtained by cross-linking a pressure-sensitive adhesive composition made of an acrylic polymer, at least one of alkyl (meth) acrylate monomers having an alkyl group having C1 to C14 carbon atoms. A total of 100 parts by weight of (meth) acrylate as a main component, which is 70 to 95 parts by weight including the seeds or more and 5 to 30 parts by weight including at least one (meth) acrylate monomer containing an aromatic group. Adhesion having tough adhesive strength and high adhesion performance by containing at least one of copolymerizable nitrogen-containing vinyl monomers as a monomer and as another copolymerizable monomer, and copolymerizing and cross-linking. The technical idea is to use an agent layer.
Further, in order to solve the above-mentioned problems, in the present invention, in the pressure-sensitive adhesive layer formed by cross-linking the pressure-sensitive adhesive composition containing the acrylic-based polymer and (D) the cross-linking agent, the acrylic-based polymer is ( A). ) combined with 70 to 95 parts by weight of the combined at least one or more alkyl (meth) acrylate monomers of the number of carbon atoms in the alkyl group is C1 to C14, containing an aromatic group at least one or more kinds of (meth) acrylate monomer With respect to a total of 100 parts by weight of 5 to 30 parts by weight, at least one or more of (B) hydroxyl group-free nitrogen-containing vinyl monomers are added to 5 to 50 parts by weight and (C) a copolymer containing a carboxyl group. Copolymerize at least one or more polymerizable vinyl monomers with 0.1 to 2 parts by weight and / or at least one or more copolymerizable vinyl monomers containing a hydroxyl group with 0.1 to 5 parts by weight. It consists copolymer having a weight average molecular weight from 200000 to 2000000 which is, the pressure-sensitive adhesive composition, wherein the (a) the number of carbon atoms in the alkyl group is at least one or more kinds of alkyl (meth) acrylate monomer C1~C14 The (D) cross-linking agent was added to a total of 100 parts by weight of 70 to 95 parts by weight of the total and 5 to 30 parts by weight of the total of at least one (meth) acrylate monomer containing an aromatic group. It is contained in a proportion of 0.01 to 5 parts by weight, the thickness of the pressure-sensitive adhesive layer is 1 μm to 20 μm, the refractive index of the pressure-sensitive adhesive layer is 1.47 to 1.50, and the adherend. The adhesive is characterized in that it is subjected to an aging treatment before the pressure-sensitive adhesive layer is bonded to the adherend, and it is not necessary to perform the aging treatment after the pressure-sensitive adhesive layer is bonded to the adherend. Provide a layer.
また、前記粘着剤組成物が、前記主成分の（メタ）アクリレートモノマー１００重量部に対して、（Ｂ）窒素含有ビニルモノマーの１種以上を５〜５０重量部と、（Ｃ）カルボキシル基を含有する共重合性ビニルモノマー及び／又はヒドロキシル基を含有する共重合性ビニルモノマーの少なくとも１種以上を０．１〜５重量部と、を含有する重量平均分子量２０万〜２００万の共重合体、及び（Ｄ）架橋剤を０．０１〜５重量部を、含有することが好ましい。 Further, the pressure-sensitive adhesive composition, the (meth) acrylate monomer 100 parts by weight of the main component, and 5 to 50 parts by weight of one or more of (B) nitrogen-containing vinyl monomer, (C) a carboxyl group A copolymer having a weight average molecular weight of 200,000 to 2 million containing at least one or more of a copolymerizable vinyl monomer and / or a copolymerizable vinyl monomer containing a hydroxyl group in an amount of 0.1 to 5 parts by weight. , And (D) the cross-linking agent are preferably contained in an amount of 0.01 to 5 parts by weight.
また、前記粘着剤組成物が、前記主成分の（メタ）アクリレートモノマー１００重量部の内、メチルアクリレートのモノマーを２０重量部以上の割合で含有することが好ましい。 Further, it is preferable that the pressure-sensitive adhesive composition contains 20 parts by weight or more of the methyl acrylate monomer in 100 parts by weight of the (meth) acrylate monomer as the main component.
また、前記粘着剤組成物が、前記主成分の（メタ）アクリレートモノマー１００重量部に対して、カルボキシル基を含有する共重合性ビニルモノマーの１種以上を２．０重量部以下、及び／又は、ヒドロキシル基を含有する共重合性ビニルモノマーの１種以上を５．０重量部以下の割合で含有することが好ましい。 Further, the pressure-sensitive adhesive composition contains 2.0 parts by weight or less of one or more copolymerizable vinyl monomers containing a carboxyl group with respect to 100 parts by weight of the (meth) acrylate monomer as the main component, and / or. , It is preferable to contain at least one type of copolymerizable vinyl monomer containing a hydroxyl group in a proportion of 5.0 parts by weight or less.
また、前記粘着剤層の屈折率が１．４７〜１．５０であることが好ましい。 Further, the refractive index of the pressure-sensitive adhesive layer is preferably 1.47 to 1.50.
また、本発明は、前記粘着剤層が、離型フィルムの片面に形成されてなり、離型フィルム／粘着剤層／離型フィルムの構成であることを特徴とする粘着フィルムを提供する。 The present invention also provides an adhesive film characterized in that the pressure-sensitive adhesive layer is formed on one side of a release film and has a structure of a release film / a pressure-sensitive adhesive layer / a release film.
また、本発明は、基材の片面上に、前記粘着剤層が積層されてなることを特徴とする粘着フィルムを提供する。 Further, the present invention provides an adhesive film characterized in that the pressure-sensitive adhesive layer is laminated on one surface of a base material.
また、本発明は、前記粘着フィルムが用いられた、偏光板の周辺部材用フィルムを提供する。 The present invention also provides a film for peripheral members of a polarizing plate using the pressure-sensitive adhesive film.
また、本発明は、前記粘着フィルムが用いられた、タッチパネル用フィルムを提供する。 The present invention also provides a touch panel film using the adhesive film.
また、本発明は、前記粘着フィルムが用いられた、電子ペーパー用フィルムを提供する。 The present invention also provides a film for electronic paper in which the pressure-sensitive adhesive film is used.
また、本発明は、前記粘着フィルムが用いられた、有機ＥＬ用フィルムを提供する。 The present invention also provides a film for organic EL in which the pressure-sensitive adhesive film is used.
また、本発明は、光学フィルムの少なくとも一方の面に、前記粘着剤層が積層されてなる粘着剤層付き光学フィルムを提供する。 The present invention also provides an optical film with an adhesive layer in which the pressure-sensitive adhesive layer is laminated on at least one surface of the optical film.
本発明によれば、従来の要求事項および問題を克服して、厚さ１μｍ〜２０μｍの薄膜にも拘わらず、高粘着力、高密着性の性能を有する粘着剤層、及びそれを用いた粘着フィルムを提供することができる。 According to the present invention, overcoming the conventional requirements and problems, a pressure-sensitive adhesive layer having high adhesive strength and high adhesion performance despite a thin film having a thickness of 1 μm to 20 μm, and adhesion using the same. Film can be provided.
以下、好適な実施の形態に基づいて本発明を説明する。
本発明の粘着剤層は、アクリル系ポリマーからなる粘着剤組成物を架橋してなる粘着剤層において、前記粘着剤組成物が、主成分の（メタ）アクリレートモノマーとして、アルキル基の炭素数がＣ１〜Ｃ１４のアルキル（メタ）アクリレートモノマーの少なくとも１種以上を含有し、他の共重合性モノマーとして、窒素含有ビニルモノマーの少なくとも１種以上と、カルボキシル基を含有する共重合性ビニルモノマー及び／又はヒドロキシル基を含有する共重合性ビニルモノマーの少なくとも１種以上と、を含有し、前記粘着剤層の厚さが１μｍ〜２０μｍであり、厚さが５μｍの時の粘着力が４．０（Ｎ／２５ｍｍ）以上であることを特徴とする。
Hereinafter, the present invention will be described based on preferred embodiments.
The pressure-sensitive adhesive layer of the present invention is a pressure-sensitive adhesive layer obtained by cross-linking a pressure-sensitive adhesive composition made of an acrylic polymer. A copolymerizable vinyl monomer containing at least one of C1 to C14 alkyl (meth) acrylate monomers, and as other copolymerizable monomers, at least one of nitrogen-containing vinyl monomers, a carboxyl group-containing copolymerizable vinyl monomer, and / Alternatively, the pressure-sensitive adhesive layer contains at least one or more copolymerizable vinyl monomers containing a hydroxyl group, the thickness of the pressure-sensitive adhesive layer is 1 μm to 20 μm, and the pressure-sensitive adhesive strength is 4.0 (when the thickness is 5 μm). N / 25 mm) or more.
アルキル基の炭素数がＣ１〜Ｃ１４のアルキル（メタ）アクリレートモノマーとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、イソノニル（メタ）アクリレート、デシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、ドデシル（メタ）アクリレート、トリデシル（メタ）アクリレート、テトラデシル（メタ）アクリレート、シクロペンチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレートなどの少なくとも１種以上が挙げられる。アルキル（メタ）アクリレートモノマーのアルキル基は、直鎖、分枝状、環状のいずれでもよい。アルキル基の炭素数がＣ１〜Ｃ１４の（メタ）アクリル酸エステルモノマーは、粘着剤組成物のアクリル系ポリマー（共重合体）１００重量部に対する割合が、５０〜９５重量部であることが好ましい。
また、本願発明に係わる粘着剤層においては、粘着剤組成物が、アルキル基の炭素数がＣ１〜Ｃ１４のアルキル（メタ）アクリレートモノマーの１種以上からなる主成分の（メタ）アクリレートモノマー１００重量部の内、メチルアクリレートのモノマーを２０重量部以上の割合で含有することにより、粘着剤層の屈折率を、１．４７以上に高めることができる。
Examples of the alkyl (meth) acrylate monomer having an alkyl group having C1 to C14 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and isobutyl. (Meta) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl At least one of (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate and the like. More than seeds can be mentioned. The alkyl group of the alkyl (meth) acrylate monomer may be linear, branched or cyclic. The ratio of the (meth) acrylic acid ester monomer having an alkyl group having C1 to C14 to 100 parts by weight of the acrylic polymer (copolymer) of the pressure-sensitive adhesive composition is preferably 50 to 95 parts by weight.
Further, in the pressure-sensitive adhesive layer according to the present invention, the pressure-sensitive adhesive composition comprises 100 weights of the main component (meth) acrylate monomer composed of one or more alkyl (meth) acrylate monomers having an alkyl group having C1 to C14 carbon atoms. By containing the monomer of methyl acrylate in a proportion of 20 parts by weight or more, the refractive index of the pressure-sensitive adhesive layer can be increased to 1.47 or more.
本発明に係わる粘着剤組成物には、さらに、主成分の（メタ）アクリレートモノマーとして、芳香族基を含有する（メタ）アクリレートモノマーの１種以上を含有させることができる。芳香族基を含有する（メタ）アクリレートモノマーとしては、べンジル（メタ）アクリレート、ナフチル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシブチル（メタ）アクリレート、２−（１−ナフチルオキシ）エチル（メタ）アクリレート、２−（２−ナフチルオキシ）エチル（メタ）アクリレート、６−（１−ナフチルオキシ）ヘキシル（メタ）アクリレート、６−（２−ナフチルオキシ）ヘキシル（メタ）アクリレート、８−（１−ナフチルオキシ）オクチル（メタ）アクリレート、８−（２−ナフチルオキシ）オクチル（メタ）アクリレートなどが挙げられる。屈折率が高い粘着剤層を得るためには、芳香族基を含有する（メタ）アクリレートモノマーの少なくとも１種以上を配合することが好ましい。 The pressure-sensitive adhesive composition according to the present invention may further contain one or more (meth) acrylate monomers containing an aromatic group as the main component (meth) acrylate monomer. Examples of the (meth) acrylate monomer containing an aromatic group include benzyl (meth) acrylate, naphthyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxybutyl (meth) acrylate, and 2- (1-naphthyloxy) ethyl. (Meta) acrylate, 2- (2-naphthyloxy) ethyl (meth) acrylate, 6- (1-naphthyloxy) hexyl (meth) acrylate, 6- (2-naphthyloxy) hexyl (meth) acrylate, 8-( Examples thereof include 1-naphthyloxy) octyl (meth) acrylate and 8- (2-naphthyloxy) octyl (meth) acrylate. In order to obtain a pressure-sensitive adhesive layer having a high refractive index, it is preferable to blend at least one (meth) acrylate monomer containing an aromatic group.
これらの芳香族基を含有する（メタ）アクリレートモノマーを、主成分のモノマーであるアルキル基の炭素数がＣ１〜Ｃ１４のアルキル（メタ）アクリレートモノマーと混合することにより、得られる粘着剤層の屈折率を上昇させて調整でき、光学部材間の屈折率差を少なくして、全反射を低減させることにより全光線透過率を向上させることができる。本発明に係わる粘着剤層において、粘着剤組成物に芳香族基を含有する（メタ）アクリレートモノマーを含有させる場合は、主成分の（メタ）アクリレートモノマー１００重量部に対して、５〜３０重量部の割合で含有させるのが好ましい。
また、芳香族基を含有する（メタ）アクリレートモノマーを共重合させることにより、上記の主成分の（メタ）アクリレートモノマー１００重量部の内、メチルアクリレートのモノマーを２０重量部以上の割合で含有させて粘着剤層の屈折率を高める効果よりも、さらに粘着剤層の屈折率を高めることができる。
また、上記のとおり、粘着剤層の屈折率を高める方法として、主成分の（メタ）アクリレートモノマー１００重量部の内、メチルアクリレートのモノマーを２０重量部以上の割合で含有させる方法と、芳香族基を含有する（メタ）アクリレートモノマーを共重合させる方法との２つの方法があり、それぞれの方法を単独で採用できるが、その２つの方法を併用することがより好ましい。
Refractive index of the pressure-sensitive adhesive layer obtained by mixing the (meth) acrylate monomer containing these aromatic groups with the alkyl (meth) acrylate monomer having an alkyl group having C1 to C14 carbon atoms, which is the main component monomer. The rate can be increased and adjusted, the difference in refractive index between the optical members can be reduced, and the total reflection can be reduced to improve the total light transmittance. In the pressure-sensitive adhesive layer according to the present invention, when the pressure-sensitive adhesive composition contains a (meth) acrylate monomer containing an aromatic group, the weight is 5 to 30% by weight based on 100 parts by weight of the (meth) acrylate monomer as the main component. It is preferable to contain it in a proportion of parts.
Further, by copolymerizing the (meth) acrylate monomer containing an aromatic group, 20 parts by weight or more of the methyl acrylate monomer is contained in 100 parts by weight of the (meth) acrylate monomer as the main component. The refractive index of the pressure-sensitive adhesive layer can be further increased rather than the effect of increasing the refractive index of the pressure-sensitive adhesive layer.
Further, as described above, as a method for increasing the refractive index of the pressure-sensitive adhesive layer, a method in which a methyl acrylate monomer is contained in a proportion of 20 parts by weight or more out of 100 parts by weight of the (meth) acrylate monomer as a main component, and an aromatic There are two methods, one is a method of copolymerizing a (meth) acrylate monomer containing a group, and each method can be adopted alone, but it is more preferable to use the two methods together.
窒素含有ビニルモノマーとしては、例えばＮ−ビニルピロリドン、Ｎ−ビニルカプロラクタム、（メタ）アクリロイルモルホリンなどの環状窒素ビニル化合物、Ｎ−エチル−Ｎ−メチル（メタ）アクリルアミド、Ｎ−メチル−Ｎ−プロピル（メタ）アクリルアミド、Ｎ−メチル−Ｎ−イソプロピル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、Ｎ，Ｎ−ジエチル（メタ）アクリルアミド、Ｎ，Ｎ−ジプロピル（メタ）アクリルアミド、Ｎ，Ｎ−ジイソプロピル（メタ）アクリルアミド、Ｎ，Ｎ−ジブチル（メタ）アクリルアミドなどのジアルキル置換（メタ）アクリルアミド、Ｎ−エチル−Ｎ−メチルアミノエチル（メタ）アクリレート、Ｎ−メチル−Ｎ−プロピルアミノエチル（メタ）アクリレート、Ｎ−メチル−Ｎ−イソプロピルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノメチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノブチル（メタ）アクリレート、Ｎ，Ｎ−ジプロピルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジブチルアミノエチル（メタ）アクリレートなどのジアルキルアミノ（メタ）アクリレート、Ｎ−エチル−Ｎ−メチルアミノプロピル（メタ）アクリルアミド、Ｎ−メチル−Ｎ−プロピルアミノプロピル（メタ）アクリルアミド、Ｎ−メチル−Ｎ−イソプロピルアミノプロピル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリルアミド、Ｎ，Ｎ−ジエチルアミノプロピル（メタ）アクリルアミド、Ｎ，Ｎ−ジプロピルアミノプロピル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリルアミド、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリルアミドなどのジアルキル置換アミノアルキル（メタ）アクリルアミドなどの少なくとも１種以上が挙げられる。 Examples of the nitrogen-containing vinyl monomer include cyclic nitrogen-vinyl compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, and (meth) acryloylmorpholin, N-ethyl-N-methyl (meth) acrylamide, and N-methyl-N-propyl (. Meta) acrylamide, N-methyl-N-isopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dipropyl (meth) acrylamide, N, N- Dialkyl-substituted (meth) acrylamides such as diisopropyl (meth) acrylamide, N, N-dibutyl (meth) acrylamide, N-ethyl-N-methylaminoethyl (meth) acrylate, N-methyl-N-propylaminoethyl (meth) Acrylate, N-methyl-N-isopropylaminoethyl (meth) acrylate, N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) Dialkylamino (meth) acrylates such as acrylate, N, N-dimethylaminobutyl (meth) acrylate, N, N-dipropylaminoethyl (meth) acrylate, N, N-dibutylaminoethyl (meth) acrylate, N-ethyl -N-Methylaminopropyl (meth) acrylamide, N-methyl-N-propylaminopropyl (meth) acrylamide, N-methyl-N-isopropylaminopropyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide , N, N-diethylaminopropyl (meth) acrylamide, N, N-dipropylaminopropyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide and other dialkyl At least one or more such as substituted aminoalkyl (meth) acrylamide may be mentioned.
前記窒素含有ビニルモノマーとしては、後述する（Ｃ）の化合物と区別可能とするため、水酸基を含有しないものが好ましく、水酸基およびカルボキシル基を含有しないものがより好ましい。このようなモノマーとしては、上に例示したモノマー、例えば、Ｎ，Ｎ−ジアルキル置換アミノ基やＮ，Ｎ−ジアルキル置換アミド基を含有するアクリル系モノマー；Ｎ−ビニルピロリドン、Ｎ−ビニルカプロラクタムなどのＮ−ビニル置換ラクタム類；Ｎ−（メタ）アクリロイルモルホリンなどのＮ−（メタ）アクリロイル置換環状アミン類が好ましい。 The nitrogen-containing vinyl monomer preferably does not contain a hydroxyl group, and more preferably does not contain a hydroxyl group or a carboxyl group, so as to be distinguishable from the compound (C) described later. Examples of such a monomer include the monomers exemplified above, for example, acrylic monomers containing an N, N-dialkyl-substituted amino group or an N, N-dialkyl-substituted amide group; N-vinylpyrrolidone, N-vinylcaprolactam and the like. N-vinyl-substituted lactams; N- (meth) acryloyl-substituted cyclic amines such as N- (meth) acryloylmorpholine are preferred.
また、本発明に係わる粘着剤層において、粘着剤組成物に含有させる窒素含有ビニルモノマーは、粘着剤層に対して必要な粘着力及び耐久性を付与させることができる。本発明に係わる粘着剤層において、粘着剤組成物に含有させる窒素含有ビニルモノマーは、主成分の（メタ）アクリレートモノマー１００重量部に対して、５〜５０重量部であることが好ましい。
また、本発明に係わる粘着剤層において、粘着剤組成物に含有させる窒素含有ビニルモノマーとしては、Ｎ−ビニルピロリドン、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、Ｎ，Ｎ−ジエチル（メタ）アクリルアミド、Ｎ，Ｎ−ジプロピル（メタ）アクリルアミド、Ｎ，Ｎ−ジイソプロピル（メタ）アクリルアミド、Ｎ，Ｎ−ジブチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリルアミド、Ｎ，Ｎ−ジエチルアミノプロピル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリルアミド、Ｎ−ビニルカプロラクタムなどが特に好適に使用される。
Further, in the pressure-sensitive adhesive layer according to the present invention, the nitrogen-containing vinyl monomer contained in the pressure-sensitive adhesive composition can impart necessary adhesive strength and durability to the pressure-sensitive adhesive layer. In the pressure-sensitive adhesive layer according to the present invention, the nitrogen-containing vinyl monomer contained in the pressure-sensitive adhesive composition is preferably 5 to 50 parts by weight with respect to 100 parts by weight of the main component (meth) acrylate monomer.
Further, in the pressure-sensitive adhesive layer according to the present invention, examples of the nitrogen-containing vinyl monomer contained in the pressure-sensitive adhesive composition include N-vinylpyrrolidone, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, and the like. N, N-dipropyl (meth) acrylamide, N, N-diisopropyl (meth) acrylamide, N, N-dibutyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) ) Acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, N-vinylcaprolactam and the like are particularly preferably used.
カルボキシル基を含有する共重合性ビニルモノマー（カルボキシル基含有モノマー）としては、例えば、（メタ）アクリル酸、カルボキシエチル（メタ）アクリレート、カルボキシペンチル（メタ）アクリレート、２−（メタ）アクリロイロキシエチルヘキサヒドロフタル酸、２−（メタ）アクリロイロキシプロピルヘキサヒドロフタル酸、２−（メタ）アクリロイロキシエチルフタル酸、２−（メタ）アクリロイロキシエチルコハク酸、２−（メタ）アクリロイロキシエチルマレイン酸、カルボキシポリカプロラクトンモノ（メタ）アクリレート、２−（メタ）アクリロイロキシエチルテトラヒドロフタル酸などの少なくとも１種以上が挙げられる。
また、本発明に係わる粘着剤層において、粘着剤組成物に含有させるカルボキシル基含有モノマーは、粘着剤層に対して必要な凝集力を付与させることができる。本発明に係わる粘着剤層において、粘着剤組成物に含有させるカルボキシル基含有モノマーは、主成分の（メタ）アクリレートモノマー１００重量部に対して、０．１〜５重量部であることが好ましい。
Examples of the carboxyl group-containing copolymerizable vinyl monomer (carboxyl group-containing monomer) include (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, and 2- (meth) acryloyloxyethyl. Hexahydrophthalic acid, 2- (meth) acryloyloxypropyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloy At least one or more of loxyethyl maleic acid, carboxypolycaprolactone mono (meth) acrylate, 2- (meth) acryloyloxyethyl tetrahydrophthalic acid and the like can be mentioned.
Further, in the pressure-sensitive adhesive layer according to the present invention, the carboxyl group-containing monomer contained in the pressure-sensitive adhesive composition can impart a necessary cohesive force to the pressure-sensitive adhesive layer. In the pressure-sensitive adhesive layer according to the present invention, the carboxyl group-containing monomer contained in the pressure-sensitive adhesive composition is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the (meth) acrylate monomer as the main component.
ヒドロキシル基を含有する共重合性ビニルモノマー（ヒドロキシル基含有モノマー）としては、例えば、８−ヒドロキシオクチル（メタ）アクリレート、６−ヒドロキシヘキシル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、ヒドロキシエチル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート類や、Ｎ−ヒドロキシ（メタ）アクリルアミド、Ｎ−ヒドロキシメチル（メタ）アクリルアミド、Ｎ−ヒドロキシエチル（メタ）アクリルアミド等のヒドロキシル基含有（メタ）アクリルアミド類などの少なくとも１種以上が挙げられる。
また、本発明に係わる粘着剤層において、粘着剤組成物に含有させるヒドロキシル基含有モノマーは、得られる粘着剤層が透明導電性フィルムのＩＴＯ表面などの腐食し易い被着体に対する腐食性に影響を与えるとされる、カルボキシル基含有モノマーの含有量を減らすための共重合性モノマーとして使用できる。そのため、ヒドロキシル基含有モノマーは、粘着剤層の粘着力を向上させ、且つ、腐食性を低減させることに役立てることができる。本発明に係わる粘着剤層において、粘着剤組成物に含有させるヒドロキシル基含有モノマーは、主成分の（メタ）アクリレートモノマー１００重量部に対して、０．１〜５重量部であることが好ましい。
Examples of the hydroxyl group-containing copolymerizable vinyl monomer (hydroxyl group-containing monomer) include 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and hydroxyethyl. Hydroxyalkyl (meth) acrylates such as (meth) acrylate, and hydroxyl group-containing (meth) acrylamides such as N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, and N-hydroxyethyl (meth) acrylamide. At least one or more such as.
Further, in the pressure-sensitive adhesive layer according to the present invention, the hydroxyl group-containing monomer contained in the pressure-sensitive adhesive composition affects the corrosiveness of the obtained pressure-sensitive adhesive layer to a corrosive adherend such as the ITO surface of a transparent conductive film. It can be used as a copolymerizable monomer for reducing the content of the carboxyl group-containing monomer, which is said to give. Therefore, the hydroxyl group-containing monomer can be useful for improving the adhesive strength of the pressure-sensitive adhesive layer and reducing the corrosiveness. In the pressure-sensitive adhesive layer according to the present invention, the hydroxyl group-containing monomer contained in the pressure-sensitive adhesive composition is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the (meth) acrylate monomer as the main component.
本発明の粘着剤層に用いる粘着剤組成物の共重合体は、（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４のアルキル（メタ）アクリレートモノマーの少なくとも１種以上を合せた主成分の（メタ）アクリレートモノマー１００重量部に対して、（Ｂ）窒素含有ビニルモノマーの１種以上を５〜５０重量部と、（Ｃ）カルボキシル基を含有する共重合性ビニルモノマー及び／又はヒドロキシル基を含有する共重合性ビニルモノマーの少なくとも１種以上を０．１〜５重量部と、を含有することが好ましい。
また、主成分の（メタ）アクリレートモノマー１００重量部に対して、カルボキシル基を含有する共重合性ビニルモノマーの１種以上を２．０重量部以下、及び／又は、ヒドロキシル基を含有する共重合性ビニルモノマーの１種以上を５．０重量部以下の割合で含有することが好ましい。
The copolymer of the pressure-sensitive adhesive composition used for the pressure-sensitive adhesive layer of the present invention is (A) a main component (meth) in which at least one or more alkyl (meth) acrylate monomers having C1 to C14 carbon atoms are combined. ) With respect to 100 parts by weight of the acrylate monomer, 5 to 50 parts by weight of (B) one or more nitrogen-containing vinyl monomers, and (C) a copolymerizable vinyl monomer containing a carboxyl group and / or a hydroxyl group are contained. It is preferable to contain at least one or more copolymerizable vinyl monomers in an amount of 0.1 to 5 parts by weight.
Further, with respect to 100 parts by weight of the (meth) acrylate monomer as the main component, 2.0 parts by weight or less of one or more copolymerizable vinyl monomers containing a carboxyl group and / or a copolymerization containing a hydroxyl group It is preferable that one or more of the sex vinyl monomers are contained in a proportion of 5.0 parts by weight or less.
共重合体の重合方法は、特に限定されるものではなく、溶液重合法、乳化重合法等、適宜、公知の重合方法が使用可能である。共重合体の重量平均分子量は、２０万〜２００万であることが好ましい。
前記共重合体は、アクリル系ポリマーであることが好ましく、（メタ）アクリル酸エステルモノマーや（メタ）アクリル酸、（メタ）アクリルアミド類などのアクリル系モノマーを５０〜１００重量％含むことが好ましい。
The polymerization method of the copolymer is not particularly limited, and known polymerization methods such as a solution polymerization method and an emulsion polymerization method can be used as appropriate. The weight average molecular weight of the copolymer is preferably 200,000 to 2,000,000.
The copolymer is preferably an acrylic polymer, and preferably contains 50 to 100% by weight of an acrylic monomer such as (meth) acrylic acid ester monomer, (meth) acrylic acid, and (meth) acrylamides.
前記粘着剤組成物は、上記の共重合体に、架橋剤や、適宜任意の添加剤を配合することで、必要とされる物性値などの特性を調整することができる。
架橋剤としては、例えば、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、ジフェニルメタンジイソシアネート、トリレンジイソシアネート、キシリレンジイソシアネート等のジイソシアネート類のビュレット変性体やイソシアヌレート変性体、トリメチロールプロパンや、グリセリン等の３価以上のポリオールとのアダクト体などのポリイソシアネート化合物、金属系キレート化合物、エポキシ化合物などの少なくとも１種以上が挙げられる。また、紫外線など光架橋により粘着剤を架橋しても良い。
架橋剤を用いて共重合体を架橋する場合、共重合体が、架橋剤と架橋反応可能な官能基（架橋剤の種類にもよるが、ヒドロキシル基やカルボキシル基など）を有することが好ましく、また、これらの官能基を側鎖に有するモノマーを含有することが好ましい。また、粘着剤組成物が、（Ｄ）架橋剤を０．０１〜５重量部を、含有することが好ましい。なお、重量部の基準は、前記共重合体における（Ａ）から（Ｃ）と同じである。
In the pressure-sensitive adhesive composition, properties such as required physical property values can be adjusted by adding a cross-linking agent and an appropriate additive to the above-mentioned copolymer.
Examples of the cross-linking agent include buretto-modified products of diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, and xylylene diisocyanate, isocyanurate-modified products, trimethylolpropane, and trivalent or higher glycerin. At least one or more of polyisocyanate compounds such as adducts with polyols, metal-based chelate compounds, and epoxy compounds can be mentioned. Further, the adhesive may be crosslinked by photocrosslinking such as ultraviolet rays.
When the copolymer is crosslinked using a cross-linking agent, it is preferable that the copolymer has a functional group capable of cross-linking with the cross-linking agent (depending on the type of the cross-linking agent, such as a hydroxyl group or a carboxyl group). Further, it is preferable to contain a monomer having these functional groups in the side chain. Further, it is preferable that the pressure-sensitive adhesive composition contains 0.01 to 5 parts by weight of the (D) cross-linking agent. The reference for parts by weight is the same as (A) to (C) in the copolymer.
その他任意の成分として、シランカップリング剤、酸化防止剤、界面活性剤、硬化促進剤、可塑剤、充填剤、架橋触媒、架橋遅延剤、硬化遅延剤、加工助剤、老化防止剤などの公知の添加剤を適宜に配合することができる。これらは、単独で、もしくは２種以上併せて用いてもよい。 Known optional components include silane coupling agents, antioxidants, surfactants, curing accelerators, plasticizers, fillers, cross-linking catalysts, cross-linking retarders, curing retarders, processing aids, anti-aging agents and the like. Additives can be appropriately blended. These may be used alone or in combination of two or more.
本発明の粘着剤層は、前記粘着剤組成物を基材や離型フィルムに塗布した後、粘着剤組成物を架橋することで得ることができる。
光学部材の層間の貼合などに用いる場合、薄い粘着剤層であることが望ましく、前記粘着剤層の厚さが１μｍ〜２０μｍであることが好ましい。また、一般に、粘着剤層の粘着力は、粘着剤層の厚さに略比例しているが、厚さが５μｍの時の粘着力が４．０（Ｎ／２５ｍｍ）以上であることが好ましい。なお、粘着剤層の厚さが５μｍでない場合、「厚さが５μｍの時の粘着力」（Ｎ／２５ｍｍ）は、粘着剤層の厚さをＴ（μｍ）、粘着剤層の粘着力をＦ（Ｎ／２５ｍｍ）として、数式「（厚さが５μｍの時の粘着力）＝５Ｆ／Ｔ」により推定することができる。
The pressure-sensitive adhesive layer of the present invention can be obtained by applying the pressure-sensitive adhesive composition to a base material or a release film, and then cross-linking the pressure-sensitive adhesive composition.
When used for bonding layers of optical members, it is desirable that the pressure-sensitive adhesive layer is thin, and the thickness of the pressure-sensitive adhesive layer is preferably 1 μm to 20 μm. In general, the adhesive strength of the pressure-sensitive adhesive layer is substantially proportional to the thickness of the pressure-sensitive adhesive layer, but the adhesive strength when the thickness is 5 μm is preferably 4.0 (N / 25 mm) or more. .. When the thickness of the pressure-sensitive adhesive layer is not 5 μm, the “adhesive strength when the thickness is 5 μm” (N / 25 mm) is that the thickness of the pressure-sensitive adhesive layer is T (μm) and the pressure-sensitive adhesive strength of the pressure-sensitive adhesive layer is T (μm). As F (N / 25 mm), it can be estimated by the formula "(adhesive strength when the thickness is 5 μm) = 5 F / T".
本発明に係わる粘着剤層を、光学部材の層間の貼合などに用いる場合、粘着剤層と光学部材との界面での光線の反射を低減させるため、屈折率の差がなるべく小さいことが望ましい。このため、前記粘着剤層の屈折率が１．４７〜１．５０であることが好ましい。 When the pressure-sensitive adhesive layer according to the present invention is used for bonding layers of optical members, it is desirable that the difference in refractive index is as small as possible in order to reduce the reflection of light rays at the interface between the pressure-sensitive adhesive layer and the optical member. .. Therefore, the refractive index of the pressure-sensitive adhesive layer is preferably 1.47 to 1.50.
本発明の粘着フィルムは、本発明の粘着剤層を、基材又は離型フィルムの片面上に形成することで製造することができる。
粘着剤層の形成に用いる基材フィルムや、粘着面を保護する離型フィルム（セパレーター）としては、ポリエステルフィルムなどの樹脂フィルム等を用いることができる。
基材フィルムには、樹脂フィルムの粘着剤層が形成された側とは反対面に、シリコーン系、フッ素系の離型剤やコート剤、シリカ微粒子等による防汚処理、帯電防止剤の塗布や練り込み等による帯電防止処理を施すことができる。
The pressure-sensitive adhesive film of the present invention can be produced by forming the pressure-sensitive adhesive layer of the present invention on one side of a base material or a release film.
As the base film used for forming the pressure-sensitive adhesive layer and the release film (separator) for protecting the pressure-sensitive adhesive surface, a resin film such as a polyester film can be used.
On the base film, on the side opposite to the side where the adhesive layer of the resin film is formed, antifouling treatment with silicone-based or fluorine-based mold release agent or coating agent, silica fine particles, etc., application of antistatic agent, etc. Antistatic treatment such as kneading can be applied.
離型フィルムには、粘着剤層の粘着面と合わされる側の面に、シリコーン系、フッ素系の離型剤などにより離型処理が施される。
１つの粘着剤層の両面に、それぞれ離型フィルムの離型処理が施された面を合わせることで、「離型フィルム／粘着剤層／離型フィルム」の構成とすることもできる。この場合、両側の離型フィルムを、順次、あるいは同時に剥離して粘着面を表出することにより、光学フィルム等の光学部材と貼合可能になる。光学フィルムとしては、偏光フィルム、位相差フィルム、反射防止フィルム、防眩（アンチグレア）フィルム、紫外線吸収フィルム、赤外線吸収フィルム、光学補償フィルム、輝度向上フィルム等が挙げられる。
The release film is subjected to a release treatment with a silicone-based or fluorine-based release agent or the like on the surface of the pressure-sensitive adhesive layer that is combined with the adhesive surface.
It is also possible to form a "release film / adhesive layer / release film" by combining the surfaces of the release film that have been subjected to the release treatment on both sides of one pressure-sensitive adhesive layer. In this case, the release films on both sides are peeled off sequentially or at the same time to expose the adhesive surface, so that the release films can be bonded to an optical member such as an optical film. Examples of the optical film include a polarizing film, a retardation film, an antireflection film, an antiglare film, an ultraviolet absorbing film, an infrared absorbing film, an optical compensation film, and a brightness improving film.
本発明の粘着フィルムは、偏光板を主とする液晶表示装置の周辺部材用の各種光学フィルム、タッチパネル用の各種光学フィルム、電子ペーパー用の各種光学フィルム、有機ＥＬ用の各種光学フィルム等の貼り合せに用いることができる。
また、これらの光学フィルムの少なくとも一方の面に、前記粘着剤層が積層されてなる粘着剤層付き光学フィルムとすることができる。具体的には、「光学フィルム／粘着剤層／光学フィルム」、「光学フィルム／粘着剤層／離型フィルム」、「光学フィルム／粘着剤層」、「光学フィルム／粘着剤層／光学フィルム／粘着剤層／光学フィルム」、「光学フィルム／粘着剤層／光学フィルム／粘着剤層／離型フィルム」、「離型フィルム／粘着剤層／光学フィルム／粘着剤層／離型フィルム」等の構成が挙げられる。
例えば、「光学フィルム／粘着剤層／離型フィルム」のように、離型フィルムで保護された粘着剤層を有する場合、離型フィルムを剥がして、「光学フィルム／粘着剤層」のように粘着剤層を表出させ、他の光学フィルムと貼合することにより、粘着剤層が層間の貼合に用いられた「光学フィルム／粘着剤層／光学フィルム」のような構成が得られる。
The adhesive film of the present invention is affixed with various optical films for peripheral members of liquid crystal display devices, mainly polarizing plates, various optical films for touch panels, various optical films for electronic paper, various optical films for organic EL, and the like. It can be used for matching.
Further, an optical film with an adhesive layer obtained by laminating the adhesive layer on at least one surface of these optical films can be obtained. Specifically, "optical film / adhesive layer / optical film", "optical film / adhesive layer / release film", "optical film / adhesive layer", "optical film / adhesive layer / optical film /""Adhesive film / optical film", "optical film / adhesive layer / optical film / adhesive layer / release film", "release film / adhesive layer / optical film / adhesive layer / release film", etc. The configuration can be mentioned.
For example, when having an adhesive layer protected by a release film such as "optical film / adhesive layer / release film", the release film is peeled off to form "optical film / adhesive layer". By exposing the pressure-sensitive adhesive layer and bonding it with another optical film, a configuration such as "optical film / pressure-sensitive adhesive layer / optical film" in which the pressure-sensitive adhesive layer is used for bonding between layers can be obtained.
以下、実施例をもって本発明を具体的に説明する。 Hereinafter, the present invention will be specifically described with reference to Examples.
＜アクリル共重合体の製造＞
［参考例１］
撹拌機、温度計、還流冷却器及び窒素導入管を備えた反応装置に、窒素ガスを導入して、反応装置内の空気を窒素ガスで置換した。その後、反応装置にブチルアクリレート７０重量部、メチルアクリレート３０重量部、Ｎ−メチルピロリドン１０重量部、アクリル酸１．５重量部、６−ヒドロキシヘキシルアクリレート０．５重量部とともに溶剤（酢酸エチル）を６０重量部加えた。その後、重合開始剤としてアゾビスイソブチロニトリル０．１重量部を２時間かけて滴下させ、６５℃で６時間反応させ、重量平均分子量５０万の、参考例１に用いるアクリル共重合体溶液１を得た。アクリル共重合体の一部を採取し、後述する酸価の測定試料として用いた。
［実施例３〜５、参考例２〜３及び比較例１〜３］
モノマーの組成を各々、表１の（Ａ）、（Ｂ）、（Ｃ−１）、（Ｃ−２）の記載のようにする以外は、上記の参考例１に用いるアクリル共重合体溶液１と同様にして、実施例３〜５、参考例２〜３及び比較例１〜３に用いるアクリル共重合体溶液を得た。なお、特に測定結果を示さないが、実施例３〜５、参考例２〜３及び比較例１〜３のアクリル共重合体溶液に含まれる共重合体の重量平均分子量は、２０万〜２００万の範囲内である。
<Manufacturing of acrylic copolymer>
[ Reference example 1]
Nitrogen gas was introduced into a reactor equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen introduction pipe, and the air in the reactor was replaced with nitrogen gas. Then, a solvent (ethyl acetate) was added to the reactor together with 70 parts by weight of butyl acrylate, 30 parts by weight of methyl acrylate, 10 parts by weight of N-methylpyrrolidone, 1.5 parts by weight of acrylic acid, and 0.5 parts by weight of 6-hydroxyhexyl acrylate. 60 parts by weight was added. Then, 0.1 part by weight of azobisisobutyronitrile as a polymerization initiator was added dropwise over 2 hours and reacted at 65 ° C. for 6 hours to obtain an acrylic copolymer solution having a weight average molecular weight of 500,000 and used in Reference Example 1. I got 1. A part of the acrylic copolymer was collected and used as a sample for measuring the acid value described later.
[Examples 3 to 5, Reference Examples 2 to 3 and Comparative Examples 1 to 3]
Acrylic copolymer solution 1 used in Reference Example 1 above, except that the composition of the monomers is as described in Table 1, (A), (B), (C-1), and (C-2), respectively. In the same manner as in the above, the acrylic copolymer solutions used in Examples 3 to 5, Reference Examples 2 to 3 and Comparative Examples 1 to 3 were obtained. Although the measurement results are not particularly shown, the weight average molecular weight of the copolymers contained in the acrylic copolymer solutions of Examples 3 to 5, Reference Examples 2 to 3 and Comparative Examples 1 to 3 is 200,000 to 2 million. Is within the range of.
＜粘着剤組成物、粘着剤層及び粘着フィルムの製造＞
［参考例１］
上記のとおり製造した参考例１のアクリル共重合体溶液１に対して、コロネートＬ−４５（トリレンジイソシアネート（ＴＤＩ）化合物のアダクト体）０．３重量部を加えて撹拌混合して参考例１の粘着剤組成物を得た。この粘着剤組成物をシリコーン樹脂コートされたポリエチレンテレフタレート（ＰＥＴ）フィルムからなる剥離フィルムの上に塗布後、９０℃で乾燥することによって溶剤を除去した後、２３℃、５０％ＲＨの雰囲気下で７日間エージングすることにより、粘着剤組成物を架橋してなる粘着剤層を、剥離フィルムの片面上に有する、参考例１の粘着フィルムを得た。
［実施例３〜５、参考例２〜３及び比較例１〜３］
添加剤の組成を各々、表１の（Ｄ）の記載のようにする以外は、上記の参考例１の粘着フィルムと同様にして、実施例３〜５、参考例２〜３及び比較例１〜３の粘着フィルムを得た。
<Manufacturing of adhesive composition, adhesive layer and adhesive film>
[ Reference example 1]
To the acrylic copolymer solution 1 of Reference Example 1 produced as described above, 0.3 part by weight of coronate L-45 (adductent of toluene diisocyanate (TDI) compound) was added and mixed by stirring, and Reference Example 1 was performed. The pressure-sensitive adhesive composition of the above was obtained. This pressure-sensitive adhesive composition is applied onto a release film made of a polyethylene terephthalate (PET) film coated with a silicone resin, and then dried at 90 ° C. to remove the solvent, and then in an atmosphere of 23 ° C. and 50% RH. By aging for 7 days, the pressure-sensitive adhesive film of Reference Example 1 having the pressure-sensitive adhesive layer formed by cross-linking the pressure-sensitive adhesive composition on one side of the release film was obtained.
[Examples 3 to 5, Reference Examples 2 to 3 and Comparative Examples 1 to 3]
Examples 3 to 5, Reference Examples 2 and 3 and Comparative Example 1 are the same as those of the above-mentioned adhesive film of Reference Example 1 except that the composition of the additive is as shown in (D) of Table 1. An adhesive film of ~ 3 was obtained.
表１では、（Ａ）群の合計を１００重量部として求めた、（Ｂ）群から（Ｄ）群までの添加割合として、重量部の数値を括弧で囲んで示す。
また、表１に用いた各成分の略記号の化合物名を、表２に示す。なお、コロネート（登録商標）Ｌ−４５は日本ポリウレタン工業株式会社の商品名であり、Ｄ−１１０Ｎは三井化学株式会社の商品名である。ＴＤＩはトリレンジイソシアネートを意味し、ＸＤＩはキシリレンジイソシアネートを意味する。
In Table 1, the total of the (A) group was determined as 100 parts by weight, and the values of the parts by weight are shown in parentheses as the addition ratios from the (B) group to the (D) group.
Table 2 shows the compound names of the abbreviations of each component used in Table 1. Coronate (registered trademark) L-45 is a trade name of Nippon Polyurethane Industry Co., Ltd., and D-110N is a trade name of Mitsui Chemicals Co., Ltd. TDI means tolylene diisocyanate and XDI means xylylene diisocyanate.
＜試験方法及び評価＞
実施例３〜５、参考例１〜３及び比較例１〜３における粘着フィルムから剥離フィルム（シリコーン樹脂コートされたＰＥＴフィルム）を剥がして、粘着剤層を表出させ、偏光板（フィルム）の片面に粘着剤層を転写した。
<Test method and evaluation>
The release film (the PET film coated with silicone resin) was peeled off from the adhesive films of Examples 3 to 5, Reference Examples 1 to 3 and Comparative Examples 1 to 3, and the adhesive layer was exposed to expose the polarizing plate (film). The pressure-sensitive adhesive layer was transferred to one side.
＜粘着力の測定方法＞
厚さ１８０μｍの偏光板（フィルム）の片面に粘着剤層を転写して、試料となる粘着フィルム（粘着剤層付き光学フィルム）を得た。
粘着フィルムをソーダライムガラスのアセトンで洗浄した非錫面に圧着ロールで貼り合わせ、５０℃、０．５ＭＰａ×２０分間の条件でオートクレーブ処理した後、２３℃×５０％ＲＨの雰囲気下に戻し、１時間経過後の粘着フィルムの剥離強度を引張試験機によって、ＪＩＳ Ｚ０２３７「粘着テープ・粘着シート試験方法」に準拠して測定し、１８０°方向に３００ｍｍ／ｍｉｎの速度で剥離した時の剥離強度を、粘着フィルムの粘着剤層の粘着力とした。
<Measurement method of adhesive strength>
The pressure-sensitive adhesive layer was transferred to one side of a polarizing plate (film) having a thickness of 180 μm to obtain a sample pressure-sensitive adhesive film (optical film with a pressure-sensitive adhesive layer).
The adhesive film was attached to a non-tin surface of soda lime glass washed with acetone with a pressure-bonding roll, autoclaved at 50 ° C. for 0.5 MPa × 20 minutes, and then returned to an atmosphere of 23 ° C. × 50% RH. The peeling strength of the adhesive film after 1 hour has been measured by a tensile tester in accordance with JIS Z0237 "Adhesive Tape / Adhesive Sheet Test Method", and the peeling strength when peeled at a speed of 300 mm / min in the 180 ° direction. Was defined as the adhesive strength of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film.
＜密着性の試験方法＞
粘着力を測定した後の試料である粘着フィルムの粘着剤層を目視で確認し、基材層の偏光板（フィルム）からの脱落状態で密着性を判断した。
○・・基材層から粘着剤層が全く脱落していない。
△・・基材層から粘着剤層が一部浮き上がり脱落している。
×・・基材層から粘着剤層が脱落して、被着体のガラスに転着している。
<Adhesion test method>
The pressure-sensitive adhesive layer of the pressure-sensitive adhesive film, which was a sample after measuring the adhesive strength, was visually confirmed, and the adhesion was judged when the base material layer was removed from the polarizing plate (film).
○ ・ ・ The adhesive layer has not fallen off from the base material layer at all.
Δ ・ ・ A part of the adhesive layer is lifted and dropped from the base material layer.
× ・ ・ The adhesive layer has fallen off from the base material layer and is transferred to the glass of the adherend.
＜耐久性の試験方法＞
粘着力の測定と同様の方法で作成した１０ｃｍ角の粘着フィルムを、同様の方法でソーダライムガラスの非錫面に貼り合わせて作成した試料を、６０℃×９０％ＲＨの雰囲気下に２５０時間放置後、２３℃×５０％ＲＨ雰囲気下に取り出し、１時間後に粘着フィルムの状態を目視で観察して耐久性を判断した。
○・・粘着フィルムの剥がれ及び発泡が全くない。
△・・粘着フィルムの一部に剥がれ及び発泡が発生している。
×・・粘着フィルムの全体に剥がれ及び発泡が発生している。
<Durability test method>
A sample prepared by laminating a 10 cm square adhesive film prepared by the same method as the measurement of adhesive strength on the non-tin surface of soda lime glass by the same method was prepared in an atmosphere of 60 ° C. × 90% RH for 250 hours. After being left to stand, it was taken out in an atmosphere of 23 ° C. × 50% RH, and after 1 hour, the state of the adhesive film was visually observed to judge the durability.
○ ・ ・ There is no peeling or foaming of the adhesive film.
Δ ・ ・ Peeling and foaming occur in a part of the adhesive film.
× ・ ・ Peeling and foaming occur on the entire adhesive film.
＜屈折率の測定方法＞
２３℃の粘着剤層の屈折率を、アッベ式屈折計（メーカ名：ＥＲＭＡ、型式：ＥＲ−２Ｓ）で測定する。
<Measurement method of refractive index>
The refractive index of the pressure-sensitive adhesive layer at 23 ° C. is measured with an Abbe refractometer (manufacturer name: ERMA, model: ER-2S).
表３に、評価結果を示す。 Table 3 shows the evaluation results.
実施例３〜５の粘着フィルムは、厚さ５μｍの粘着剤層の粘着力が４．０Ｎ／２５ｍｍ以上であり、粘着剤層の屈折率が１．４７〜１．５０の範囲内であり、密着性、及び耐久性にも優れていた。すなわち、実施例３〜５の粘着フィルムでは、要求事項および問題を克服することができた。
表４に、参考例１、実施例３の粘着剤組成物を用いて、同様の方法で製造した、厚さ３μｍ、５μｍ、１０μｍ、１５μｍ、２０μｍの粘着剤層の粘着フィルムについて、粘着力を測定した結果を示す。参考例１、実施例３の粘着剤組成物を用いた粘着剤層の粘着力は、一般に知られているように、粘着剤層の厚さに略比例していることが分かる。
In the adhesive films of Examples 3 to 5 , the adhesive strength of the adhesive layer having a thickness of 5 μm is 4.0 N / 25 mm or more, and the refractive index of the adhesive layer is in the range of 1.47 to 1.50. It was also excellent in adhesion and durability. That is, the adhesive films of Examples 3 to 5 were able to overcome the requirements and problems.
Table 4, Reference Example 1, using the adhesive composition of Example 3 was prepared in a similar manner, a thickness of 3 [mu] m, 5 [mu] m, 10 [mu] m, 15 [mu] m, the adhesive film 20μm of the pressure-sensitive adhesive layer, the adhesive strength The measurement result is shown. It can be seen that the adhesive strength of the pressure-sensitive adhesive layer using the pressure-sensitive adhesive compositions of Reference Examples 1 and 3 is substantially proportional to the thickness of the pressure-sensitive adhesive layer, as is generally known.
比較例１の粘着フィルムは、粘着剤組成物に窒素含有モノマーを含まないためか、厚さ５μｍの粘着剤層の粘着力が弱い。また、粘着剤層の屈折率が低く、密着性、及び耐久性にも劣っていた。
比較例２の粘着フィルムは、粘着剤組成物にカルボキシル基を含有する共重合性ビニルモノマーの配合量が多すぎるためか、厚さ５μｍの粘着剤層の粘着力が弱い。また、粘着剤層の屈折率が低く、密着性、及び耐久性にも、やや劣っていた。
比較例３の粘着フィルムは、粘着剤組成物にカルボキシル基を含有する共重合性ビニルモノマーもヒドロキシル基を含有する共重合性ビニルモノマーも含まないためか、厚さ５μｍの粘着剤層の粘着力が弱い。また、粘着剤層の屈折率が低く、密着性、及び耐久性にも劣っていた。
このように、比較例１〜３の粘着フィルムでは、従来の要求事項および問題を克服することができなかった。
The adhesive film of Comparative Example 1 has a weak adhesive force of the adhesive layer having a thickness of 5 μm, probably because the adhesive composition does not contain a nitrogen-containing monomer. In addition, the refractive index of the pressure-sensitive adhesive layer was low, and the adhesiveness and durability were also inferior.
In the pressure-sensitive adhesive film of Comparative Example 2, the pressure-sensitive adhesive strength of the pressure-sensitive adhesive layer having a thickness of 5 μm is weak, probably because the amount of the copolymerizable vinyl monomer containing a carboxyl group in the pressure-sensitive adhesive composition is too large. In addition, the refractive index of the pressure-sensitive adhesive layer was low, and the adhesiveness and durability were slightly inferior.
The adhesive film of Comparative Example 3 does not contain a copolymerizable vinyl monomer containing a carboxyl group or a copolymerizable vinyl monomer containing a hydroxyl group in the pressure-sensitive adhesive composition, and probably because the pressure-sensitive adhesive composition does not contain the adhesive strength of the pressure-sensitive adhesive layer having a thickness of 5 μm. Is weak. In addition, the refractive index of the pressure-sensitive adhesive layer was low, and the adhesiveness and durability were also inferior.
As described above, the adhesive films of Comparative Examples 1 to 3 could not overcome the conventional requirements and problems.
Claims (5)
前記アクリル系ポリマーが、
（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４のアルキル（メタ）アクリレートモノマーの少なくとも１種以上を合せた７０〜９５重量部と、芳香族基を含有する（メタ）アクリレートモノマーの少なくとも１種以上を合せた５〜３０重量部との合計１００重量部に対して、
（Ｂ）ヒドロキシル基を含有しない窒素含有ビニルモノマーの少なくとも１種以上を５〜５０重量部と、
（Ｃ）カルボキシル基を含有する共重合性ビニルモノマーの少なくとも１種以上を０．１〜２重量部、及び／又は、ヒドロキシル基を含有する共重合性ビニルモノマーの少なくとも１種以上を０．１〜５重量部と、
を共重合させた重量平均分子量２０万〜２００万の共重合体からなり、
前記粘着剤組成物が、前記（Ａ）アルキル基の炭素数がＣ１〜Ｃ１４のアルキル（メタ）アクリレートモノマーの少なくとも１種以上を合せた７０〜９５重量部と、芳香族基を含有する（メタ）アクリレートモノマーの少なくとも１種以上を合せた５〜３０重量部との合計１００重量部に対して、前記（Ｄ）架橋剤を０．０１〜５重量部の割合で含有してなり、
前記粘着剤層の厚さが１μｍ〜２０μｍであり、
前記粘着剤層の屈折率が１．４７〜１．５０であり、
被着体に、前記粘着剤層を貼り合せる前に、エージング処理が施されており、被着体に、前記粘着剤層を貼り合せた後には、エージング処理を施す必要がないことを特徴とする粘着剤層。 In the pressure-sensitive adhesive layer formed by cross-linking a pressure-sensitive adhesive composition containing an acrylic polymer and (D) a cross-linking agent.
The acrylic polymer
(A) 70 to 95 parts by weight of at least one alkyl (meth) acrylate monomer having an alkyl group having C1 to C14, and at least one (meth) acrylate monomer containing an aromatic group. For a total of 100 parts by weight, including 5 to 30 parts by weight
(B) At least one kind of nitrogen-containing vinyl monomer containing no hydroxyl group is added to 5 to 50 parts by weight.
(C) 0.1 to 2 parts by weight of at least one or more copolymerizable vinyl monomer containing a carboxyl group, and / or 0.1 at least one or more copolymerizable vinyl monomer containing a hydroxyl group. ~ 5 parts by weight,
Consists of a copolymer having a weight average molecular weight of 200,000 to 2 million obtained by copolymerizing
The pressure-sensitive adhesive composition contains 70 to 95 parts by weight of the (A) alkyl group having at least one or more of alkyl (meth) acrylate monomers having C1 to C14 carbon atoms and an aromatic group (meth). ) The cross-linking agent (D) is contained in an amount of 0.01 to 5 parts by weight with respect to 100 parts by weight in total including 5 to 30 parts by weight of at least one of the acrylate monomers.
The thickness of the pressure-sensitive adhesive layer is 1 μm to 20 μm.
The refractive index of the pressure-sensitive adhesive layer is 1.47 to 1.50.
The feature is that the aging treatment is applied to the adherend before the adhesive layer is attached, and it is not necessary to apply the aging treatment after the adhesive layer is attached to the adherend. Adhesive layer to do.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020000437A JP6920483B2 (en) | 2018-12-27 | 2020-01-06 | Adhesive layer and adhesive film |
| JP2021120628A JP7193588B2 (en) | 2018-12-27 | 2021-07-21 | Adhesive layer and adhesive film |
| JP2022196037A JP7522814B2 (en) | 2018-12-27 | 2022-12-08 | Pressure-sensitive adhesive layer, pressure-sensitive adhesive film, and optical film with pressure-sensitive adhesive layer |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018245415A JP6644129B2 (en) | 2018-12-27 | 2018-12-27 | Adhesive layer and adhesive film |
| JP2020000437A JP6920483B2 (en) | 2018-12-27 | 2020-01-06 | Adhesive layer and adhesive film |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2018245415A Division JP6644129B2 (en) | 2018-12-27 | 2018-12-27 | Adhesive layer and adhesive film |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2021120628A Division JP7193588B2 (en) | 2018-12-27 | 2021-07-21 | Adhesive layer and adhesive film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2020073683A JP2020073683A (en) | 2020-05-14 |
| JP6920483B2 true JP6920483B2 (en) | 2021-08-18 |
Family
ID=66441809
Family Applications (4)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2018245415A Active JP6644129B2 (en) | 2018-12-27 | 2018-12-27 | Adhesive layer and adhesive film |
| JP2020000437A Active JP6920483B2 (en) | 2018-12-27 | 2020-01-06 | Adhesive layer and adhesive film |
| JP2021120628A Active JP7193588B2 (en) | 2018-12-27 | 2021-07-21 | Adhesive layer and adhesive film |
| JP2022196037A Active JP7522814B2 (en) | 2018-12-27 | 2022-12-08 | Pressure-sensitive adhesive layer, pressure-sensitive adhesive film, and optical film with pressure-sensitive adhesive layer |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2018245415A Active JP6644129B2 (en) | 2018-12-27 | 2018-12-27 | Adhesive layer and adhesive film |
Family Applications After (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2021120628A Active JP7193588B2 (en) | 2018-12-27 | 2021-07-21 | Adhesive layer and adhesive film |
| JP2022196037A Active JP7522814B2 (en) | 2018-12-27 | 2022-12-08 | Pressure-sensitive adhesive layer, pressure-sensitive adhesive film, and optical film with pressure-sensitive adhesive layer |
Country Status (1)
| Country | Link |
|---|---|
| JP (4) | JP6644129B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6644129B2 (en) * | 2018-12-27 | 2020-02-12 | 藤森工業株式会社 | Adhesive layer and adhesive film |
Family Cites Families (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2386847A1 (en) | 1999-10-28 | 2001-05-03 | Cheryl L. Moore | High refractive index pressure-sensitive adhesives |
| JP4640740B2 (en) | 2000-12-04 | 2011-03-02 | 日東電工株式会社 | Pressure-sensitive adhesive composition, pressure-sensitive adhesive sheet, and optical film |
| JP2002322439A (en) | 2001-04-10 | 2002-11-08 | Three M Innovative Properties Co | Printing tape and releasable liner |
| JP2007297452A (en) | 2006-04-28 | 2007-11-15 | Daio Paper Corp | Adhesive sheet |
| JP5340649B2 (en) | 2007-10-22 | 2013-11-13 | 日東電工株式会社 | Optical film pressure-sensitive adhesive composition, optical film pressure-sensitive adhesive layer, production method thereof, pressure-sensitive adhesive optical film, and image display device |
| JP5379409B2 (en) * | 2008-02-15 | 2013-12-25 | 日東電工株式会社 | Adhesive composition for optical film, adhesive optical film, and image display device |
| JP5540394B2 (en) * | 2008-05-12 | 2014-07-02 | サイデン化学株式会社 | Adhesive composition for polarizing plate |
| JP5394661B2 (en) | 2008-06-17 | 2014-01-22 | リンテック株式会社 | Adhesive sheet |
| JP5544954B2 (en) | 2010-03-18 | 2014-07-09 | サイデン化学株式会社 | Optical pressure-sensitive adhesive composition |
| JP5622427B2 (en) | 2010-04-19 | 2014-11-12 | 日東電工株式会社 | Optical member pressure-sensitive adhesive composition, optical member pressure-sensitive adhesive layer, pressure-sensitive adhesive optical member, and image display device |
| JP5800469B2 (en) * | 2010-05-27 | 2015-10-28 | 綜研化学株式会社 | Adhesive composition for optical member and adhesive sheet |
| WO2012050049A1 (en) * | 2010-10-12 | 2012-04-19 | 日本合成化学工業株式会社 | Adhesive composition for optical components, adhesive for optical components, optical component with adhesive layer, and image display device |
| JP2012135951A (en) * | 2010-12-27 | 2012-07-19 | Mitsubishi Plastics Inc | Polyester film for double-sided adhesive tape |
| JP5842439B2 (en) * | 2011-03-10 | 2016-01-13 | 住友化学株式会社 | Optical film with adhesive and optical laminate using the same |
| JP5887066B2 (en) * | 2011-05-17 | 2016-03-16 | 綜研化学株式会社 | Adhesive composition for optical member and processed product thereof |
| JP2012021164A (en) | 2011-09-15 | 2012-02-02 | Hitachi Chem Co Ltd | Adhesive film |
| JP6013898B2 (en) | 2012-12-17 | 2016-10-25 | 藤森工業株式会社 | Adhesive layer and adhesive film |
| JP6057693B2 (en) | 2012-12-17 | 2017-01-11 | 藤森工業株式会社 | Adhesive layer and adhesive film |
| JP6207109B2 (en) | 2016-08-19 | 2017-10-04 | 藤森工業株式会社 | Adhesive layer and adhesive film |
| JP6507394B2 (en) | 2017-09-01 | 2019-05-08 | 藤森工業株式会社 | Adhesive layer and adhesive film |
| JP6644129B2 (en) * | 2018-12-27 | 2020-02-12 | 藤森工業株式会社 | Adhesive layer and adhesive film |
| JP6644128B2 (en) | 2018-12-27 | 2020-02-12 | 藤森工業株式会社 | Adhesive layer and adhesive film |
-
2018
- 2018-12-27 JP JP2018245415A patent/JP6644129B2/en active Active
-
2020
- 2020-01-06 JP JP2020000437A patent/JP6920483B2/en active Active
-
2021
- 2021-07-21 JP JP2021120628A patent/JP7193588B2/en active Active
-
2022
- 2022-12-08 JP JP2022196037A patent/JP7522814B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP6644129B2 (en) | 2020-02-12 |
| JP2023016999A (en) | 2023-02-02 |
| JP7522814B2 (en) | 2024-07-25 |
| JP2021169627A (en) | 2021-10-28 |
| JP7193588B2 (en) | 2022-12-20 |
| JP2019070149A (en) | 2019-05-09 |
| JP2020073683A (en) | 2020-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6013898B2 (en) | Adhesive layer and adhesive film | |
| JP6026260B2 (en) | Adhesive layer and adhesive film | |
| JP2024114915A (en) | Pressure-sensitive adhesive layer, pressure-sensitive adhesive film, and optical film with pressure-sensitive adhesive layer | |
| JP7522814B2 (en) | Pressure-sensitive adhesive layer, pressure-sensitive adhesive film, and optical film with pressure-sensitive adhesive layer | |
| JP6717884B2 (en) | Adhesive layer and adhesive film | |
| JP6644128B2 (en) | Adhesive layer and adhesive film | |
| JP6744289B2 (en) | Adhesive layer and adhesive film | |
| JP6507394B2 (en) | Adhesive layer and adhesive film | |
| JP6207109B2 (en) | Adhesive layer and adhesive film | |
| JP6367885B2 (en) | Adhesive layer and adhesive film | |
| JP6270972B2 (en) | Adhesive layer and adhesive film | |
| JP6810185B2 (en) | Adhesive layer and adhesive film | |
| JP6871308B2 (en) | Adhesive layer and adhesive film | |
| JP7144501B2 (en) | Adhesive layer and adhesive film | |
| JP6793233B2 (en) | Light diffusion adhesive film | |
| JP7019782B2 (en) | Light diffusion adhesive film | |
| JP6508685B2 (en) | Adhesive layer and adhesive film | |
| JP2022058817A (en) | Light-diffusing adhesive film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20200106 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20210112 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20210222 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20210622 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20210726 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6920483 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |