JP5683370B2 - Adhesive composition and surface protective film - Google Patents
Adhesive composition and surface protective film Download PDFInfo
- Publication number
- JP5683370B2 JP5683370B2 JP2011096011A JP2011096011A JP5683370B2 JP 5683370 B2 JP5683370 B2 JP 5683370B2 JP 2011096011 A JP2011096011 A JP 2011096011A JP 2011096011 A JP2011096011 A JP 2011096011A JP 5683370 B2 JP5683370 B2 JP 5683370B2
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- Prior art keywords
- meth
- acrylate
- weight
- pressure
- sensitive adhesive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000853 adhesive Substances 0.000 title claims description 65
- 230000001070 adhesive effect Effects 0.000 title claims description 65
- 239000000203 mixture Substances 0.000 title claims description 41
- 230000001681 protective effect Effects 0.000 title description 47
- -1 isocyanate compound Chemical class 0.000 claims description 87
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 58
- 239000000178 monomer Substances 0.000 claims description 49
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 45
- 238000004132 cross linking Methods 0.000 claims description 40
- 229920001577 copolymer Polymers 0.000 claims description 28
- 239000010410 layer Substances 0.000 claims description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 15
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 239000012948 isocyanate Substances 0.000 claims description 13
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 claims description 8
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical class CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 4
- 230000000052 comparative effect Effects 0.000 description 15
- 230000003287 optical effect Effects 0.000 description 15
- 239000012790 adhesive layer Substances 0.000 description 12
- 239000003431 cross linking reagent Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000004721 Polyphenylene oxide Substances 0.000 description 6
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 6
- 229920006243 acrylic copolymer Polymers 0.000 description 6
- 238000011109 contamination Methods 0.000 description 6
- 239000004973 liquid crystal related substance Substances 0.000 description 6
- 229920000570 polyether Polymers 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 230000003373 anti-fouling effect Effects 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000005056 polyisocyanate Substances 0.000 description 4
- 229920001228 polyisocyanate Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920002799 BoPET Polymers 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000002216 antistatic agent Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 229920002050 silicone resin Polymers 0.000 description 3
- 150000003606 tin compounds Chemical class 0.000 description 3
- 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
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 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
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- CVBUKMMMRLOKQR-UHFFFAOYSA-N 1-phenylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1=CC=CC=C1 CVBUKMMMRLOKQR-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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-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
- JSCDRVVVGGYHSN-UHFFFAOYSA-N 8-hydroxyoctyl prop-2-enoate Chemical compound OCCCCCCCCOC(=O)C=C JSCDRVVVGGYHSN-UHFFFAOYSA-N 0.000 description 1
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000000903 blocking effect Effects 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
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 210000002858 crystal cell Anatomy 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
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- LQRUPWUPINJLMU-UHFFFAOYSA-N dioctyl(oxo)tin Chemical compound CCCCCCCC[Sn](=O)CCCCCCCC LQRUPWUPINJLMU-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- KCHWKBCUPLJWJA-UHFFFAOYSA-N dodecyl 3-oxobutanoate Chemical compound CCCCCCCCCCCCOC(=O)CC(C)=O KCHWKBCUPLJWJA-UHFFFAOYSA-N 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 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
- 238000001879 gelation Methods 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
- NDOGLIPWGGRQCO-UHFFFAOYSA-N hexane-2,4-dione Chemical compound CCC(=O)CC(C)=O NDOGLIPWGGRQCO-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
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000008040 ionic compounds Chemical class 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
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002780 morpholines Chemical class 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
- BMOMBHKAYGMGCR-UHFFFAOYSA-N octadecyl 3-oxobutanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CC(C)=O BMOMBHKAYGMGCR-UHFFFAOYSA-N 0.000 description 1
- IKYDDBGYKFPTGF-UHFFFAOYSA-N octyl 3-oxobutanoate Chemical compound CCCCCCCCOC(=O)CC(C)=O IKYDDBGYKFPTGF-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000004885 piperazines Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 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
- 238000012545 processing Methods 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
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 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 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
Description
本発明は、液晶ディスプレイの製造工程に利用される表面保護フィルムに関するものである。さらに詳しくは、液晶ディスプレイを構成する偏光板、位相差板などの光学部材の表面に貼着することにより、偏光板、位相差板などの光学部材の表面を保護するために使用される表面保護フィルム用の粘着剤組成物、及びそれを用いた表面保護フィルムに関するものである。 The present invention relates to a surface protective film used in a manufacturing process of a liquid crystal display. More specifically, surface protection used to protect the surface of optical members such as polarizing plates and retardation plates by sticking to the surface of optical members such as polarizing plates and retardation plates constituting liquid crystal displays. The present invention relates to a pressure-sensitive adhesive composition for a film and a surface protective film using the same.
従来から、液晶ディスプレイを構成する部材である偏光板、位相差板などの光学部材の製造工程においては、光学部材の表面を一時的に保護するための表面保護フィルムが貼着される。このような表面保護フィルムは、光学部材を製造する工程のみに使用され、光学部材を液晶ディスプレイに組み込む時点で、光学部材から剥離して除去される。このような光学部材の表面を保護するための表面保護フィルムは、製造工程においてのみに使用されるため、一般には、工程フィルムと呼ばれることもある。 Conventionally, in a manufacturing process of an optical member such as a polarizing plate and a retardation plate that are members constituting a liquid crystal display, a surface protective film for temporarily protecting the surface of the optical member is attached. Such a surface protective film is used only in the process of manufacturing the optical member, and is peeled off from the optical member when the optical member is incorporated into the liquid crystal display. Since such a surface protective film for protecting the surface of the optical member is used only in the production process, it may be generally called a process film.
このように光学部材を製造する工程において使用される表面保護フィルムは、光学的に透明性を有するポリエチレンテレフタレート（ＰＥＴ）樹脂フィルムの片面に粘着剤層が形成されているが、光学部材に貼り合わせるまで、その粘着剤層を保護するための剥離処理された剥離フィルムが、粘着剤層の上に貼り合わされている。
また、偏光板、位相差板などの光学部材は、表面保護フィルムを貼り合わされた状態で、液晶表示板の表示能力、色相、コントラスト、異物混入などの光学的評価を伴う製品検査を行うため、表面保護フィルムに対する要求性能としては、粘着剤層に気泡や異物が付着していないことが求められている。
また、偏光板、位相差板などの光学部材に表面保護フィルムを貼り合わせるときに、各種の理由により、一旦、表面保護フィルムを剥がして、再度、表面保護フィルムを貼り直すことがあり、そのときに被着体の光学部材から剥がし易いこと（リワーク性）が求められている。
また、最終的に偏光板、位相差板などの光学部材から表面保護フィルムを剥がすときには、速やかに剥離できることが求められている。いわゆる、高速剥離によっても、速やかに剥離できるように、粘着力が剥離速度によっても変化が少ないことが求められている。
In this way, the surface protective film used in the process of manufacturing the optical member has an adhesive layer formed on one side of an optically transparent polyethylene terephthalate (PET) resin film, but is bonded to the optical member. Until then, the release film subjected to the release treatment for protecting the pressure-sensitive adhesive layer is bonded onto the pressure-sensitive adhesive layer.
In addition, optical members such as polarizing plates and retardation plates are subjected to product inspection with optical evaluation such as display capability, hue, contrast, and foreign matter mixing of the liquid crystal display plate in a state where the surface protective film is bonded. As the required performance for the surface protective film, it is required that no bubbles or foreign substances adhere to the pressure-sensitive adhesive layer.
In addition, when a surface protective film is bonded to an optical member such as a polarizing plate or a retardation plate, for various reasons, the surface protective film may be peeled off once, and then the surface protective film may be reattached. In addition, it is required to be easily peeled from the optical member of the adherend (reworkability).
In addition, when the surface protective film is finally peeled off from an optical member such as a polarizing plate or a retardation plate, it is required to be able to be peeled off quickly. It is required that the adhesive force change little depending on the peeling speed so that it can be quickly peeled even by so-called high-speed peeling.
このように、近年においては、表面保護フィルムを構成する粘着剤層に対する要求性能として、（１）低速度剥離領域及び高速度剥離領域においての粘着力のバランスを取ること、（２）糊残りの発生防止、及び（３）リワーク性能などが、表面保護フィルムを使用するに当たっての使い易さの点から求められている。
しかし、表面保護フィルムを構成する粘着剤層に対する要求性能である、これら（１）〜（３）のそれぞれ、個々の要求性能を満たすことは出来ても、表面保護フィルムの粘着剤層に求められる（１）〜（３）の全ての要求性能を、同時に満たすことは非常に困難な課題であった。
Thus, in recent years, as required performance for the pressure-sensitive adhesive layer constituting the surface protective film, (1) balancing the adhesive force in the low-speed peeling region and the high-speed peeling region, (2) adhesive residue Occurrence prevention and (3) rework performance are demanded from the viewpoint of ease of use in using a surface protective film.
However, these (1) to (3), which are required performances for the pressure-sensitive adhesive layer constituting the surface protective film, are required for the pressure-sensitive adhesive layer of the surface protective film even though each of the required performances can be satisfied. It was a very difficult task to satisfy all the required performances (1) to (3) at the same time.
例えば、（１）低速度剥離領域及び高速度剥離領域においての粘着力のバランスを取ること、及び（２）糊残りの発生防止については、次のような提案が知られている。 For example, the following proposals are known for (1) balancing the adhesive force in the low-speed peeling region and the high-speed peeling region and (2) preventing the occurrence of adhesive residue.
炭素数が７以下のアルキル基を有する（メタ）アクリル酸アルキルエステルとカルボキシル基含有共重合性化合物との共重合体を主成分とし、これを架橋剤で架橋処理してなるアクリル系の粘着剤層では、長期間接着した場合に粘着剤が被着体側へ移着し、また被着体に対する接着力の経時上昇性が大きいという問題があった。これを回避するため、炭素数８〜１０のアルキル基を有する（メタ）アクリル酸アルキルエステルとアルコ―ル性水酸基を有する共重合性化合物との共重合体を用い、これを架橋剤で架橋処理した粘着剤層を設けたものが知られている（特許文献１）。
また、上記と同様の共重合体に（メタ）アクリル酸アルキルエステルとカルボキシル基含有共重合性化合物との共重合体を少量配合し、これを架橋剤で架橋処理した粘着剤層を設けたものなどが提案されている。しかし、これらは、表面張力が低くて表面が平滑なプラスチック板などの表面保護に使用すると、加工時や保存時の加熱により浮きなどの剥離現象を生じる問題や、手作業領域である高速での剥離時の再剥離性に劣るという問題もあった。
An acrylic pressure-sensitive adhesive comprising a copolymer of a (meth) acrylic acid alkyl ester having an alkyl group having 7 or less carbon atoms and a carboxyl group-containing copolymerizable compound as a main component and a crosslinking treatment with a crosslinking agent. In the layer, there is a problem that the adhesive is transferred to the adherend side when adhered for a long period of time, and the adhesive strength with respect to the adherend is highly increased over time. In order to avoid this, a copolymer of a (meth) acrylic acid alkyl ester having an alkyl group having 8 to 10 carbon atoms and a copolymerizable compound having an alcoholic hydroxyl group is used, and this is crosslinked with a crosslinking agent. The thing which provided the adhesive layer which carried out is known (patent document 1).
In addition, the same copolymer as described above is blended with a small amount of a copolymer of a (meth) acrylic acid alkyl ester and a carboxyl group-containing copolymer, and a pressure-sensitive adhesive layer obtained by crosslinking with a crosslinking agent is provided. Etc. have been proposed. However, they can be used for surface protection of plastic plates with a low surface tension and a smooth surface. There was also a problem that the removability at the time of peeling was inferior.
これらの問題を解決するため、ａ）炭素数８〜１０のアルキル基を有する（メタ）アクリル酸アルキルエステルを主成分とする（メタ）アクリル酸アルキルエステル１００重量部に、ｂ）カルボキシル基含有共重合性化合物１〜１５重量部と、ｃ）炭素数１〜５の脂肪族カルボン酸のビニルエステル３〜１００重量部とを加えてなる単量体混合物の共重合体に、上記のｂ）成分のカルボキシル基に対して当量以上の架橋剤を配合した粘着剤組成物が提案されている（特許文献２）。
特許文献２に記載の粘着剤組成物では、加工時や保存時などに浮きなどの剥離現象を生じることがなく、そのうえ接着力の経時上昇性が小さくて再剥離性に優れており、長期保存、特に高温雰囲気下で長期保存しても小さな力で再剥離でき、その際被着体上に糊残りを生じず、また高速剥離を行ったときでも小さな力で再剥離できるとしている。
In order to solve these problems, a) 100 parts by weight of a (meth) acrylic acid alkyl ester having an alkyl group having 8 to 10 carbon atoms as a main component and b) a carboxyl group-containing copolymer The above component b) is added to a copolymer of a monomer mixture obtained by adding 1 to 15 parts by weight of a polymerizable compound and c) 3 to 100 parts by weight of a vinyl ester of an aliphatic carboxylic acid having 1 to 5 carbon atoms. A pressure-sensitive adhesive composition in which an equivalent amount or more of a crosslinking agent is blended with respect to the carboxyl group is proposed (Patent Document 2).
The pressure-sensitive adhesive composition described in Patent Document 2 does not cause a peeling phenomenon such as floating during processing or storage, and has a low adhesive strength with time and is excellent in removability, and is stored for a long time. In particular, even if stored for a long time in a high-temperature atmosphere, re-peeling can be performed with a small force. At that time, no adhesive residue is formed on the adherend, and re-peeling can be performed with a small force even when high-speed peeling is performed.
また、（３）リワーク性能については、例えば、アクリル樹脂中に、イソシアネート系化合物の硬化剤と、特定のシリケートオリゴマーをアクリル系樹脂１００重量部に対して０．０００１〜１０重量部で配合した粘着剤組成物が提案されている（特許文献３）。
特許文献３では、アルキル基の炭素数２〜１２程度のアクリル酸アルキルエステルやアルキル基の炭素数４〜１２程度のメタクリル酸アルキルエステル等を主モノマー成分とし、例えば、カルボキシル基含有モノマーなどの他の官能基含有モノマー成分を含むことができるとしている。一般的には上記主モノマーを５０重量％以上含有させることが好ましい、又、官能基含有モノマー成分の含有量は０．００１〜５０重量％、好ましくは０．００１〜２５重量％、更に好ましくは０．０１〜２５重量％であることが望まれる、としている。このような特許文献３に記載の粘着剤組成物は、高温下又は高温高湿下でも凝集力及び接着力の経時変化が小さく、かつ、曲面接着力にも優れた効果を示すことから、リワーク性を有するとしている。
一般に、粘着剤層を柔らかい性状のものにすると、糊残りが発生し易くなり、リワーク性が低下しやすい。すなわち、誤って貼合したときに剥離がし難く、貼り直しが困難となりやすい。このことから、カルボキシル基などの官能基を有するモノマーを主剤に架橋させて、粘着剤層を一定の硬さにすることが、リワーク性を持たせるためには必要と考えられる。
As for (3) rework performance, for example, an adhesive in which an acrylic compound curing agent and a specific silicate oligomer are mixed in an acrylic resin at 0.0001 to 10 parts by weight with respect to 100 parts by weight of the acrylic resin. An agent composition has been proposed (Patent Document 3).
In Patent Document 3, an alkyl group having about 2 to 12 carbon atoms in an alkyl group or a methacrylic acid alkyl ester having about 4 to 12 carbon atoms in an alkyl group is used as a main monomer component. The functional group-containing monomer component can be included. In general, the main monomer is preferably contained in an amount of 50% by weight or more, and the content of the functional group-containing monomer component is 0.001 to 50% by weight, preferably 0.001 to 25% by weight, more preferably It is said that it is desired to be 0.01 to 25% by weight. Such a pressure-sensitive adhesive composition described in Patent Document 3 has a small effect on cohesive force and adhesive force over time even under high temperature or high temperature and high humidity, and exhibits an excellent effect on curved surface adhesive force. It is said to have sex.
In general, when the pressure-sensitive adhesive layer has a soft property, adhesive residue tends to be generated, and the reworkability tends to be lowered. That is, it is difficult to peel off when pasted by mistake, and it is difficult to re-paste. From this, it is considered necessary to make the pressure-sensitive adhesive layer have a certain hardness by crosslinking a monomer having a functional group such as a carboxyl group to the main agent in order to have reworkability.
従来技術においては、表面保護フィルムを構成する粘着剤層に対する要求性能として、（１）低速度剥離領域及び高速度剥離領域においての粘着力のバランスを取ること、（２）糊残りの発生防止、及び（３）リワーク性能などが求められてきたが、これら（１）〜（３）のそれぞれ、個々の要求性能を満たすことは出来ても、表面保護フィルムの粘着剤層に求められる（１）〜（３）の全ての要求性能を、同時に満たすことは困難であり実現することが出来なかった。 In the prior art, as required performance for the pressure-sensitive adhesive layer constituting the surface protective film, (1) balancing the adhesive force in the low-speed peeling region and the high-speed peeling region, (2) preventing the occurrence of adhesive residue, And (3) Although rework performance etc. have been calculated | required, although each of these (1)-(3) can satisfy each performance requirement, it is calculated | required by the adhesive layer of a surface protection film (1). It was difficult to satisfy all the required performances of (3) at the same time and could not be realized.
本発明は、上記の事情に鑑みてなされたものであり、（１）低速度剥離領域及び高速度剥離領域においての粘着力のバランスを取ること、（２）糊残りの発生防止、及び（３）リワーク性能の全ての要求性能を、同時に満たすことが可能な粘着剤組成物及び表面保護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, (1) balancing the adhesive strength in the low-speed peeling region and the high-speed peeling region, (2) preventing the occurrence of adhesive residue, and (3 ) It is an object to provide a pressure-sensitive adhesive composition and a surface protective film that can simultaneously satisfy all the required performances of rework performance.
前記課題を解決するため、本発明は、（Ａ）アルキル基の炭素数がＣ４〜Ｃ１０の（メタ）アクリル酸エステルモノマーと、（Ｂ）水酸基を含有する共重合可能なモノマーと、（Ｃ）カルボキシル基を含有する共重合可能なモノマーと、を含む共重合体からなり、さらに、（Ｄ）３官能以上のイソシアネート化合物、（Ｅ）架橋遅延剤、（Ｆ）架橋触媒、（Ｇ）ポリエーテル変性シロキサン化合物を含有してなることを特徴とする粘着剤組成物を提供する。
前記（Ｂ）水酸基を含有する共重合可能なモノマーが、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、２−ヒドロキシエチル（メタ）アクリレート、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）アクリルアミドからなる化合物群の中から選択された、少なくとも一種以上であり、前記（Ａ）アルキル基の炭素数がＣ４〜Ｃ１０の（メタ）アクリル酸エステルモノマーの１００重量部に対して、前記（Ｂ）水酸基を含有する共重合可能なモノマーが０．１〜５．０重量部含まれ、かつ、前記（Ｂ）水酸基を含有する共重合可能なモノマーのうち、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）アクリレートの合計量が０〜０．９重量部であることが好ましい。
前記（Ｃ）カルボキシル基を含有する共重合可能なモノマーが、（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）アクリレートからなる化合物群の中から選択された、少なくとも一種以上であり、前記（Ａ）アルキル基の炭素数がＣ４〜Ｃ１０の（メタ）アクリル酸エステルモノマーの１００重量部に対して、前記（Ｃ）カルボキシル基を含有する共重合可能なモノマーが０．３５〜１．０重量部含まれることが好ましい。
前記（Ｄ）３官能以上のイソシアネート化合物が、ヘキサメチレンジイソシアネート化合物のイソシアヌレート体、イソホロンジイソシアネート化合物のイソシアヌレート体、ヘキサメチレンジイソシアネート化合物のアダクト体、イソホロンジイソシアネート化合物のアダクト体、ヘキサメチレンジイソシアネート化合物のビュレット体、イソホロンジイソシアネート化合物のビュレット体からなる化合物群の中から選択された、少なくとも一種以上であり、前記共重合体の１００重量部に対して、前記（Ｄ）３官能以上のイソシアネート化合物が０．５〜５．０重量部含まれることが好ましい。
前記（Ｇ）ポリエーテル変性シロキサン化合物が、ＨＬＢ値が７〜１２であるポリエーテル変性シロキサン化合物であり、前記共重合体の１００重量部に対して、前記（Ｇ）ポリエーテル変性シロキサン化合物が０．０１〜０．５重量部含まれることが好ましい。
前記（Ｅ）架橋遅延剤が、ケトエノール互変異性化合物であり、前記共重合体の１００重量部に対して、前記（Ｅ）架橋遅延剤が１．０〜５．０重量部含まれることが好ましい。
前記（Ｆ）架橋触媒が、有機錫化合物であり、前記共重合体の１００重量部に対して、前記（Ｆ）架橋触媒が０．０１〜０．５重量部含まれることが好ましい。
前記粘着剤組成物を架橋させてなる粘着剤層の、低速度剥離領域０．３ｍ／ｍｉｎでの粘着力が０．０５〜０．１Ｎ／２５ｍｍであり、高速度剥離領域３０ｍ／ｍｉｎでの粘着力が１．０Ｎ／２５ｍｍ以下であることが好ましい。
また、本発明は、上記の粘着剤組成物を架橋してなる粘着剤層を、樹脂フィルムの片面または両面に形成してなることを特徴とする粘着フィルムを提供する。
また、本発明は、上記の粘着剤組成物を架橋してなる粘着剤層を、樹脂フィルムの片面に形成してなる表面保護フィルムであって、前記粘着剤層を介して表面保護フィルムの上をボールペンでなぞった後に被着体に汚染移行の無いことを特徴とする表面保護フィルムを提供する。
前記表面保護フィルムは、偏光板の表面保護フィルムの用途として使用することができる。
前記樹脂フィルムの前記粘着剤層が形成された側とは反対面に、帯電防止および防汚処理がされていることが好ましい。
In order to solve the above problems, the present invention provides (A) a (meth) acrylic acid ester monomer having an alkyl group having C4 to C10 carbon atoms, (B) a copolymerizable monomer containing a hydroxyl group, and (C) A copolymer containing a carboxyl group-containing copolymer, and (D) a trifunctional or higher functional isocyanate compound, (E) a crosslinking retarder, (F) a crosslinking catalyst, and (G) a polyether. A pressure-sensitive adhesive composition comprising a modified siloxane compound is provided.
The copolymerizable monomer containing the (B) hydroxyl group is 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate. , N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, and at least one selected from the group consisting of compounds consisting of N-hydroxyethyl (meth) acrylamide, 0.1 to 5.0 parts by weight of the copolymerizable monomer containing the hydroxyl group (B) is included with respect to 100 parts by weight of the (meth) acrylic acid ester monomer having C4 to C10, and Among the copolymerizable monomers containing the hydroxyl group (B), 8-hydroxyoctyl (Meth) acrylate, 6-hydroxyhexyl (meth) acrylate, it is preferred that the total amount of 4-hydroxybutyl (meth) acrylate is 0 to 0.9 parts by weight.
The copolymerizable monomer containing the (C) carboxyl group is at least one selected from the group consisting of (meth) acrylic acid, carboxyethyl (meth) acrylate, and carboxypentyl (meth) acrylate. And (A) the copolymerizable monomer (C) containing a carboxyl group is 0.35 to 100 parts by weight of the (meth) acrylic acid ester monomer having an alkyl group with C4 to C10 carbon atoms. It is preferable that 1.0 part by weight is contained.
(D) Isocyanurate of hexamethylene diisocyanate compound, isocyanurate of isophorone diisocyanate compound, adduct of hexamethylene diisocyanate compound, adduct of isophorone diisocyanate compound, buret of hexamethylene diisocyanate compound And at least one compound selected from the group consisting of burettes of isophorone diisocyanate compounds, and (D) the trifunctional or higher functional isocyanate compound is 0.1% relative to 100 parts by weight of the copolymer. It is preferable that 5-5.0 weight part is contained.
The (G) polyether-modified siloxane compound is a polyether-modified siloxane compound having an HLB value of 7 to 12, and the (G) polyether-modified siloxane compound is 0 with respect to 100 parts by weight of the copolymer. It is preferable that 0.01-0.5 weight part is contained.
The (E) crosslinking retarder is a ketoenol tautomer, and 1.0 to 5.0 parts by weight of the (E) crosslinking retarder is included with respect to 100 parts by weight of the copolymer. preferable.
The (F) crosslinking catalyst is an organotin compound, and the amount of the (F) crosslinking catalyst is preferably 0.01 to 0.5 parts by weight with respect to 100 parts by weight of the copolymer.
The pressure-sensitive adhesive layer obtained by crosslinking the pressure-sensitive adhesive composition has a pressure-sensitive adhesive strength of 0.05 to 0.1 N / 25 mm at a low-speed peeling area of 0.3 m / min and a high-speed peeling area of 30 m / min. The adhesive strength is preferably 1.0 N / 25 mm or less.
Moreover, this invention provides the adhesive film formed by forming the adhesive layer formed by bridge | crosslinking said adhesive composition on the single side | surface or both surfaces of a resin film.
Further, the present invention is a surface protective film formed by forming a pressure-sensitive adhesive layer obtained by crosslinking the above-mentioned pressure-sensitive adhesive composition on one side of a resin film, and the surface of the surface protective film is interposed between the pressure-sensitive adhesive layer. There is provided a surface protective film characterized in that the adherend has no contamination transfer after tracing with a ballpoint pen.
The said surface protection film can be used as a use of the surface protection film of a polarizing plate.
It is preferable that antistatic and antifouling treatment is performed on the surface of the resin film opposite to the side on which the pressure-sensitive adhesive layer is formed.
本発明によれば、（１）低速度剥離領域及び高速度剥離領域においての粘着力のバランスを取ること、（２）糊残りの発生防止、及び（３）リワーク性能の全ての要求性能を、同時に満たすことが可能な粘着剤組成物及び表面保護フィルムを提供することができる。 According to the present invention, (1) balancing the adhesive force in the low-speed peeling region and the high-speed peeling region, (2) preventing the occurrence of adhesive residue, and (3) all the required performance of rework performance, An adhesive composition and a surface protective film that can be simultaneously filled 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。
本発明の粘着剤組成物は、その主剤が、（Ａ）アルキル基の炭素数がＣ４〜Ｃ１０の（メタ）アクリル酸エステルモノマーと、（Ｂ）水酸基を含有する共重合可能なモノマーと、（Ｃ）カルボキシル基を含有する共重合可能なモノマーと、を含む共重合体からなり、さらに、（Ｄ）３官能以上のイソシアネート化合物、（Ｅ）架橋遅延剤、（Ｆ）架橋触媒、（Ｇ）ポリエーテル変性シロキサン化合物を含有してなることを特徴とする。
Hereinafter, the present invention will be described based on preferred embodiments.
In the pressure-sensitive adhesive composition of the present invention, the main ingredients are (A) a (meth) acrylic acid ester monomer having an alkyl group having C4 to C10 carbon atoms, and (B) a copolymerizable monomer containing a hydroxyl group; C) a copolymerizable monomer containing a carboxyl group, and (D) a trifunctional or higher functional isocyanate compound, (E) a crosslinking retarder, (F) a crosslinking catalyst, (G) It contains a polyether-modified siloxane compound.
（Ａ）アルキル基の炭素数がＣ４〜Ｃ１０の（メタ）アクリル酸エステルモノマーとしては、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）アクリレートなどが挙げられる。 (A) As a (meth) acrylic acid ester monomer having a C4-C10 alkyl group, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) ) Acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, and the like.
（Ｂ）水酸基を含有する共重合可能なモノマーとしては、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、２−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水酸基含有（メタ）アクリルアミド類などが挙げられる。
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、２−ヒドロキシエチル（メタ）アクリレート、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）アクリルアミドからなる化合物群の中から選択された、少なくとも一種以上であることが好ましい。
（Ａ）アルキル基の炭素数がＣ４〜Ｃ１０の（メタ）アクリル酸エステルモノマーの１００重量部に対して、前記（Ｂ）水酸基を含有する共重合可能なモノマーが０．１〜５．０重量部含まれることが好ましい。
なおかつ、（Ｂ）水酸基を含有する共重合可能なモノマーのうち、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）アクリレートの合計量は、１重量部未満（含有しない場合も許容される）が好ましく、０〜０．９重量部であることが好ましい。
(B) As a copolymerizable monomer containing a hydroxyl group, 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate And hydroxyalkyl (meth) acrylates such as N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, and hydroxyl-containing (meth) acrylamides such as N-hydroxyethyl (meth) acrylamide.
8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-hydroxy (meth) acrylamide, N-hydroxymethyl (meta It is preferably at least one selected from the group consisting of acrylamide and N-hydroxyethyl (meth) acrylamide.
(A) The copolymerizable monomer containing the hydroxyl group (B) is 0.1 to 5.0 weight with respect to 100 parts by weight of the (meth) acrylic acid ester monomer having an alkyl group with C4 to C10 carbon atoms. Part is preferably included.
In addition, among the copolymerizable monomers containing (B) hydroxyl groups, the total amount of 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate is 1 weight. The amount is preferably less than part (allowable even when not contained), and preferably 0 to 0.9 part by weight.
（Ｃ）カルボキシル基を含有する共重合可能なモノマーが、（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）アクリレートからなる化合物群の中から選択された、少なくとも一種以上であることが好ましい。
（Ａ）アルキル基の炭素数がＣ４〜Ｃ１０の（メタ）アクリル酸エステルモノマーの１００重量部に対して、（Ｃ）カルボキシル基を含有する共重合可能なモノマーが０．３５〜１．０重量部含まれることが好ましい。
(C) The copolymerizable monomer containing a carboxyl group is at least one selected from the group consisting of (meth) acrylic acid, carboxyethyl (meth) acrylate, and carboxypentyl (meth) acrylate. It is preferable.
(A) The copolymerizable monomer containing a carboxyl group (0.35 to 1.0 weight) with respect to 100 parts by weight of the (meth) acrylic acid ester monomer having an alkyl group with C4 to C10 carbon atoms Part is preferably included.
（Ｄ）３官能以上のイソシアネート化合物としては、１分子中に少なくとも３個以上のイソシアネート（ＮＣＯ）基を有するポリイソシアネート化合物であればよく、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（１分子中に２個のＮＣＯ基を有する化合物）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（１分子中に少なくとも３個以上のＯＨ基を有する化合物）とのアダクト体（ポリオール変性体）などが挙げられる。
（Ｄ）３官能以上のイソシアネート化合物が、１分子中に少なくとも３個以上のイソシアネート（ＮＣＯ）基を有するポリイソシアネート化合物であり、特にヘキサメチレンジイソシアネート化合物のイソシアヌレート体、イソホロンジイソシアネート化合物のイソシアヌレート体、ヘキサメチレンジイソシアネート化合物のアダクト体、イソホロンジイソシアネート化合物のアダクト体、ヘキサメチレンジイソシアネート化合物のビュレット体、イソホロンジイソシアネート化合物のビュレット体からなる化合物群の中から選択された、少なくとも一種以上であることが好ましい。（Ｄ）３官能以上のイソシアネート化合物は、共重合体の１００重量部に対して、０．５〜５．０重量部含まれることが好ましい。
(D) The trifunctional or higher functional isocyanate compound may be a polyisocyanate compound having at least three isocyanate (NCO) groups in one molecule, such as hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, A buret modified product or isocyanurate modified product of a diisocyanate such as xylylene diisocyanate (compound having two NCO groups in one molecule), a trivalent or higher polyol such as trimethylolpropane or glycerin (at least 3 in one molecule). And adduct bodies (polyol-modified bodies) with a compound having at least one OH group.
(D) The trifunctional or higher functional isocyanate compound is a polyisocyanate compound having at least three or more isocyanate (NCO) groups in one molecule, in particular, an isocyanurate form of a hexamethylene diisocyanate compound, an isocyanurate form of an isophorone diisocyanate compound. Preferably, at least one selected from the group consisting of adducts of hexamethylene diisocyanate compounds, adducts of isophorone diisocyanate compounds, burettes of hexamethylene diisocyanate compounds, and burettes of isophorone diisocyanate compounds. (D) It is preferable that 0.5-5.0 weight part of isocyanate compounds more than trifunctional are contained with respect to 100 weight part of a copolymer.
（Ｅ）架橋遅延剤としては、アセト酢酸メチル、アセト酢酸エチル、アセト酢酸オクチル、アセト酢酸オレイル、アセト酢酸ラウリル、アセト酢酸ステアリル等のβ−ケトエステルや、アセチルアセトン、２，４−ヘキサンジオン、ベンゾイルアセトン等のβ−ジケトンが挙げられる。これらはケトエノール互変異性化合物であり、ポリイソシアネート化合物を架橋剤とする粘着剤組成物において、架橋剤の有するイソシアネート基をブロックすることにより、架橋剤の配合後における粘着剤組成物の過剰な粘度上昇やゲル化を抑制し、粘着剤組成物のポットライフを延長することができる。
（Ｅ）架橋遅延剤は、ケトエノール互変異性化合物であるのが好ましく、特にアセチルアセトン、アセト酢酸エチルからなる化合物群の中から選択された、少なくとも一種以上であることが好ましい。
（Ｅ）架橋遅延剤は、共重合体の１００重量部に対して、１．０〜５．０重量部含まれることが好ましい。
(E) Crosslinking retarders include methyl acetoacetate, ethyl acetoacetate, octyl acetoacetate, oleyl acetoacetate, lauryl acetoacetate, stearyl acetoacetate, acetylacetone, 2,4-hexanedione, benzoylacetone Β-diketones such as These are ketoenol tautomeric compounds, and in an adhesive composition having a polyisocyanate compound as a crosslinking agent, the excess viscosity of the adhesive composition after blending of the crosslinking agent is blocked by blocking the isocyanate group of the crosslinking agent. The rise and gelation can be suppressed, and the pot life of the pressure-sensitive adhesive composition can be extended.
(E) The crosslinking retarder is preferably a ketoenol tautomer, and particularly preferably at least one selected from the group consisting of acetylacetone and ethyl acetoacetate.
(E) The crosslinking retarder is preferably contained in an amount of 1.0 to 5.0 parts by weight with respect to 100 parts by weight of the copolymer.
（Ｆ）架橋触媒は、ポリイソシアネート化合物を架橋剤とする場合に、前記共重合体と架橋剤との反応（架橋反応）に対して触媒として機能する物質であればよく、第三級アミン等のアミン系化合物、有機錫化合物、有機鉛化合物、有機亜鉛化合物等の有機金属化合物等が挙げられる。
第三級アミンとしては、トリアルキルアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラアルキルジアミン、Ｎ，Ｎ−ジアルキルアミノアルコール、トリエチレンジアミン、モルホリン誘導体、ピペラジン誘導体等が挙げられる。
有機錫化合物としては、ジアルキル錫オキシドや、ジアルキル錫の脂肪酸塩、第１錫の脂肪酸塩等が挙げられる。
（Ｆ）架橋触媒は、有機錫化合物であるのが好ましく、特にジオクチル錫オキシド、ジオクチル錫ジラウレートからなる化合物群の中から選択された、少なくとも一種以上であることが好ましい。
（Ｆ）架橋触媒は、共重合体の１００重量部に対して、０．０１〜０．５重量部含まれることが好ましい。
(F) The crosslinking catalyst may be any substance that functions as a catalyst for the reaction (crosslinking reaction) between the copolymer and the crosslinking agent when a polyisocyanate compound is used as a crosslinking agent, such as a tertiary amine. And organic metal compounds such as amine compounds, organic tin compounds, organic lead compounds, and organic zinc compounds.
Examples of the tertiary amine include trialkylamine, N, N, N ′, N′-tetraalkyldiamine, N, N-dialkylamino alcohol, triethylenediamine, morpholine derivative, piperazine derivative and the like.
Examples of the organic tin compound include dialkyl tin oxide, fatty acid salt of dialkyl tin, fatty acid salt of stannous and the like.
(F) The crosslinking catalyst is preferably an organic tin compound, and particularly preferably at least one selected from the group consisting of dioctyltin oxide and dioctyltin dilaurate.
(F) It is preferable that a crosslinking catalyst is contained 0.01-0.5 weight part with respect to 100 weight part of a copolymer.
（Ｇ）ポリエーテル変性シロキサン化合物は、ポリエーテル基を有するシロキサン化合物であり、通常のシロキサン単位〔−ＳｉＲ１ ２−Ｏ−〕の他に、ポリエーテル基を有するシロキサン単位〔−ＳｉＲ１（Ｒ２Ｏ（Ｒ３Ｏ）ｎＲ４）−Ｏ−〕を有する。ここで、Ｒ１は１種又は２種以上のアルキル基又はアリール基、Ｒ２及びＲ３は１種又は２種以上のアルキレン基、Ｒ４は１種又は２種以上のアルキル基やアシル基等（末端基）を示す。ポリエーテル基としては、ポリオキシエチレン基〔（Ｃ２Ｈ４Ｏ）ｎ〕やポリオキシプロピレン基〔（Ｃ３Ｈ６Ｏ）ｎ〕等のポリオキシアルキレン基が挙げられる。
（Ｇ）ポリエーテル変性シロキサン化合物が、ＨＬＢ値が７〜１２であるポリエーテル変性シロキサン化合物であり、前記共重合体の１００重量部に対して、前記（Ｇ）ポリエーテル変性シロキサン化合物が０．０１〜０．５重量部含まれることが好ましい。より好ましくは、０．１〜０．５重量部である。
ＨＬＢとは、例えばＪＩＳ Ｋ３２１１（界面活性剤用語）等に規定する親水親油バランス（親水性親油性比）である。
ポリエーテル変性シロキサン化合物は、例えば、水素化ケイ素基を有するポリオルガノシロキサン主鎖に対し、不飽和結合及びポリオキシアルキレン基を有する有機化合物をヒドロシリル化反応によりグラフトさせることによって得ることができる。具体的には、ジメチルシロキサン・メチル（ポリオキシエチレン）シロキサン共重合体、ジメチルシロキサン・メチル（ポリオキシエチレン）シロキサン・メチル（ポリオキシプロピレン）シロキサン共重合体、ジメチルシロキサン・メチル（ポリオキシプロピレン）シロキサン重合体等が挙げられる。
（Ｇ）ポリエーテル変性シロキサン化合物を粘着剤組成物に配合することにより、粘着剤の粘着力及びリワーク性能を改善することができる。
(G) The polyether-modified siloxane compound is a siloxane compound having a polyether group, and in addition to a normal siloxane unit [—SiR 1 2 —O—], a siloxane unit having a polyether group [—SiR 1 (R having 2 O (R 3 O) n R 4) -O- ]. Here, R 1 is one or more alkyl groups or aryl groups, R 2 and R 3 are one or more alkylene groups, and R 4 is one or more alkyl groups or acyl groups. Etc. (terminal group). Examples of the polyether group include polyoxyalkylene groups such as a polyoxyethylene group [(C 2 H 4 O) n ] and a polyoxypropylene group [(C 3 H 6 O) n ].
(G) The polyether-modified siloxane compound is a polyether-modified siloxane compound having an HLB value of 7 to 12, and the (G) polyether-modified siloxane compound is 0.1% relative to 100 parts by weight of the copolymer. It is preferably contained in an amount of 01 to 0.5 parts by weight. More preferably, it is 0.1-0.5 weight part.
HLB is a hydrophilic / lipophilic balance (hydrophilic / lipophilic ratio) defined in, for example, JIS K3211 (surfactant term).
The polyether-modified siloxane compound can be obtained, for example, by grafting an organic compound having an unsaturated bond and a polyoxyalkylene group to a polyorganosiloxane main chain having a silicon hydride group by a hydrosilylation reaction. Specifically, dimethylsiloxane-methyl (polyoxyethylene) siloxane copolymer, dimethylsiloxane-methyl (polyoxyethylene) siloxane-methyl (polyoxypropylene) siloxane copolymer, dimethylsiloxane-methyl (polyoxypropylene) Examples thereof include siloxane polymers.
(G) By mix | blending a polyether modified siloxane compound with an adhesive composition, the adhesive force and rework performance of an adhesive can be improved.
さらに、その他成分として、アルキレンオキサイドを含有する共重合可能な（メタ）アクリルモノマー、（メタ）アクリルアミドモノマー、ジアルキル置換アクリルアミドモノマー、界面活性剤、硬化促進剤、可塑剤、充填剤、硬化遅延剤、加工助剤、老化防止剤、酸化防止剤、帯電防止剤などの公知の添加剤を適宜に配合することが出来る。これらは、単独でもしくは２種以上併せて用いられる。帯電防止剤としては、イオン性化合物が挙げられる。また、イオン性のアクリル系モノマーを主剤の共重合体に共重合させることで帯電防止性能を付与することもできる。 Further, as other components, copolymerizable (meth) acrylic monomer containing alkylene oxide, (meth) acrylamide monomer, dialkyl-substituted acrylamide monomer, surfactant, curing accelerator, plasticizer, filler, curing retarder, Known additives such as processing aids, anti-aging agents, antioxidants, and antistatic agents can be appropriately blended. These may be used alone or in combination of two or more. Examples of the antistatic agent include ionic compounds. Antistatic performance can also be imparted by copolymerizing an ionic acrylic monomer with a copolymer of the main agent.
本発明の粘着剤組成物に用いられる主剤の共重合体は、（Ａ）アルキル基の炭素数がＣ４〜Ｃ１０の（メタ）アクリル酸エステルモノマーと、（Ｂ）水酸基を含有する共重合可能なモノマーと、（Ｃ）カルボキシル基を含有する共重合可能なモノマーとを重合させることで合成することができる。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、乳化重合等、適宜の重合方法が使用可能である。
本発明の粘着剤組成物は、上記の共重合体に、（Ｄ）３官能以上のイソシアネート化合物、（Ｅ）架橋遅延剤、（Ｆ）架橋触媒、（Ｇ）ポリエーテル変性シロキサン化合物、さらに適宜任意の添加剤を配合することで調製することができる。
The copolymer of the main agent used in the pressure-sensitive adhesive composition of the present invention is copolymerizable with (A) a (meth) acrylic acid ester monomer having an alkyl group having C4 to C10 and (B) a hydroxyl group. It can be synthesized by polymerizing the monomer and (C) a copolymerizable monomer containing a carboxyl group. The polymerization method of the copolymer is not particularly limited, and an appropriate polymerization method such as solution polymerization or emulsion polymerization can be used.
The pressure-sensitive adhesive composition of the present invention comprises (D) a trifunctional or higher functional isocyanate compound, (E) a crosslinking retarder, (F) a crosslinking catalyst, (G) a polyether-modified siloxane compound, and more appropriately. It can prepare by mix | blending arbitrary additives.
前記粘着剤組成物を架橋させてなる粘着剤層の、低速度剥離領域０．３ｍ／ｍｉｎでの粘着力が０．０５〜０．１Ｎ／２５ｍｍであり、高速度剥離領域３０ｍ／ｍｉｎでの粘着力が１．０Ｎ／２５ｍｍ以下であることが好ましい。これにより、粘着力が剥離速度によっても変化が少ない性能が得られ、高速剥離によっても、速やかに剥離することが可能になる。また、貼り直しのため、一旦、表面保護フィルムを剥がすときにも、過大な力を必要とせず、被着体から剥がし易い。 The pressure-sensitive adhesive layer obtained by crosslinking the pressure-sensitive adhesive composition has a pressure-sensitive adhesive strength of 0.05 to 0.1 N / 25 mm at a low-speed peeling area of 0.3 m / min and a high-speed peeling area of 30 m / min. The adhesive strength is preferably 1.0 N / 25 mm or less. Thereby, the performance with little change in the adhesive force depending on the peeling speed can be obtained, and it is possible to peel quickly even by high speed peeling. In addition, when the surface protective film is once peeled off for re-sticking, excessive force is not required and it is easy to peel off from the adherend.
本発明の粘着剤組成物を架橋してなる粘着剤層（架橋後の粘着剤）のゲル分率は、９５〜１００％であることが好ましい。このようにゲル分率が高いことにより、低速度剥離領域における粘着力が過大にならず、共重合体からの未重合モノマーあるいはオリゴマーの溶出が低減して、リワーク性や高温・高湿度における耐久性が改善され、被着体の汚染を抑制することができる。 The gel fraction of the pressure-sensitive adhesive layer (cross-linked pressure-sensitive adhesive) obtained by crosslinking the pressure-sensitive adhesive composition of the present invention is preferably 95 to 100%. Because of this high gel fraction, the adhesive strength in the low-velocity release region does not become excessive, the elution of unpolymerized monomers or oligomers from the copolymer is reduced, and reworkability and durability at high temperatures and high humidity are reduced. Property is improved, and contamination of the adherend can be suppressed.
本発明の粘着フィルムは、本発明の粘着剤組成物を架橋してなる粘着剤層を、樹脂フィルムの片面または両面に形成してなる。また、本発明の表面保護フィルムは、本発明の粘着剤組成物を架橋してなる粘着剤層を、樹脂フィルムの片面に形成してなる表面保護フィルムである。本発明の粘着剤組成物は、上記の（Ａ）〜（Ｇ）の各成分がバランスよく配合されているため、（１）低速度剥離領域及び高速度剥離領域においての粘着力のバランスを取ること、（２）糊残りの発生防止、及び（３）リワーク性能（粘着剤層を介して表面保護フィルムの上をボールペンでなぞった後に被着体に汚染移行の無いこと）の全ての要求性能を、同時に満たすことが可能である。このため、偏光板の表面保護フィルムの用途として好適に使用することができる。 The pressure-sensitive adhesive film of the present invention is formed by forming a pressure-sensitive adhesive layer obtained by crosslinking the pressure-sensitive adhesive composition of the present invention on one side or both sides of a resin film. Moreover, the surface protective film of this invention is a surface protective film formed by forming the adhesive layer formed by bridge | crosslinking the adhesive composition of this invention on the single side | surface of a resin film. In the pressure-sensitive adhesive composition of the present invention, since the components (A) to (G) are blended in a well-balanced manner, (1) the pressure-sensitive adhesive strength is balanced in the low-speed peeling region and the high-speed peeling region. (2) All the required performance of (2) Prevention of adhesive residue and (3) Rework performance (no contamination transfer on the adherend after tracing the surface protection film with a ballpoint pen through the adhesive layer) Can be satisfied at the same time. For this reason, it can be used suitably as a use of the surface protection film of a polarizing plate.
粘着剤層の基材フィルムや、粘着面を保護する剥離フィルム（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。
剥離フィルムには、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。
As the base film of the pressure-sensitive adhesive layer and the release film (separator) that protects 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, fluorine-based release agent or coating agent, silica fine particles, etc., application of antistatic agent, An antistatic treatment such as kneading can be performed.
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 to be combined with the pressure-sensitive adhesive surface.
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＞
［実施例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２−エチルヘキシルアクリレート１００重量部、８−ヒドロキシオクチルアクリレート０．９重量部、アクリル酸０．５重量部とともに溶剤（酢酸エチル）を６０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、実施例１に用いるアクリル共重合体溶液１を得た。
［実施例２〜９及び比較例１〜９］
単量体の組成を各々、表１の（Ａ）〜（Ｃ）の記載のようにする以外は、上記の実施例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２〜９及び比較例１〜９に用いるアクリル共重合体溶液を得た。
<Manufacture of acrylic copolymer>
[Example 1]
Nitrogen gas was introduced into a reactor equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube, and the air in the reactor was replaced with nitrogen gas. Thereafter, 100 parts by weight of 2-ethylhexyl acrylate, 0.9 part by weight of 8-hydroxyoctyl acrylate, 0.5 part by weight of acrylic acid and 60 parts of a solvent (ethyl acetate) were added to the reactor. Thereafter, 0.1 part by weight of azobisisobutyronitrile as a polymerization initiator was dropped over 2 hours and reacted at 65 ° C. for 6 hours, and the acrylic copolymer solution used in Example 1 having a weight average molecular weight of 500,000 was used. 1 was obtained.
[Examples 2 to 9 and Comparative Examples 1 to 9]
Examples 2 to 9 were carried out in the same manner as in the acrylic copolymer solution 1 used in Example 1 except that the monomer compositions were as described in (A) to (C) of Table 1. And the acrylic copolymer solution used for Comparative Examples 1-9 was obtained.
＜粘着剤組成物及び表面保護フィルムの製造＞
［実施例１］
上記のとおり製造したアクリル共重合体溶液１（そのうちアクリル共重合体が１００重量部）に対して、ＫＦ−３５１Ａ（ＨＬＢ＝１２のポリエーテル変性シロキサン化合物）０．１重量部、アセチルアセトン２．５重量部を加え撹拌したのち、コロネートＨＸ（ヘキサメチレンジイソシアネート化合物のイソシアヌレート体）１．５重量部、ジオクチル錫ジラウレート０．０２重量部を加えて撹拌混合して実施例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、粘着剤層の厚さが２５μｍである粘着シートを得た。
その後、一方の面に帯電防止及び防汚処理されたポリエチレンテレフタレート（ＰＥＴ）フィルムの帯電防止及び防汚処理された面とは反対の面に粘着シートを転写させ、「帯電防止及び防汚処理されたＰＥＴフィルム／粘着剤層／剥離フィルム（シリコーン樹脂コートされたＰＥＴフィルム）」の積層構成を有する実施例１の表面保護フィルムを得た。
［実施例２〜９及び比較例１〜９］
添加剤の組成を各々、表１の（Ｄ）〜（Ｇ）の記載のようにする以外は、上記の実施例１の表面保護フィルムと同様にして、実施例２〜９及び比較例１〜９の表面保護フィルムを得た。
<Production of pressure-sensitive adhesive composition and surface protective film>
[Example 1]
0.1 parts by weight of KF-351A (polyether-modified siloxane compound with HLB = 12) and 2.5 parts of acetylacetone with respect to the acrylic copolymer solution 1 (of which the acrylic copolymer is 100 parts by weight) produced as described above. After adding parts by weight and stirring, 1.5 parts by weight of coronate HX (isocyanurate of hexamethylene diisocyanate compound) and 0.02 parts by weight of dioctyltin dilaurate were added and stirred to mix the pressure-sensitive adhesive composition of Example 1. Obtained. After applying this adhesive composition on a release film made of a polyethylene terephthalate (PET) film coated with a silicone resin, the solvent is removed by drying at 90 ° C., and the adhesive layer has a thickness of 25 μm A sheet was obtained.
Then, the adhesive sheet was transferred to the opposite side of the antistatic and antifouling surface of the polyethylene terephthalate (PET) film that had been antistatic and antifouling treated on one side. A surface protective film of Example 1 having a laminated structure of “PET film / adhesive layer / release film (silicone resin-coated PET film)” was obtained.
[Examples 2 to 9 and Comparative Examples 1 to 9]
Examples 2 to 9 and Comparative Examples 1 to 1 were made in the same manner as the surface protective film of Example 1 except that the compositions of the additives were as described in (D) to (G) of Table 1. 9 surface protective films were obtained.
表１において、各成分の配合比は、（Ａ）群の合計を１００重量部として求めた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）ＨＸ及び同ＨＬは日本ポリウレタン工業株式会社の商品名であり、タケネート（登録商標）Ｄ−１４０Ｎは三井化学株式会社の商品名であり、デュラネート（登録商標）２４Ａ―１００は旭化成ケミカルズ株式会社の商品名であり、ＫＦ−３５１Ａ、ＫＦ−３５２Ａ、ＫＦ−３５３、ＫＦ−６４０及びＸ−２２−６１９１は信越化学株式会社の商品名である。 In Table 1, the compounding ratio of each component is shown by enclosing the numerical value of parts by weight enclosed in parentheses with the total of group (A) as 100 parts by weight. In addition, Table 2 shows the names of the abbreviations of each component used in Table 1. Coronate (registered trademark) HX and HL are trade names of Nippon Polyurethane Industry Co., Ltd., Takenate (registered trademark) D-140N is a trade name of Mitsui Chemicals, and Duranate (registered trademark) 24A-100. Are trade names of Asahi Kasei Chemicals Corporation, and KF-351A, KF-352A, KF-353, KF-640 and X-22-6191 are trade names of Shin-Etsu Chemical Co., Ltd.
＜試験方法及び評価＞
実施例１〜９及び比較例１〜９における表面保護フィルムを２３℃、５０％ＲＨの雰囲気下で７日間エージングした後、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たものを、ゲル分率の測定試料とした。
さらに、この粘着剤層を表出させた表面保護フィルムを、粘着剤層を介して液晶セルに貼られた偏光板の表面に貼り合わせ、１日放置した後、５０℃、５気圧、２０分間オートクレーブ処理し、室温でさらに１２時間放置したものを、粘着力及び耐久性の測定試料とした。
<Test method and evaluation>
The surface protective films in Examples 1 to 9 and Comparative Examples 1 to 9 were aged for 7 days in an atmosphere of 23 ° C. and 50% RH, and then the release film (silicone resin-coated PET film) was peeled off to form an adhesive layer. Was used as a sample for measuring the gel fraction.
Further, the surface protective film on which the pressure-sensitive adhesive layer was exposed was bonded to the surface of the polarizing plate attached to the liquid crystal cell via the pressure-sensitive adhesive layer, and allowed to stand for 1 day, then at 50 ° C., 5 atm, 20 minutes. What was autoclaved and allowed to stand at room temperature for another 12 hours was used as a sample for measuring adhesive strength and durability.
＜ゲル分率＞
エージング終了後、偏光板に貼り合わせる前の測定試料の質量を正確に測定し、トルエン中に２４時間浸漬後、２００メッシュの金網で濾過する。その後、濾過物を１００℃、１時間乾燥した後、残渣の質量を正確に測定して、以下の式から粘着剤層（架橋後の粘着剤）のゲル分率を算出した。
ゲル分率（％）＝不溶部分質量（ｇ）／粘着剤質量（ｇ）×１００
<Gel fraction>
After the aging is completed, the mass of the measurement sample before being bonded to the polarizing plate is accurately measured, immersed in toluene for 24 hours, and then filtered through a 200 mesh wire net. Then, after drying a filtered material at 100 degreeC for 1 hour, the mass of the residue was measured correctly and the gel fraction of the adhesive layer (adhesive after bridge | crosslinking) was computed from the following formula | equation.
Gel fraction (%) = insoluble partial mass (g) / adhesive mass (g) × 100
＜粘着力＞
上記で得られた測定試料（２５ｍｍ幅の表面保護フィルムを偏光板の表面に貼り合わせたもの）を１８０°方向に引張試験機を用いて低速度（０．３ｍ／ｍｉｎ）及び高速度（３０ｍ／ｍｉｎ）において剥がして測定した剥離強度を粘着力とした。
<Adhesive strength>
The measurement sample obtained above (a 25 mm wide surface protective film bonded to the surface of the polarizing plate) was rotated at a low speed (0.3 m / min) and a high speed (30 m) in a 180 ° direction using a tensile tester. / Min) was taken as the peel strength measured after peeling off.
＜リワーク性＞
上記で得られた測定試料の表面保護フィルムの上をボールペンでなぞった後、偏光板から表面保護フィルムを剥離して偏光板の表面を観察し、偏光板に汚染移行の無いことを確認した。評価目標基準は、偏光板に汚染移行の無い場合を「○」、ボールペンでなぞった軌跡に沿って少なくとも一部に汚染移行が確認された場合を「×」と評価した。
<Reworkability>
After the surface protective film of the measurement sample obtained above was traced with a ballpoint pen, the surface protective film was peeled off from the polarizing plate, the surface of the polarizing plate was observed, and it was confirmed that the polarizing plate had no contamination transfer. The evaluation target criteria were evaluated as “◯” when there was no contamination transfer on the polarizing plate, and “X” when contamination transfer was confirmed at least partially along the trace traced with the ballpoint pen.
＜耐久性＞
上記で得られた測定試料を６０℃、９０％ＲＨの雰囲気下に２５０時間放置後、室温に取り出し、さらに１２時間放置した後、粘着力を測定して初期の粘着力と比較して明らかな増加が無いことを確認した。評価目標基準は、試験後の粘着力が初期粘着力の１．５倍以下である場合を「○」、１．５倍を超えた場合を「×」と評価した。
<Durability>
The measurement sample obtained above was allowed to stand in an atmosphere of 60 ° C. and 90% RH for 250 hours, then taken out to room temperature, and further allowed to stand for 12 hours. Then, the adhesive strength was measured and clearly compared with the initial adhesive strength. It was confirmed that there was no increase. As the evaluation target criteria, a case where the adhesive strength after the test was 1.5 times or less of the initial adhesive strength was evaluated as “◯”, and a case where the adhesive strength exceeded 1.5 times was evaluated as “X”.
表３に、評価結果を示す。 Table 3 shows the evaluation results.
実施例１〜９の表面保護フィルムは、低速度剥離領域０．３ｍ／ｍｉｎでの粘着力が０．０５〜０．１Ｎ／２５ｍｍであり、高速度剥離領域３０ｍ／ｍｉｎでの粘着力が１．０Ｎ／２５ｍｍ以下であり、粘着剤層を介して表面保護フィルムの上をボールペンでなぞった後に被着体に汚染移行の無く、６０℃、９０％ＲＨの雰囲気下に２５０時間放置したときの耐久性にも優れていた。
すなわち、（１）低速度剥離領域及び高速度剥離領域においての粘着力のバランスを取ること、（２）糊残りの発生防止、及び（３）リワーク性能の全ての要求性能を、同時に満たしている。
The surface protective films of Examples 1 to 9 have an adhesive strength of 0.05 to 0.1 N / 25 mm at a low speed peeling area of 0.3 m / min, and an adhesive strength of 1 at a high speed peeling area of 30 m / min. 0.0N / 25 mm or less, and when the surface protective film was traced with a ballpoint pen through the adhesive layer, the adherend was not contaminated and left in an atmosphere of 60 ° C. and 90% RH for 250 hours. Excellent durability.
That is, (1) balance the adhesive force in the low-speed peeling area and the high-speed peeling area, (2) prevent occurrence of adhesive residue, and (3) satisfy all the required performance of rework performance at the same time. .
比較例１の表面保護フィルムは、（Ｂ）水酸基含有モノマーが過多であったためか、低速度剥離領域０．３ｍ／ｍｉｎでの粘着力が低い結果となった。
比較例２の表面保護フィルムでは、（Ｂ）水酸基含有モノマーが過少、（Ｄ）イソシアネート化合物が過多、（Ｇ）ポリエーテル変性シロキサン化合物のＨＬＢ値が過小であったためか、低速度剥離領域０．３ｍ／ｍｉｎでの粘着力と高速度剥離領域３０ｍ／ｍｉｎでの粘着力が大きすぎ、リワーク性と耐久性が劣り、ゲル分率が低くなった。
比較例３の表面保護フィルムでは、（Ｂ）水酸基含有モノマーが過多、（Ｃ）酸含有モノマーが過多、（Ｇ）ポリエーテル変性シロキサン化合物のＨＬＢ値が過大であったためか、低速度剥離領域０．３ｍ／ｍｉｎでの粘着力が低く、リワーク性と耐久性が劣っていた。
The surface protective film of Comparative Example 1 resulted in low adhesive strength in the low-speed release region of 0.3 m / min, probably because (B) the hydroxyl group-containing monomer was excessive.
In the surface protective film of Comparative Example 2, (B) the hydroxyl group-containing monomer was insufficient, (D) the isocyanate compound was excessive, and (G) the polyether-modified siloxane compound had an excessively low HLB value. The adhesive strength at 3 m / min and the adhesive strength at 30 m / min in the high speed peeling region were too large, the reworkability and durability were inferior, and the gel fraction was low.
In the surface protective film of Comparative Example 3, (B) the hydroxyl group-containing monomer is excessive, (C) the acid-containing monomer is excessive, and (G) the polyether modified siloxane compound has an excessive HLB value. The adhesive strength at 3 m / min was low, and the reworkability and durability were inferior.
比較例４の表面保護フィルムでは、（Ｃ）酸含有モノマーが過少であったためか、低速度剥離領域０．３ｍ／ｍｉｎでの粘着力が低く、耐久性が劣っていた。
比較例５の表面保護フィルムでは、（Ｂ）水酸基含有モノマーが過多、（Ｄ）イソシアネート化合物が過少であったためか、低速度剥離領域０．３ｍ／ｍｉｎでの粘着力と高速度剥離領域３０ｍ／ｍｉｎでの粘着力が大きすぎ、リワーク性と耐久性が劣り、ゲル分率が低くなった。
比較例６の表面保護フィルムは、（Ｅ）架橋遅延剤を配合せず、（Ｆ）架橋触媒が過多であったためか、ポットライフが短くなりすぎ、塗布前に架橋が進行したため、塗工をすることができなかった。
In the surface protective film of Comparative Example 4, (C) the acid-containing monomer was too small, or the adhesive strength in the low-speed peeling region of 0.3 m / min was low and the durability was inferior.
In the surface protective film of Comparative Example 5, (B) the hydroxyl group-containing monomer was excessive, and (D) the isocyanate compound was excessive, the adhesive strength in the low-speed release region 0.3 m / min and the high-speed release region 30 m / min. The adhesive strength in min was too large, the reworkability and durability were inferior, and the gel fraction was low.
The surface protective film of Comparative Example 6 was not blended with (E) a crosslinking retarder and (F) the crosslinking catalyst was excessive, or the pot life was too short and the crosslinking proceeded before coating. I couldn't.
比較例７の表面保護フィルムは、（Ａ）アルキル基を有する（メタ）アクリル酸エステルモノマーにＣ１のアルキル基を有するＭＡを含有し、（Ｆ）架橋触媒を配合しなかったためか、低速度剥離領域０．３ｍ／ｍｉｎでの粘着力と高速度剥離領域３０ｍ／ｍｉｎでの粘着力が大きすぎ、リワーク性と耐久性が劣っていた。
比較例８の表面保護フィルムでは、（Ｇ）ポリエーテル変性シロキサン化合物を配合しなかったためか、低速度剥離領域０．３ｍ／ｍｉｎでの粘着力と高速度剥離領域３０ｍ／ｍｉｎでの粘着力が大きすぎ、リワーク性が劣っていた。
比較例９の表面保護フィルムでは、（Ｇ）ポリエーテル変性シロキサン化合物が過多であったためか、低速度剥離領域０．３ｍ／ｍｉｎでの粘着力が低く、耐久性が劣っていた。
このように、比較例１〜９の表面保護フィルムでは、（１）低速度剥離領域及び高速度剥離領域においての粘着力のバランスを取ること、（２）糊残りの発生防止、及び（３）リワーク性能の全ての要求性能を、同時に満たすことができなかった。
The surface protective film of Comparative Example 7 contains (A) a (meth) acrylic acid ester monomer having an alkyl group containing MA having a C1 alkyl group, and (F) a low-speed peeling because it did not contain a crosslinking catalyst. The adhesive strength in the region 0.3 m / min and the adhesive strength in the high-speed peeling region 30 m / min were too large, and the reworkability and durability were inferior.
In the surface protective film of Comparative Example 8, (G) the polyether-modified siloxane compound was not blended, the adhesive strength in the low-speed peeling area 0.3 m / min and the adhesive strength in the high-speed peeling area 30 m / min. It was too big and the reworkability was inferior.
In the surface protective film of Comparative Example 9, (G) the polyether-modified siloxane compound was excessive, or the adhesive strength in the low-speed peeling area of 0.3 m / min was low, and the durability was inferior.
Thus, in the surface protective films of Comparative Examples 1 to 9, (1) balancing the adhesive strength in the low-speed peeling region and the high-speed peeling region, (2) preventing occurrence of adhesive residue, and (3) It was not possible to satisfy all the rework performance requirements at the same time.
Claims (9)
前記（Ａ）アルキル基の炭素数がＣ４〜Ｃ１０の（メタ）アクリル酸エステルモノマーの１００重量部に対して、前記（Ｃ）カルボキシル基を含有する共重合可能なモノマーが０．３５〜１．０重量部と、前記（Ｂ）水酸基を含有する共重合可能なモノマーが０．１〜５．０重量部含まれ、かつ、前記（Ｂ）水酸基を含有する共重合可能なモノマーのうち、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）アクリレートの合計量が０〜０．９重量部（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）アクリレート及び４−ヒドロキシブチル（メタ）アクリレートを含有しない場合も許容される）であることを特徴とする粘着剤組成物。 (A) a (meth) acrylic acid ester monomer having an alkyl group with C4 to C10 carbon atoms, (B) a copolymerizable monomer containing a hydroxyl group, and (C) a copolymerizable monomer containing a carboxyl group And (D) a trifunctional or higher functional isocyanate compound, (E) a crosslinking retarder, (F) a crosslinking catalyst, and (G) a polyether-modified siloxane compound having an HLB value of 7 to 12. Containing
The copolymerizable monomer containing the (C) carboxyl group is 0.35 to 1.100 parts by weight of the (meth) acrylic acid ester monomer having (A) alkyl group having C4 to C10 carbon atoms . 0 part by weight and 0.1 to 5.0 parts by weight of the copolymerizable monomer (B) containing a hydroxyl group, and among the copolymerizable monomers (B) containing a hydroxyl group, 8 -The total amount of hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate is 0 to 0.9 parts by weight (8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (Meth) acrylate and 4-hydroxybutyl (meth) acrylate are also acceptable) Thing.
前記共重合体の１００重量部に対して、前記（Ｄ）３官能以上のイソシアネート化合物が０．５〜５．０重量部含まれることを特徴とする請求項１〜３のいずれかに記載の粘着剤組成物。 (D) Isocyanurate of hexamethylene diisocyanate compound, isocyanurate of isophorone diisocyanate compound, adduct of hexamethylene diisocyanate compound, adduct of isophorone diisocyanate compound, buret of hexamethylene diisocyanate compound And at least one selected from the group of compounds consisting of burettes of isophorone diisocyanate compounds,
The said (D) trifunctional or more than trifunctional isocyanate compound is contained 0.5-5.0 weight part with respect to 100 weight part of the said copolymer, The Claim 1 characterized by the above-mentioned. Adhesive composition.
前記共重合体の１００重量部に対して、前記（Ｅ）架橋遅延剤が１．０〜５．０重量部含まれることを特徴とする請求項１〜５のいずれかに記載の粘着剤組成物。 (E) the crosslinking retarder is a ketoenol tautomer,
The pressure-sensitive adhesive composition according to claim 1, wherein 1.0 to 5.0 parts by weight of the (E) crosslinking retarder is contained with respect to 100 parts by weight of the copolymer. object.
前記共重合体の１００重量部に対して、前記（Ｆ）架橋触媒が０．０１〜０．５重量部含まれることを特徴とする請求項１〜６のいずれかに記載の粘着剤組成物。 The (F) crosslinking catalyst is an organotin compound,
The pressure-sensitive adhesive composition according to any one of claims 1 to 6, wherein 0.01 to 0.5 parts by weight of the (F) crosslinking catalyst is contained with respect to 100 parts by weight of the copolymer. .
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| TW103140756A TWI516563B (en) | 2011-04-22 | 2012-03-23 | Adhesive composition |
| TW101110083A TWI515282B (en) | 2011-04-22 | 2012-03-23 | Adhesive composition and surface protective film |
| KR1020120041660A KR101524621B1 (en) | 2011-04-22 | 2012-04-20 | Adhesive composition and surface protection film |
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| JP5770607B2 (en) * | 2011-11-21 | 2015-08-26 | 藤森工業株式会社 | Adhesive composition and surface protective film |
| JP5687722B2 (en) * | 2012-03-30 | 2015-03-18 | 日東電工株式会社 | Adhesive sheet and optical member |
| JP2014111705A (en) * | 2012-03-30 | 2014-06-19 | Nitto Denko Corp | Pressure sensitive adhesive sheet |
| JP6221091B2 (en) * | 2012-11-16 | 2017-11-01 | 藤森工業株式会社 | Surface protection film |
| JP6056434B2 (en) * | 2012-12-07 | 2017-01-11 | 大日本印刷株式会社 | Adhesive composition and surface protective film |
| JP6026260B2 (en) * | 2012-12-17 | 2016-11-16 | 藤森工業株式会社 | Adhesive layer and adhesive film |
| JP6062811B2 (en) * | 2013-06-15 | 2017-01-18 | 日東電工株式会社 | Adhesive composition, adhesive layer and adhesive sheet |
| JP5908870B2 (en) * | 2013-07-23 | 2016-04-26 | 藤森工業株式会社 | Adhesive composition, adhesive film and surface protective film |
| JP6203563B2 (en) * | 2013-07-31 | 2017-09-27 | 日東電工株式会社 | Adhesive sheet and optical member |
| JP6239302B2 (en) * | 2013-07-31 | 2017-11-29 | 日東電工株式会社 | Adhesive sheet and optical member |
| KR20150017859A (en) * | 2013-08-08 | 2015-02-23 | 동우 화인켐 주식회사 | Pressure-sensitive adhesive composition and complexed polarization plate using the same |
| KR101710443B1 (en) * | 2013-09-20 | 2017-02-27 | 후지모리 고교 가부시키가이샤 | Adhesive composition and surface protection film |
| JP5953289B2 (en) * | 2013-11-29 | 2016-07-20 | 藤森工業株式会社 | Adhesive composition and surface protective film |
| JP6246021B2 (en) * | 2014-02-27 | 2017-12-13 | 日本カーバイド工業株式会社 | Adhesive composition and optical member surface protective film |
| JP6804843B2 (en) * | 2015-01-30 | 2020-12-23 | 日東電工株式会社 | Optical surface protective film with separator |
| JP6142045B2 (en) * | 2015-06-25 | 2017-06-07 | 日東電工株式会社 | Method for producing adhesive film and method for producing polarizer |
| CN105315928A (en) * | 2015-10-29 | 2016-02-10 | 四川羽玺新材料有限公司 | Post-curing-free adhesive and preparation method thereof |
| JP6923623B2 (en) * | 2018-04-18 | 2021-08-25 | 藤森工業株式会社 | Surface protective film |
| JP6621863B2 (en) * | 2018-04-18 | 2019-12-18 | 藤森工業株式会社 | Adhesive composition, adhesive film and surface protective film |
| KR102581044B1 (en) * | 2019-01-25 | 2023-09-20 | 주식회사 엘지화학 | Surface protective film and method for manufacturing organic light emitting electronic device |
| JP6876855B2 (en) * | 2020-06-16 | 2021-05-26 | 藤森工業株式会社 | Release film for antistatic surface protection film |
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| KR100385720B1 (en) * | 1999-04-30 | 2003-05-27 | 주식회사 엘지화학 | Acrylic pressure-sensitive adhesive composition for optical use having improved rework property and laminates coated therewith |
| JP2003073638A (en) * | 2001-08-31 | 2003-03-12 | Nippon Synthetic Chem Ind Co Ltd:The | Self-adhesive composition |
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| JP5407204B2 (en) * | 2008-07-16 | 2014-02-05 | 王子ホールディングス株式会社 | Adhesive, double-sided adhesive sheet, optical filter, and display |
| CN101768415B (en) * | 2008-12-30 | 2013-03-27 | 第一毛织株式会社 | Antistatic adhesive composition, adhesive film using the same, method for producing the adhesive film, and method of fabricating liquid crystal display |
| JP5187973B2 (en) * | 2009-04-30 | 2013-04-24 | 日東電工株式会社 | Optical film adhesive composition, optical film adhesive layer, adhesive optical film, and image display device |
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