JP5361244B2 - Adhesive composition for optical member surface protective film and optical member surface protective film - Google Patents
Adhesive composition for optical member surface protective film and optical member surface protective film Download PDFInfo
- Publication number
- JP5361244B2 JP5361244B2 JP2008128256A JP2008128256A JP5361244B2 JP 5361244 B2 JP5361244 B2 JP 5361244B2 JP 2008128256 A JP2008128256 A JP 2008128256A JP 2008128256 A JP2008128256 A JP 2008128256A JP 5361244 B2 JP5361244 B2 JP 5361244B2
- Authority
- JP
- Japan
- Prior art keywords
- protective film
- surface protective
- weight
- optical member
- acrylic
- 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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- 230000001681 protective effect Effects 0.000 title claims description 65
- 239000000203 mixture Substances 0.000 title claims description 55
- 230000003287 optical effect Effects 0.000 title claims description 48
- 239000000853 adhesive Substances 0.000 title claims description 33
- 230000001070 adhesive effect Effects 0.000 title claims description 33
- 229920006243 acrylic copolymer Polymers 0.000 claims description 79
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 64
- 239000000178 monomer Substances 0.000 claims description 59
- -1 alkali metal salt Chemical class 0.000 claims description 58
- 239000010410 layer Substances 0.000 claims description 35
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 30
- 125000002947 alkylene group Chemical group 0.000 claims description 18
- 230000009477 glass transition Effects 0.000 claims description 18
- 229910052783 alkali metal Inorganic materials 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 10
- 239000012948 isocyanate Substances 0.000 claims description 9
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Polymers C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 7
- 238000007334 copolymerization reaction Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 150000003377 silicon compounds Chemical class 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000003431 cross linking reagent Substances 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000003522 acrylic cement Substances 0.000 claims 3
- 238000010030 laminating Methods 0.000 claims 1
- 239000010408 film Substances 0.000 description 73
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- 239000004973 liquid crystal related substance Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000005056 polyisocyanate Substances 0.000 description 9
- 229920001228 polyisocyanate Polymers 0.000 description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 8
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000012790 adhesive layer Substances 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 125000005907 alkyl ester group Chemical group 0.000 description 6
- 210000002858 crystal cell Anatomy 0.000 description 6
- 230000005611 electricity Effects 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
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- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 230000003068 static effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 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 4
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 238000007689 inspection Methods 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 4
- 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 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 206010052128 Glare Diseases 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 230000005641 tunneling Effects 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 2
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
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- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
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- 150000002148 esters Chemical class 0.000 description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
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- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
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- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
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- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- HXDLWJWIAHWIKI-UHFFFAOYSA-N 2-hydroxyethyl acetate Chemical compound CC(=O)OCCO HXDLWJWIAHWIKI-UHFFFAOYSA-N 0.000 description 1
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
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- 239000002608 ionic liquid Substances 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
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- NCWQJOGVLLNWEO-UHFFFAOYSA-N methylsilicon Chemical group [Si]C NCWQJOGVLLNWEO-UHFFFAOYSA-N 0.000 description 1
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- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
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- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- MDYPDLBFDATSCF-UHFFFAOYSA-N nonyl prop-2-enoate Chemical compound CCCCCCCCCOC(=O)C=C MDYPDLBFDATSCF-UHFFFAOYSA-N 0.000 description 1
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- 239000012788 optical film Substances 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
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- 239000004814 polyurethane Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
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- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
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- 235000007586 terpenes Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 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
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- CMHHITPYCHHOGT-UHFFFAOYSA-N tributylborane Chemical compound CCCCB(CCCC)CCCC CMHHITPYCHHOGT-UHFFFAOYSA-N 0.000 description 1
- HFFLGKNGCAIQMO-UHFFFAOYSA-N trichloroacetaldehyde Chemical compound ClC(Cl)(Cl)C=O HFFLGKNGCAIQMO-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Polarising Elements (AREA)
- Liquid Crystal (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、液晶表示板など光学部材表面の一次保護のために使用される保護フィルム用粘着剤組成物に関するものであり、詳しくは、製造工程中で光学部材表面に一時的に貼り付けられ、保護を要する工程のあいだ表面を保護し、工程終了後剥離される表面保護フィルム用粘着剤組成物であって、帯電が少なく、剥離時の作業性が良い粘着剤組成物に関する。 The present invention relates to a pressure-sensitive adhesive composition for a protective film used for primary protection of the surface of an optical member such as a liquid crystal display panel, and in particular, is temporarily attached to the surface of the optical member during the production process. The present invention relates to a pressure-sensitive adhesive composition for a surface protective film that protects the surface during a process requiring protection and is peeled off after completion of the process, and has a low charge and good workability at the time of peeling.
液晶表示板は、薄型軽量であること、消費電力が少なくて済むことなどから、近年、各種の情報関連機器、例えばワ−プロやノ−ト型パソコンなどの画面表示装置として利用されている。このような液晶表示板には、本体である液晶を内包したガラスセル（液晶セル）と共に偏光板や位相差板などの光学部材が用いられている。 Since the liquid crystal display panel is thin and light and consumes less power, it has been used in recent years as a screen display device for various information-related devices such as word processors and notebook personal computers. In such a liquid crystal display plate, an optical member such as a polarizing plate or a retardation plate is used together with a glass cell (liquid crystal cell) containing liquid crystal as a main body.
これらの光学部材は、通常、打抜加工、検査、輸送、液晶表示板の組立などの各工程を経る間にその表面が汚染されたり損傷したりしないように、さらに表面保護フィルムで接着被覆されて長尺の光学部材積層体として形成され、該表面保護フィルムは表面保護が不要となった段階で光学部材から剥離除去される。 These optical members are usually further coated with a surface protective film so that the surface is not contaminated or damaged during each process such as punching, inspection, transportation, and assembly of the liquid crystal display panel. The surface protection film is peeled and removed from the optical member when the surface protection is no longer necessary.
このような表面保護フィルムは、光学部材の表面保護が必要とされる間、該部材の表面上でずれを生じたり表面から脱落したりすることがない程度にその表面に接着していると共に、液晶の性能など各種の検査に支障を来さないように、高度に透明であること及びフクレ、トンネリング、ハガレなど接着剤層内及び該接着剤層と光学部材との界面に欠陥がないことが要求される。光学部材からの該フィルムの剥離に際しては、剥離に伴う歪みによって光学部材や液晶セルを損傷することがないように、また液晶セルから光学部材が剥離してしまうなどの不都合が生じないように、容易に剥離できることが必要である。
近年、作業効率の向上を目的として表面保護フィルムの剥離の速度が高速化される傾向にあり高速剥離における作業性も接着剤の特性として要求されるようになった。
While such a surface protective film is required to protect the surface of the optical member, the surface protective film adheres to the surface to such an extent that the optical member does not slip or fall off from the surface. In order not to interfere with various inspections such as the performance of the liquid crystal, it must be highly transparent, and there should be no defects in the adhesive layer such as bulge, tunneling, peeling, and the interface between the adhesive layer and the optical member. Required. When peeling the film from the optical member, in order not to damage the optical member or the liquid crystal cell due to the distortion caused by the peeling, and so as not to cause inconvenience such as the optical member peeling from the liquid crystal cell, It must be easily peelable.
In recent years, the speed of peeling of the surface protective film tends to be increased for the purpose of improving working efficiency, and workability in high-speed peeling has been required as a characteristic of the adhesive.
これらの問題点を解消するため、従来から幾多の提案が知られている。例えば、特許文献１（特開平９−２０８９１０号公報）には、アルキル基の炭素数が１〜９のアクリル酸アルキルエステルを主成分とし、これに水酸基及び／又はカルボキシル基を含有する共重合可能な不飽和モノマ−、アルキル基の炭素数が１６〜２２の（メタ）アクリル酸アルキルエステル及び反応性乳化剤をそれぞれ特定量共重合してなるアクリル系共重合体に、イソシアネ−ト系などの架橋剤を特定量配合してなる粘着剤組成物及びそれを用いた表面保護フィルムが開示されている。 In order to solve these problems, many proposals have been known. For example, Patent Document 1 (Japanese Patent Application Laid-Open No. 9-208910) describes a copolymerizable alkyl ester having an alkyl group having 1 to 9 carbon atoms as a main component and containing a hydroxyl group and / or a carboxyl group. An unsaturated copolymer, an acrylic copolymer obtained by copolymerizing a specific amount of a (meth) acrylic acid alkyl ester having 16 to 22 carbon atoms in the alkyl group and a reactive emulsifier, respectively. An adhesive composition comprising a specific amount of an agent and a surface protective film using the same are disclosed.
しかしながら上記提案の粘着剤を用いた表面保護フィルムでは、確かにフクレやトンネリングの発生を抑制することは可能であったが、再剥離性はまだ必ずしも十分とはいいがたく、その剥離力が実用に供し得ないほど大きなものとなることが判明した。 However, the surface protection film using the above-mentioned pressure-sensitive adhesive was able to suppress the occurrence of swelling and tunneling, but re-peelability is still not sufficient, and its peel strength is practical. It turned out to be so large that it could not be used.
例えば、特許文献２（特開２００１−３３６２４号公報）には、温度や湿度等の環境変化によっても光学部材から剥離することがなく、且つ剥離時には糊残りなく光学部材から剥離分離できるという基本的性能を満足させつつ、エ−ジング等の加熱処理後においても光学部材の損傷や液晶セルからの剥離なしに容易に剥離分離できる表面保護フィルムを得ることを目的とした表面保護フィルムであって、剥離速度３００ｍｍ／分で１８０゜剥離において、８０℃放置の接着力が常温放置の接着力の１．３倍以内である表面保護フィルムが開示されている。 For example, in Patent Document 2 (Japanese Patent Laid-Open No. 2001-33624), there is basically no separation from an optical member due to environmental changes such as temperature and humidity, and separation and separation from the optical member without any adhesive residue at the time of separation. A surface protective film intended to obtain a surface protective film that can be easily peeled and separated without damage to the optical member or peeling from the liquid crystal cell even after heat treatment such as aging while satisfying the performance, A surface protective film is disclosed in which the adhesive strength when left at 80 ° C. is within 1.3 times the adhesive strength when left at room temperature at 180 ° peeling at a peeling speed of 300 mm / min.
しかしながら、上記第２の提案の粘着剤は、被着体としてステンレス鋼板を用いた接着力試験では、８０℃放置の接着力が常温放置の接着力１．３倍以内となってはいたが、被着体として、例えば表面にアンチグレア層を有する偏光板を用いたときには、オ−トクレ−ブ処理後に９０℃で２時間エ−ジング処理を行ったところ、偏光板表面と表面保護フィルムとの間に多数のフクレが発生するなどの問題があることが判明した。 However, the adhesive of the second proposal has an adhesive strength test using a stainless steel plate as an adherend, and the adhesive strength after standing at 80 ° C. is within 1.3 times the adhesive strength when left at room temperature. For example, when a polarizing plate having an antiglare layer on the surface is used as the adherend, an aging treatment is carried out at 90 ° C. for 2 hours after the autoclave treatment. It has been found that there are problems such as the occurrence of numerous blisters.
本発明者等は、アクリル系粘着剤の改良研究を行い、特許文献３（特開平２００３−４１２２９号公報）、特許文献４（特開２００５−９７４５１号公報）等において、光学部材表面保護フィルム用粘着剤組成物を提案している。 The inventors of the present invention have made researches on improving acrylic pressure-sensitive adhesives, and in Patent Document 3 (Japanese Patent Laid-Open No. 2003-41229), Patent Document 4 (Japanese Patent Laid-Open No. 2005-97451), etc. An adhesive composition is proposed.
特許文献４で提案した組成物は、小面積の液晶表示部材に使用される場合はバランス良く良好な性質を示すものであったが、液晶表示部材の大型化が進んだことによる、大面積の表示部材を保護する用途においては、高速剥離での接着力が大きすぎて剥離作業に支障をきたすものであった。そこで、大面積を保護する保護フィルムにおいて十分な接着力（低速での剥離力）を保持しつつ、高速での剥離力を低下させることが必要となっている。 The composition proposed in Patent Document 4 showed good properties in a good balance when used in a liquid crystal display member having a small area, but the large area due to the increase in the size of the liquid crystal display member. In the application for protecting the display member, the adhesive force at high-speed peeling is too large, which hinders the peeling work. Therefore, it is necessary to reduce the peeling force at high speed while maintaining a sufficient adhesive force (peeling force at low speed) in the protective film protecting a large area.
一方、一般にフィルムを貼り付けたり、剥離したりする際の静電気の発生は避けられないものであり、本用途において表面保護フィルムに静電気が発生すると、光学フィルム表面にごみやホコリが吸着され製品に不都合が生じる。また、保護フィルムを剥離する際に、大きな静電気が発生すると表示部材の回路が破壊してしまうおそれもある。
そこで表面保護フィルムの一部に帯電防止剤を含む帯電防止層を設けて帯電防止性能を持たせることも行われており、例えば特許文献５（特開２０００−２７３４１７号公報）には第４級アンモニウム塩を含む帯電防止層を有する表面保護フィルムが開示されている。しかしながら、この表面保護フィルムでは、支持体側に帯電防止処理が施されているため、表面保護フィルム側の帯電防止は図れるものの、被保護体の帯電防止は図れず、表面保護フィルムを剥離した際に被保護体が帯電するという不具合があった。
On the other hand, the generation of static electricity is generally unavoidable when a film is applied or peeled off. When static electricity is generated on the surface protection film in this application, dust and dust are adsorbed on the surface of the optical film and become a product. Inconvenience arises. Moreover, when big static electricity generate | occur | produces when peeling a protective film, there exists a possibility that the circuit of a display member may be destroyed.
Therefore, an antistatic layer containing an antistatic agent is provided on a part of the surface protective film to impart antistatic performance. For example, Patent Document 5 (Japanese Patent Laid-Open No. 2000-273417) discloses a fourth class. A surface protective film having an antistatic layer containing an ammonium salt is disclosed. However, in this surface protection film, since the antistatic treatment is performed on the support side, the surface protection film side can be prevented from being charged, but the object to be protected cannot be prevented from being charged. There was a problem that the object to be protected was charged.
さらに特許文献６（特開２００５−３３０４６４号公報）、特許文献７（特開２００５−１３１９５７号公報）、特許文献８（特開２００７−２９７４４６号公報）等において、粘着剤層に、イオン性液体、アルキルトリメチルアンモニウム塩、ポリエーテルポリオール類等を帯電防止成分として添加することにより、剥離帯電により発生する静電気量を低減した粘着剤が開示されている。しかしながら、粘着剤層を有する表面保護フィルムにおいては、帯電防止効果は図れるものの、表面保護フィルムとしての耐久性（耐熱性、耐湿熱性）や接着力の低下等において問題があった。 Further, in Patent Document 6 (Japanese Patent Laid-Open No. 2005-330464), Patent Document 7 (Japanese Patent Laid-Open No. 2005-131957), Patent Document 8 (Japanese Patent Laid-Open No. 2007-297446), etc., an ionic liquid is used as the adhesive layer. In addition, a pressure-sensitive adhesive is disclosed in which the amount of static electricity generated by peeling charging is reduced by adding an alkyltrimethylammonium salt, polyether polyol, or the like as an antistatic component. However, the surface protective film having the pressure-sensitive adhesive layer has an antistatic effect, but has problems in terms of durability (heat resistance, moist heat resistance) as a surface protective film and a decrease in adhesive strength.
本発明者らはさらに研究を続けた結果、特許文献９（特開２００８−６９２０２号公報）においてブレンド系樹脂を不均一に架橋した粘着剤層に特定の帯電防止剤を使用することを提案した。しかしながら、大画面化に伴い静電気発生量が増大し十分な帯電防止を図ることが困難であった。さらに、表面保護フィルムが被保護体から剥離されるまでの工程で凝集力不足のため剥がれてしまう等の問題があった。
本願の解決すべき課題はアンチグレア層など微細な凹凸を有する層を設けた偏光板などの光学部材であっても、被着体を汚染することなく、光学部材表面保護フィルムとして、大面積の光学部材からの該フィルムの剥離に際して高速剥離においても剥離帯電による静電気の発生が少なく、接着性 信頼性に優れた表面保護フィルム用アクリル系粘着剤組成物ならびに、それを用いてなるアクリル系粘着剤層を提供することである。 The problem to be solved by the present application is that an optical member such as a polarizing plate provided with a layer having fine irregularities such as an antiglare layer can be used as a surface protection film for an optical member without damaging the adherend. Acrylic pressure-sensitive adhesive composition for surface protective film with less adhesive generation and high reliability in high-speed peeling when peeling the film from a member, and an acrylic pressure-sensitive adhesive layer using the same Is to provide.
本発明者らはさらに研究を続けた結果、水酸基を有する単量体を共重合成分として０．１〜１０重量％含有し、重量平均分子量が３０万〜１００万であり、ガラス転移温度（Tg）が−５０℃以下であるアクリル系共重合体（A）１００重量部に対して、
重量平均分子量０．３万〜１０万であり、ガラス転移温度（Tg）が−2０℃〜2０℃であって、分子内にアルキレンオキシド単位 ２０以上のアルキレンオキシド鎖を有するアルキレンオキシド鎖含有アクリル系共重合体（B）０．０５ 〜２．０重量部、
および アルカリ金属塩（C） ０．００５〜０．６重量部
（ただしアルカリ金属塩（C）の量はアクリル系共重合体（B）の量を超えない。）
を含む表面保護フィルム用アクリル系粘着剤組成物。
が本課題を解決できることを見いだし、さらに研究を進めて本発明を完成した。
As a result of further research, the present inventors have contained 0.1 to 10% by weight of a monomer having a hydroxyl group as a copolymerization component, a weight average molecular weight of 300,000 to 1,000,000, and a glass transition temperature (Tg ) With respect to 100 parts by weight of the acrylic copolymer (A) having a temperature of −50 ° C. or lower,
An alkylene oxide chain-containing acrylic system having a weight average molecular weight of 30,000 to 100,000, a glass transition temperature (Tg) of −20 ° C. to 20 ° C., and having 20 or more alkylene oxide chains in the molecule Copolymer (B) 0.05 to 2.0 parts by weight,
And alkali metal salt (C) 0.005 to 0.6 parts by weight
(However, the amount of alkali metal salt (C) does not exceed the amount of acrylic copolymer (B).)
An acrylic pressure-sensitive adhesive composition for a surface protective film.
Found that this problem could be solved, and further researched to complete the present invention.
本発明のアクリル系粘着剤組成物は、架橋点として反応性官能基を含む特定の分子量範囲、特定のガラス転移温度範囲のアクリル系共重合体（Ａ）に特定の構造、特定のガラス転移温度範囲のアルキレンオキシド鎖含有アクリル系共重合体（Ｂ）及び アルカリ金属塩を配合した帯電防止性を有する粘着剤組成物である。 The acrylic pressure-sensitive adhesive composition of the present invention has a specific structure and a specific glass transition temperature for the acrylic copolymer (A) having a specific molecular weight range containing a reactive functional group as a crosslinking point and a specific glass transition temperature range. It is a pressure-sensitive adhesive composition having antistatic properties in which an alkylene oxide chain-containing acrylic copolymer (B) in the range and an alkali metal salt are blended.
このように構成されることによって本発明のアクリル系粘着剤組成物を用いた表面保護フィルムは、光学部材の表面保護性及び高度な透明性を有すると共に、良好ななじみ性も有し、また例えば、表面にアンチグレア層など微細な凹凸を有する層を設けた偏光板などの光学部材に使用する場合でも、オ−トクレ−ブ処理やその後の作業上及び使用上の熱履歴を経た後にも、フクレ、トンネリング、ハガレなどの接着剤層欠陥の発生が見られず、さらにまた、大面積の光学部材からの該フィルムの剥離に際して高速剥離においても剥離帯電による静電気の発生が少なく、良好な剥離特性を示し、該光学部材や液晶セルの配向の乱れや、セルギャップの拡大、液晶セルからの光学部材の剥離などの不都合を生じさせることなく容易に剥離することができ、樹脂をブレンドすることなく帯電防止成分の組み合わせによって少量の添加で効果的な帯電防止性を付与することができるものである。 By being configured in this manner, the surface protective film using the acrylic pressure-sensitive adhesive composition of the present invention has the surface protection and high transparency of the optical member, and also has good conformability, Even if it is used for an optical member such as a polarizing plate provided with a layer having fine irregularities such as an anti-glare layer on its surface, it does not move even after an autoclave treatment or subsequent work and heat history during use. In addition, no defects in the adhesive layer such as tunneling, peeling, etc. were observed, and even when the film was peeled from a large area optical member, there was little generation of static electricity due to peeling charging even at high speed peeling, and good peeling characteristics were obtained. And easy peeling without causing inconveniences such as disorder of alignment of the optical member or liquid crystal cell, expansion of the cell gap, peeling of the optical member from the liquid crystal cell, etc. Can, in which the resin can impart effective antistatic properties at a small amount by the combination of antistatic components without blending.
本発明の粘着剤組成物は、特定のアクリル系共重合体（Ａ）、特定のアクリル系共重合体（Ｂ）及び、アルカリ金属塩（Ｃ）を含有する粘着剤組成物である。 The pressure-sensitive adhesive composition of the present invention is a pressure-sensitive adhesive composition containing a specific acrylic copolymer (A), a specific acrylic copolymer (B), and an alkali metal salt (C).
本発明のアクリル系共重合体（Ａ）とは、重量平均分子量（Mw）が３０万〜１００万のアクリル系共重合体（Ａ）であり、該重量平均分子量（Mw）は、好ましくは４０万〜８０万であるのがよい。該重量平均分子量（Mw）が該下限値以上あれば、再剥離時の接着力が大きくなりすぎることがなく、特に加熱処理などを行っても光学部材の損傷や光学部材の不具合を生じることなしに表面保護フィルムを容易に剥離することができるので好ましい。一方該上限値以下であれば、得られる感圧接着剤層の流動性が優れており、表面の微小の凹凸を有する偏光板に用いたときにでも感圧接着剤が偏光板表面を十分に濡らすことができるため、偏光板表面と表面保護フィルムの感圧接着剤層との間にフクレを生じることがないので好ましい。 The acrylic copolymer (A) of the present invention is an acrylic copolymer (A) having a weight average molecular weight (Mw) of 300,000 to 1,000,000, and the weight average molecular weight (Mw) is preferably 40. It should be 10,000 to 800,000. If the weight average molecular weight (Mw) is equal to or greater than the lower limit, the adhesive force during re-peeling will not be too high, and damage to the optical member or failure of the optical member will not occur even if heat treatment is performed. It is preferable because the surface protective film can be easily peeled off. On the other hand, if the upper limit is not exceeded, the fluidity of the resulting pressure-sensitive adhesive layer is excellent, and the pressure-sensitive adhesive sufficiently covers the surface of the polarizing plate even when used for a polarizing plate having minute irregularities on the surface. Since it can be wetted, it is preferable because no swelling occurs between the polarizing plate surface and the pressure-sensitive adhesive layer of the surface protective film.
なお、アクリル系共重合体（Ａ）の重量平均分子量（Mw）は、下記の方法により測定された値である。重量平均分子量（Mw）の測定方法 下記(1)〜(3)に従って測定する。 (1) アクリル系共重合体溶液を剥離シートに塗布し、１００℃で２分間乾燥し、フィルム状のアクリル系共重合体を得る。 (2) 上記(1)で得られたフィルム状のアクリル系共重合体をテトラヒドロフランにて固形分０．２％になるように溶解させる。 (3) 下記条件にて、ゲルパーミエーションクロマトグラフィー（GPC）を用いて、アクリル系共重合体（Ａ）の重量平均分子量（Mw）を測定する。 The weight average molecular weight (Mw) of the acrylic copolymer (A) is a value measured by the following method. Measuring method of weight average molecular weight (Mw) It measures according to the following (1)-(3). (1) An acrylic copolymer solution is applied to a release sheet and dried at 100 ° C. for 2 minutes to obtain a film-like acrylic copolymer. (2) The film-like acrylic copolymer obtained in (1) above is dissolved in tetrahydrofuran so that the solid content is 0.2%. (3) The weight average molecular weight (Mw) of the acrylic copolymer (A) is measured using gel permeation chromatography (GPC) under the following conditions.
（条件）GPC ：HLC-８２２０ GPC〔東ソー(株)製〕カラム ：TSK-GEL GMHXL ４本使用移動相溶媒：テトラヒドロフラン流速 ：０．６ml／min カラム温度：40℃ (Conditions) GPC: HLC-8220 GPC [manufactured by Tosoh Corporation] Column: TSK-GEL GMHXL 4 mobile phase solvents: tetrahydrofuran flow rate: 0.6 ml / min Column temperature: 40 ° C
上記アクリル系共重合体(A)のガラス転移温度（Tg）は、好ましくは−５０℃以下、更に好ましくは−５５〜−８０℃であるのがよい。Tgが該温度を超えて高すぎては、感圧接着剤層が硬く流動しにくくなり、特に表面にアンチグレア層などを有する偏光板に用いたとき、感圧接着剤が表面の凹凸を十分に濡らすことができず、そのため偏光板表面と表面保護フィルムの感圧接着剤層との間にフクレを生じることがあるので好ましくない。 The glass transition temperature (Tg) of the acrylic copolymer (A) is preferably −50 ° C. or lower, more preferably −55 to −80 ° C. If Tg is too high above the temperature, the pressure-sensitive adhesive layer is hard and difficult to flow, and particularly when used for a polarizing plate having an anti-glare layer on the surface, the pressure-sensitive adhesive has sufficient surface irregularities. This is not preferable because it cannot be wetted and, therefore, swelling may occur between the polarizing plate surface and the pressure-sensitive adhesive layer of the surface protective film.
なお本発明において、アクリル系共重合体（Ａ）のガラス転移温度（Tg）は下記により測定し決定された値である。 ガラス転移温度（Tg） 下記(1)〜(3)に従って測定する。 (1) アクリル系共重合体溶液を剥離シートに塗布し、１００℃で２分間乾燥し、フィルム状のアクリル系共重合体を得る。 (2) 厚さ約０．０５mmアルミニウム箔製の、内径約５mm、深さ約５mmの円筒型のセルに、(1)で得た試料約１０mgを秤量したものを測定試料とする。 (3)セイコー電子工業(株)製ＳＳＣ−５０００型示差走査熱量計（Differential Scanning Calorimeter ）を用い、−１５０℃から昇温速度１０℃/minで測定する。 In the present invention, the glass transition temperature (Tg) of the acrylic copolymer (A) is a value determined by measurement as follows. Glass transition temperature (Tg) Measured according to the following (1) to (3). (1) An acrylic copolymer solution is applied to a release sheet and dried at 100 ° C. for 2 minutes to obtain a film-like acrylic copolymer. (2) A measurement sample is prepared by weighing about 10 mg of the sample obtained in (1) into a cylindrical cell made of aluminum foil with a thickness of about 0.05 mm and having an inner diameter of about 5 mm and a depth of about 5 mm. (3) Using an SSC-5000 type differential scanning calorimeter manufactured by Seiko Denshi Kogyo Co., Ltd., the temperature is measured from −150 ° C. at a heating rate of 10 ° C./min.
本発明のアクリル系共重合体(A)は水酸基を有する単量体を含有する。水酸基を有する単量体としては、水酸基を有する（メタ）アクリル単量体及びその他の水酸基を有する単量体を挙げることができるが、上記水酸基を有する（メタ）アクリル単量体としては、例えば、2-ヒドロキシエチル（メタ）アクリレート、2-ヒドロキシプロピル（メタ）アクリレート、3-ヒドロキシプロピル（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、3-メチル-3-ヒドロキシブチル（メタ）アクリレート、1,1-ジメチル-3-ブチル（メタ）アクリレート、1,3-ジメチル-3-ヒドロキシブチル（メタ）アクリレート、2,2,4-トリメチル-3-ヒドロキシペンチル（メタ）アクリレート、2-エチル-3-ヒドロキシヘキシル（メタ）アクリレート、グリセリンモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、ポリ（エチレングリコール−プロピレングリコール）モノ（メタ）アクリレート、等を挙げることができ、その他の水酸基を有する単量体としては、Ｎ−メチロールアクリルアミド、アリルアルコール、メタリルアルコール等を挙げることができる。 The acrylic copolymer (A) of the present invention contains a monomer having a hydroxyl group. Examples of the monomer having a hydroxyl group include a (meth) acrylic monomer having a hydroxyl group and another monomer having a hydroxyl group. Examples of the (meth) acrylic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-methyl-3-hydroxybutyl (meth) acrylate, 1,1-dimethyl-3-butyl (meth) acrylate, 1,3-dimethyl-3-hydroxybutyl (meth) acrylate, 2,2,4-trimethyl-3-hydroxypentyl (meth) acrylate, 2-ethyl- 3-hydroxyhexyl (meth) acrylate, glycerol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate , Polyethylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene glycol) mono (meth) acrylate, and the like. Other monomers having a hydroxyl group include N-methylolacrylamide, allyl alcohol, And methallyl alcohol.
これらの単量体の中で、他の単量体と共重合してアクリル共重合体（A）を合成する際の他の単量体との相溶性及び共重合性が良好である、並びに架橋剤との架橋反応が良好である観点から、2-ヒドロキシエチル（メタ）アクリレート、4-ヒドロキシブチル（メタ）アクリレートが好ましい。 Among these monomers, good compatibility and copolymerization with other monomers when copolymerizing with other monomers to synthesize acrylic copolymer (A), and From the viewpoint of good crosslinking reaction with the crosslinking agent, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferred.
上記水酸基含有単量体の上記アクリル共重合体（A）分子中に共重合性分として含まれる含有量は、アクリル系共重合体（Ａ）に対し０．１〜１０．０重量％、好ましくは２．０〜８．０重量％含有されることにより、共重合量が該下限値以上であれば被着体への汚染がないので好ましく、一方該上限値未満であれば、なじみ性（濡れ性）に問題を生じない。 The content of the hydroxyl group-containing monomer contained in the acrylic copolymer (A) molecule as a copolymerizable component is 0.1 to 10.0% by weight, preferably based on the acrylic copolymer (A). Is preferably contained in an amount of 2.0 to 8.0% by weight so that if the copolymerization amount is not less than the lower limit value, there is no contamination of the adherend, while if less than the upper limit value, the compatibility ( No problem with wettability.
本発明においては、アクリル系共重合体（Ａ）を構成する全単量体成分（共重合体を構成する単量体を単に共重合成分と記載することがある。）の５０重量％以上、好ましくは９０重量％以上がアクリル単量体である共重合体をいう。 In the present invention, 50% by weight or more of all monomer components constituting the acrylic copolymer (A) (the monomer constituting the copolymer may be simply referred to as a copolymer component), Preferably, it refers to a copolymer in which 90% by weight or more is an acrylic monomer.
上記アクリル単量体としては、例えば、メチルアクリレート、エチルアクリレート、n-ブチルアクリレート、i-ブチルアクリレート、n-オクチルアクリレート、i-オクチルアクリレート、2-エチルヘキシルアクリレート、n-ノニルアクリレート、i-ノニルアクリレート、n-デシルアクリレート、n-ドデシルアクリレート、ステアリルアクリレート等のアクリル酸の炭素数１〜18の直鎖もしくは分枝アルキルエステル；例えば、メチルメタクリレート、エチルメタクリレート、n-ブチルメタクリレート、2-エチルヘキシルメタクリレート、n-ドデシルメタクリレート、ステアリルメタクリレート等のメタクリル酸の炭素数１〜18の直鎖もしくは分枝アルキルエステル、更にはこれらの各種誘導体の１種又は２種以上を選ぶことができる。 Examples of the acrylic monomer include methyl acrylate, ethyl acrylate, n-butyl acrylate, i-butyl acrylate, n-octyl acrylate, i-octyl acrylate, 2-ethylhexyl acrylate, n-nonyl acrylate, and i-nonyl acrylate. A linear or branched alkyl ester having 1 to 18 carbon atoms of acrylic acid such as n-decyl acrylate, n-dodecyl acrylate, stearyl acrylate; for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, A linear or branched alkyl ester having 1 to 18 carbon atoms of methacrylic acid such as n-dodecyl methacrylate and stearyl methacrylate, and one or more of these various derivatives can be selected.
上記アクリル系共重合体（Ａ）は、アクリル単量体を主成分とした共重合体であるが、その他の種類の単量体を、前記の単量体の構成量を損なわれない範囲内でアクリル系共重合体（Ａ）の重合成分として使用することができる。 The acrylic copolymer (A) is a copolymer having an acrylic monomer as a main component, but other types of monomers are within the range in which the constituent amount of the monomer is not impaired. And can be used as a polymerization component of the acrylic copolymer (A).
上記その他の種類の単量体としては、例えば、スチレン、αーメチルスチレン、tーブチルスチレン、pー クロロスチレン、クロロメチルスチレン、ビニルトルエン等の芳香族モノビニル単量体；例えば、アクリロニトリル、メタクリロニトリル等のシアン化ビニル単量体；例えば、蟻酸ビニル、酢酸ビニル、プロピオン酸ビニル、バーサチック酸ビニル等、更にこれらの各種誘導体を挙げることができる。 Examples of the other types of monomers include aromatic monovinyl monomers such as styrene, α-methyl styrene, t-butyl styrene, p-chloro styrene, chloromethyl styrene, and vinyl toluene; for example, acrylonitrile and methacrylonitrile. Vinyl cyanide monomers; for example, vinyl formate, vinyl acetate, vinyl propionate, vinyl versatate, and various other derivatives thereof.
上記アクリル共重合体（A）に水酸基以外の官能基を有する単量体が共重合性分として含有されていてもよく、例えば、カルボキシル基含有単量体、グリシジル基含有単量体、アミド基，Ｎ−置換アミド基含有単量体、三級アミノ基含有単量体等の１種又は２種以上を使用することができる。 The acrylic copolymer (A) may contain a monomer having a functional group other than a hydroxyl group as a copolymerizable component. For example, a carboxyl group-containing monomer, a glycidyl group-containing monomer, an amide group , N-substituted amide group-containing monomers, tertiary amino group-containing monomers and the like can be used alone or in combination.
上記カルボキシル基含有単量体としては、例えば、アクリル酸、メタクリル酸、マレイン酸、無水マレイン酸、フマル酸、クロトン酸、イタコン酸、シトラコン酸、桂皮酸、コハク酸モノヒドロキシエチル(メタ)アクリ レート、マレイン酸モノヒドロキシエチル(メタ)アクリレート、フマル酸モノヒドロキシエチル(メタ)アクリレート、フタル酸モノヒドロキシエチル(メタ)アクリレート、1,2-ジカルボキシシクロヘキサンモノヒドロキシエチル(メタ)アクリレート、(メタ)アクリル酸ダイマー、ω-カルボキシ-ポリカプロラクトンモノ(メタ) アクリレート等を挙げることができる。 Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, citraconic acid, cinnamic acid, and monohydroxyethyl (meth) acrylate succinate. , Monohydroxyethyl (meth) acrylate maleate, monohydroxyethyl (meth) acrylate fumarate, monohydroxyethyl (meth) acrylate phthalate, 1,2-dicarboxycyclohexane monohydroxyethyl (meth) acrylate, (meth) acrylic And acid dimer, ω-carboxy-polycaprolactone mono (meth) acrylate, and the like.
グリシジル基含有単量体としては、例えば、グリシジル（メタ）アクリレート、3,4-エポキシシクロヘキシルメチル（メタ）アクリレート、グリシジルビニルエーテル、3,4-エポキシシクロヘキシルビニルエーテル、グリシジル（メタ）アリルエーテル、3,4-エポキシシクロヘキシル（メタ）アリルエーテル等が挙げられる。 Examples of the glycidyl group-containing monomer include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl vinyl ether, 3,4-epoxycyclohexyl vinyl ether, glycidyl (meth) allyl ether, 3,4 -Epoxy cyclohexyl (meth) allyl ether etc. are mentioned.
アミド基，Ｎ−置換アミド基含有単量体としては、例えば、アクリルアミド、メタクリルアミド、Ｎ−メチル（メタ）アクリルアミド、Ｎ−エチル（メタ）アクリルアミド、Ｎ−メトキシメチル（メタ）アクリルアミド、Ｎ−エトキシメチル（メタ）アクリルアミド、Ｎ−プロポキシメチル（メタ）アクリルアミド、Ｎ−ブトキシメチル（メタ）アクリルアミド、Ｎ−ｔｅｒｔ−ブチルアクリルアミド、Ｎ−オクチルアクリルアミド、ジアセトンアクリルアミド等が挙げられる。 Examples of amide group and N-substituted amide group-containing monomers include acrylamide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, and N-ethoxy. Examples include methyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-tert-butylacrylamide, N-octylacrylamide, diacetone acrylamide and the like.
三級アミノ基含有単量体としては、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、ジメチルアミノプロピル（メタ）アクリルアミド等が挙げられる。 Examples of the tertiary amino group-containing monomer include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, and the like.
本発明のアクリル系粘着剤組成物は 特定の構造、特定のガラス転移温度範囲のアルキレンオキシド鎖を含有する アクリル系共重合体（Ｂ）を含有する。 The acrylic pressure-sensitive adhesive composition of the present invention contains an acrylic copolymer (B) containing an alkylene oxide chain having a specific structure and a specific glass transition temperature range.
本発明のアクリル系共重合体（Ｂ）とは、アルキレンオキシド鎖含有アクリル単量体を共重合成分として含む 平均分子量（Mw）が０．３万〜１０万 好ましくは０．５万〜６．０万のアクリル系共重合体（Ｂ）である。平均分子量（Mw）が０．３万以上であれば十分な接着力が得られ、６.０万未満であれば十分な相溶性が得られる。 The acrylic copolymer (B) of the present invention has an average molecular weight (Mw) containing an alkylene oxide chain-containing acrylic monomer as a copolymerization component of 30,000 to 100,000, preferably 50,000 to 6. It is a 100,000 acrylic copolymer (B). If the average molecular weight (Mw) is 30,000 or more, sufficient adhesive strength is obtained, and if it is less than 60,000, sufficient compatibility is obtained.
なお、アクリル系共重合体（Ｂ）の重量平均分子量（Mw）は、アクリル系共重合体（Ａ）の重量平均分子量（Mw）を測定したのと同様の方法で測定できる。 The weight average molecular weight (Mw) of the acrylic copolymer (B) can be measured by the same method as the weight average molecular weight (Mw) of the acrylic copolymer (A).
上記アクリル系共重合体(Ｂ)のガラス転移温度（Tg）は、好ましくは−２０℃〜２０℃、更に好ましくは −１０〜１５℃であるのがよい。Ｔｇが−２０℃以上であれば、十分な接着力が得られ、２０℃以下であれば基材密着性が低下することはない。 The glass transition temperature (Tg) of the acrylic copolymer (B) is preferably −20 ° C. to 20 ° C., more preferably −10 to 15 ° C. If Tg is −20 ° C. or higher, sufficient adhesive strength can be obtained, and if it is 20 ° C. or lower, substrate adhesion does not decrease.
また、上記下限値以上であると、凝集力不足などが生ずることがなく耐久性が確保できるので好ましい。 Moreover, it is preferable that it is more than the said lower limit since durability cannot be ensured without the cohesion force deficiency etc. arising.
なお本発明において、アクリル系共重合体（Ｂ）のガラス転移温度（Tg）はアクリル系共重合体（Ａ）のガラス転移温度（Tg）を測定したのと同様の方法で測定する。 In the present invention, the glass transition temperature (Tg) of the acrylic copolymer (B) is measured by the same method as that for measuring the glass transition temperature (Tg) of the acrylic copolymer (A).
上記アクリル系共重合体（Ｂ）とは、本発明においては、アクリル系共重合体（Ｂ）を構成する全単量体成分（共重合体を構成する単量体を単に共重合成分と記載することがある。）の５０重量％以上、好ましくは７０重量％以上がアクリル単量体である共重合体をいう。 In the present invention, the acrylic copolymer (B) refers to all monomer components constituting the acrylic copolymer (B) (the monomer constituting the copolymer is simply referred to as a copolymer component). Of 50% by weight or more, preferably 70% by weight or more of the acrylic monomer.
上記アクリル単量体としてアクリル系共重合体（Ａ）に記載したものと同様のアクリル単量体が使用できる。 As the acrylic monomer, the same acrylic monomer as that described in the acrylic copolymer (A) can be used.
本発明においてアクリル系共重合体（Ｂ）は分子内にアルキレンオキシド鎖を有するアルキレンオキシド鎖含有アクリル系単量体を共重合成分として含むものである。 In the present invention, the acrylic copolymer (B) contains an alkylene oxide chain-containing acrylic monomer having an alkylene oxide chain in the molecule as a copolymer component.
本発明に用いられる、アルキレンオキシド鎖を有するアクリル系単量体として、たとえば、エチレンオキシド鎖、プロピレンオキサイド鎖を有するアクリル系単量体が挙げられ、ポリエチレングリコール（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、メトキシポリプロピレングリコール（メタ）アクリレート、ポリプロピレングリコール（メタ）アクリレート等を挙げることができ、メトキシポリエチレングリコール（メタ）アクリレートが好ましい。
Examples of the acrylic monomer having an alkylene oxide chain used in the present invention include an acrylic monomer having an ethylene oxide chain and a propylene oxide chain, such as polyethylene glycol (meth) acrylate and methoxypolyethylene glycol (meth). Examples include acrylate, methoxypolypropylene glycol (meth) acrylate, and polypropylene glycol (meth) acrylate, and methoxypolyethylene glycol (meth) acrylate is preferable.
アルキレンオキシド単位は２０以上であることが必要であり、４０以上であることが好ましい。アルキレンオキシド単位が２０以上のアクリル系単量体を共重合成分として含むものであれば後述するアルカリ金属塩との組み合わせによって顕著な帯電防止効果を発揮することができる。
The alkylene oxide unit needs to be 20 or more, and preferably 40 or more. If the alkylene oxide unit contains an acrylic monomer having 20 or more as a copolymerization component, a remarkable antistatic effect can be exhibited by a combination with an alkali metal salt described later.
さらに、上記アクリル系共重合体（Ｂ）中に、構成成分としてカルボキシル基、水酸基等の官能基を有する他の単量体を含んでもよい。 Further, the acrylic copolymer (B) may contain another monomer having a functional group such as a carboxyl group or a hydroxyl group as a constituent component.
上記官能基を有する単量体としては、他にアクリル系共重合体（Ａ）に記載したものと同様の官能基を有する単量体が使用できる。 As the monomer having the functional group, other monomers having the same functional group as those described in the acrylic copolymer (A) can be used.
本発明に用いられるアクリル系共重合体（A）およびアクリル系共重合体（Ｂ）の重合方法は、特に制限されるものではなく、溶液重合、乳化重合、懸濁重合などの公知の方法により重合できるが、重合により得られたアクリル系共重合体を用いて本発明の粘着剤組成物を製造するに当り、処理工程が比較的簡単で且つ短時間で行えることから溶液重合により重合することが好ましい。 The polymerization method of the acrylic copolymer (A) and the acrylic copolymer (B) used in the present invention is not particularly limited, and may be a known method such as solution polymerization, emulsion polymerization, suspension polymerization. Although it is possible to polymerize, when the pressure-sensitive adhesive composition of the present invention is produced using the acrylic copolymer obtained by polymerization, it is polymerized by solution polymerization because the treatment process is relatively simple and can be performed in a short time. Is preferred.
溶液重合は、一般に、重合槽内に所定の有機溶媒、単量体、重合開始剤、及び、必要に応じて用いられる連鎖移動剤を仕込み、窒素気流中又は有機溶媒の還流温度で、撹拌しながら数時間加熱反応させることにより行なうなど公知の方法を使用することができる。 In solution polymerization, a predetermined organic solvent, a monomer, a polymerization initiator, and a chain transfer agent used as needed are generally charged in a polymerization tank, and stirred in a nitrogen stream or at the reflux temperature of the organic solvent. However, a known method can be used, for example, by performing a heating reaction for several hours.
なお、本発明のアクリル系共重合体（A）およびアクリル系共重合体（Ｂ）の重量平均分子量は、反応温度、時間、溶剤量、触媒の種類や量により容易に調節することができる。 In addition, the weight average molecular weights of the acrylic copolymer (A) and the acrylic copolymer (B) of the present invention can be easily adjusted by the reaction temperature, time, amount of solvent, type and amount of catalyst.
前記 アクリル系共重合体（Ａ）
およびアクリル系共重合体（Ｂ）の重合に際し、重合用有機溶媒としては、例えば、ベンゼン、トルエン、エチルベンゼン、ｎ-プロピルベンゼン、ｔ-ブチルベンゼン、ｏ-キシレン、ｍ-キシレン、ｐ-キシレン、テトラリン、デカリン、芳香族ナフサなどの芳香族炭化水素類；例えば、ｎ-ヘキサン、ｎ-ヘプタン、ｎ-オクタン、ｉ-オクタン、ｎ-デカン、ジペンテン、石油スピリット、石油ナフサ、テレピン油などの脂肪系もしくは脂環族系炭化水素類；例えば、酢酸エチル、酢酸ｎ-ブチル、酢酸ｎ-アミル、酢酸２-ヒドロキシエチル、酢酸２-ブトキシエチル、酢酸３-メトキシブチル、安息香酸メチルなどのエステル類；例えば、アセトン、メチルエチルケトン、メチル-ｉ-ブチルケトン、イソホロン、シクロヘキサノン、メチルシクロヘキサノンなどのケトン類；例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテルなどのグリコールエーテル類；例えば、メチルアルコール、エチルアルコール、ｎ-プロピルアルコール、ｉ-プロピルアルコール、ｎ-ブチルアルコール、ｉ-ブチルアルコール、ｓ-ブチルアルコール、ｔ-ブチルアルコールなどのアルコール類；などを挙げることができる。これらの有機溶媒はそれぞれ単独で、又は２種以上混合して用いることができる。
Acrylic copolymer (A)
In the polymerization of the acrylic copolymer (B), examples of the organic solvent for polymerization include benzene, toluene, ethylbenzene, n-propylbenzene, t-butylbenzene, o-xylene, m-xylene, p-xylene, Aromatic hydrocarbons such as tetralin, decalin, aromatic naphtha; fats such as n-hexane, n-heptane, n-octane, i-octane, n-decane, dipentene, petroleum spirit, petroleum naphtha, turpentine oil Or alicyclic hydrocarbons; for example, esters such as ethyl acetate, n-butyl acetate, n-amyl acetate, 2-hydroxyethyl acetate, 2-butoxyethyl acetate, 3-methoxybutyl acetate, and methyl benzoate For example, acetone, methyl ethyl ketone, methyl-i-butyl ketone, isophorone, cyclohexanone, methylcyclohex Ketones such as non; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether; and alcohols such as n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol, s-butyl alcohol and t-butyl alcohol. These organic solvents can be used alone or in admixture of two or more.
これら重合用有機溶媒のうち、前記アクリル系共重合体（Ａ）
およびアクリル系共重合体（Ｂ）の重合に際しては、重合反応中に連鎖移動を生じにくい有機溶媒、例えば、エステル類、ケトン類を使用することが好ましく、特に、アクリル系共重合体の溶解性、重合反応の容易さなどの点から、酢酸エチル、アセトンなどの使用が好ましい。
Among these organic solvents for polymerization, the acrylic copolymer (A)
In the polymerization of the acrylic copolymer (B), it is preferable to use an organic solvent that does not easily cause chain transfer during the polymerization reaction, for example, esters and ketones, and particularly the solubility of the acrylic copolymer. From the viewpoint of ease of polymerization reaction, use of ethyl acetate, acetone or the like is preferable.
前記の重合開始剤としては、通常の溶液重合で使用できる有機過酸化物、アゾ化合物などを使用することが可能である。
このような有機過酸化物としては、例えば、ｔ-ブチルハイドロパーオキサイド、クメンハイドロオキサイド、ジクミルパーオキサイド、ベンゾイルパーオキシド、ラウロイルパーオキシド、カプロイルパーオキシド、ジ-ｉ-プロピルパーオキシジカーボネート、ジ-２-エチルヘキシルパーオキシジカーボネート、ｔ-ブチルパーオキシビバレート、２，２-ビス(４，４-ジ-ｔ-ブチルパーオキシシクロヘキシル)プロパン、２，２-ビス(４，４-ジ-ｔ-アミルパーオキシシクロヘキシル)プロパン、２，２-ビス(４，４-ジ-ｔ-オクチルパーオキシシクロヘキシル)プロパン、２，２-ビス(４，４-ジ-α-クミルパーオキシシクロヘキシル)プロパン、２，２-ビス(４，４-ジ-ｔ-ブチルパーオキシシクロヘキシル)ブタン、２，２-ビス(４，４-ジ-ｔ-オクチルパーオキシシクロヘキシル)ブタンなどが挙げられ、アゾ化合物としては、例えば、２，２’-アゾビス-i-ブチロニトリル、２，２’-アゾビス-２，４-ジメチルバレロニトリル、２，２’-アゾビス-４-メトキシ-２，４-ジメチルバレロニトリルなどを挙げることができる。
As said polymerization initiator, it is possible to use the organic peroxide, an azo compound, etc. which can be used by normal solution polymerization.
Examples of such organic peroxides include t-butyl hydroperoxide, cumene hydroxide, dicumyl peroxide, benzoyl peroxide, lauroyl peroxide, caproyl peroxide, and di-i-propyl peroxydicarbonate. , Di-2-ethylhexyl peroxydicarbonate, t-butyl peroxybivalate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, 2,2-bis (4,4- Di-t-amylperoxycyclohexyl) propane, 2,2-bis (4,4-di-t-octylperoxycyclohexyl) propane, 2,2-bis (4,4-di-α-cumylperoxycyclohexyl) Propane, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) butane, 2,2-bis (4,4-di-t-octylpero Examples of azo compounds include 2,2′-azobis-i-butyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, and 2,2′-azobis-4. And -methoxy-2,4-dimethylvaleronitrile.
これら有機過酸化物のうち、前記アクリル系共重合体（Ａ）およびアクリル系共重合体（Ｂ）の重合に際しては、重合反応中にグラフト反応を起こさない重合開始剤が好ましく、特にアゾビス系が好ましい。その使用量は、通常、単量体合計１００重量部に対して０．０１〜２．０重量部、好ましくは０．１〜１．０重量部である。 Among these organic peroxides, in the polymerization of the acrylic copolymer (A) and the acrylic copolymer (B), a polymerization initiator that does not cause a graft reaction during the polymerization reaction is preferable. preferable. The amount used is usually 0.01 to 2.0 parts by weight, preferably 0.1 to 1.0 parts by weight, based on 100 parts by weight of the total amount of monomers.
また、本発明に用いられるアクリル系共重合体（Ａ）およびアクリル系共重合体（Ｂ）の製造に際しては、連鎖移動剤は使用しないのが普通であるが、本発明の目的及び効果を損なわない範囲で、必要に応じて使用することは可能である。
このような連鎖移動剤としては、例えば、シアノ酢酸；シアノ酢酸の炭素数１〜８のアルキルエステル類；ブロモ酢酸；ブロモ酢酸の炭素数１〜８のアルキルエステル類；アントラセン、フェナントレン、フルオレン、９-フェニルフルオレンなどの芳香族化合物類；ｐ-ニトロアニリン、ニトロベンゼン、ジニトロベンゼン、ｐ-ニトロ安息香酸、ｐ-ニトロフェノール、ｐ-ニトロトルエンなどの芳香族ニトロ化合物類；ベンゾキノン、２，３，５，６-テトラメチル-ｐ-ベンゾキノンなどのベンゾキノン誘導体類；トリブチルボランなどのボラン誘導体；四臭化炭素、四塩化炭素、１，１，２，２-テトラブロモエタン、トリブロモエチレン、トリクロロエチレン、ブロモトリクロロメタン、トリブロモメタン、３-クロロ-１-プロペンなどのハロゲン化炭化水素類；クロラール、フラルデヒドなどのアルデヒド類：炭素数１〜１８のアルキルメルカプタン類；チオフェノール、トルエンメルカプタンなどの芳香族メルカプタン類；メルカプト酢酸、メルカプト酢酸の炭素数１〜１０のアルキルエステル類；炭素数１〜１２のヒドロキシアルキルメルカプタン類；ビネン、ターピノレンなどのテルペン類；などを挙げることができる。
In the production of the acrylic copolymer (A) and the acrylic copolymer (B) used in the present invention, it is normal not to use a chain transfer agent, but the object and effect of the present invention are impaired. It is possible to use it as necessary within a range.
Examples of such chain transfer agents include cyanoacetic acid; alkyl esters having 1 to 8 carbon atoms of cyanoacetic acid; bromoacetic acid; alkyl esters having 1 to 8 carbon atoms of bromoacetic acid; anthracene, phenanthrene, fluorene, 9 -Aromatic compounds such as phenyl fluorene; aromatic nitro compounds such as p-nitroaniline, nitrobenzene, dinitrobenzene, p-nitrobenzoic acid, p-nitrophenol, p-nitrotoluene; benzoquinone, 2, 3, 5, Benzoquinone derivatives such as 6-tetramethyl-p-benzoquinone; borane derivatives such as tributylborane; carbon tetrabromide, carbon tetrachloride, 1,1,2,2-tetrabromoethane, tribromoethylene, trichloroethylene, bromotrichloro Halo such as methane, tribromomethane, 3-chloro-1-propene Hydrochlorinated hydrocarbons; Aldehydes such as chloral and furaldehyde: alkyl mercaptans having 1 to 18 carbon atoms; Aromatic mercaptans such as thiophenol and toluene mercaptan; alkyl esters having 1 to 10 carbon atoms of mercaptoacetic acid and mercaptoacetic acid C1-C12 hydroxyalkyl mercaptans; Terpenes such as vinylene and terpinolene;
重合温度としては、一般に約３０〜１８０℃、好ましくは４０〜１５０℃、より好ましくは５０〜９０℃の範囲である。 The polymerization temperature is generally about 30 to 180 ° C, preferably 40 to 150 ° C, more preferably 50 to 90 ° C.
なお、溶液重合法などで得られた重合物中に未反応の単量体が含まれる場合は、該単量体を除くために、メタノールなどによる再沈澱法で精製することも可能である。 When an unreacted monomer is contained in a polymer obtained by a solution polymerization method or the like, it can be purified by a reprecipitation method using methanol or the like in order to remove the monomer.
本発明に用いられるアルカリ金属塩（C）は、リチウム、ナトリウム、カリウムをカチオンとする金属塩である。
具体的には、Ｌｉ＋、Ｎａ＋、Ｋ＋ 等のカチオンと、Ｃｌ−、Ｂｒ−、Ｉ−、ＢＦ４ −、ＰＦ６ −、ＳＣＮ−、ＣｌＯ４ −、ＣＦ３ＳＯ３ −、（ＣＦ３ＳＯ２）２Ｎ−、（Ｃ２Ｆ５ＳＯ２）２Ｎ−、（ＣＦ３ＳＯ２）３Ｃ−等の アニオンから構成される金属塩が好適に用いられる。 特に、ＬｉＢｒ、ＬｉＩ、ＬｉＢＦ４、ＬｉＰＦ６、ＬｉＳＣＮ、ＬｉＣｌＯ４、ＬｉＣＦ３ＳＯ３、Ｌｉ（ＣＦ３ＳＯ２）２Ｎ、Ｌｉ（Ｃ２Ｆ５ＳＯ２）２Ｎ、Ｌｉ（ＣＦ３ＳＯ２）３Ｃ などのリチウム塩が好ましく用いられる。中でも ＬｉＣＦ３ＳＯ３、Ｌｉ（ＣＦ３ＳＯ２）２Ｎ、Ｌｉ（Ｃ２Ｆ５ＳＯ２）２Ｎ、Ｌｉ（ＣＦ３ＳＯ２）３Ｃ 等の フルオロメチルスルフォニルリチウム塩は、帯電防止効果、金属腐食性が良好であるため特に好ましい。 これらのアルカリ金属塩は単独で使用してもよく、また２種以上を混合して使用してもよい。
The alkali metal salt (C) used in the present invention is a metal salt having lithium, sodium or potassium as a cation.
Specifically, cations such as Li + , Na + , K + , Cl − , Br − , I − , BF 4 − , PF 6 − , SCN − , ClO 4 − , CF 3 SO 3 − , (CF 3 sO 2) 2 N -, (C 2 F 5 sO 2) 2 N -, (CF 3 sO 2) 3 C - metal salt composed of anions or the like is preferably used. In particular, LiBr, LiI, LiBF 4 , LiPF 6 , LiSCN, LiClO 4 , LiCF 3 SO 3 , Li (CF 3 SO 2 ) 2 N, Li (C 2 F 5 SO 2 ) 2 N, Li (CF 3 SO 2 ) Lithium salts such as 3 C are preferably used. Among them, fluoromethylsulfonyllithium salts such as LiCF 3 SO 3 , Li (CF 3 SO 2 ) 2 N, Li (C 2 F 5 SO 2 ) 2 N, Li (CF 3 SO 2 ) 3 C have antistatic effects, It is particularly preferable because of its good metal corrosivity. These alkali metal salts may be used alone or in combination of two or more.
上記粘着剤組成物のアルカリ金属塩の配合量については、アクリル系共重合体（A）１００重量部に対して、アルカリ金属塩を０．００５〜０．６重量部、好ましいくは０．００５〜０．３重量部配より好ましくは、０．０１〜０．２重量部配合することがよい。０．００５重量部より以上であれば十分な帯電特性が得られな、一方、０．６重量部未満であれば配合量に対する帯電防止効果率が十分であるので好ましい。 About the compounding quantity of the alkali metal salt of the said adhesive composition, 0.005-0.6 weight part of alkali metal salt is preferable with respect to 100 weight part of acrylic copolymers (A), Preferably 0.005. More preferably, it is added in an amount of 0.01 to 0.2 parts by weight. If it is more than 0.005 parts by weight, sufficient charging characteristics cannot be obtained.
本発明の光学部材表面保護フィルム用粘着剤を、イソシアネート化合物（Ｄ）により架橋し、表面保護フィルム用アクリル系粘着剤層を形成する。
本発明で使用することのできるポリイソシアネート化合物（D）としては、例えば、キシリレ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、トリフェニルメタントリイソシアネート、トリレンジイソシアネート等の芳香族ポリイソシアネート；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、該芳香族ポリイソシアネート化合物の水素添加物等の脂肪族又は脂環族ポリイソシアネート；それらポリイソシアネートの２量体もしくは３量体又はそれらポリイソシアネートと、トリメチロールプロパンなどのポリオールとのアダクト体などの各種ポリイソシアネートに由来するポリイソシアネート化合物を挙げることができるが、これらのイソシアネート化合物の中では、ヘキサメチレンジイソシアネートが特に好ましい。
これらのイソシアネート化合物は、単独でまたは2種類以上混合して使用することができる。
The pressure-sensitive adhesive for a surface protective film of the present invention is crosslinked with an isocyanate compound (D) to form an acrylic pressure-sensitive adhesive layer for a surface protective film.
Examples of the polyisocyanate compound (D) that can be used in the present invention include aromatic polyisocyanates such as xylylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, and tolylene diisocyanate; for example, hexamethylene diisocyanate and isophorone diisocyanate. Aliphatic or alicyclic polyisocyanates such as hydrogenated products of the aromatic polyisocyanate compounds; dimers or trimers of these polyisocyanates or adducts of these polyisocyanates with polyols such as trimethylolpropane, etc. Polyisocyanate compounds derived from various polyisocyanates of the above can be mentioned, but among these isocyanate compounds, hexamethylene diisocyanate is Particularly preferred.
These isocyanate compounds can be used alone or in admixture of two or more.
これらのイソシアネート化合物は、例えば「コロネートＨＸ」、「コロネートＨＬ−Ｓ」、「コロネート２２３４」「アクアネート２００」、「アクアネート２１０」〔以上日本ポリウレタン(株)製〕、「デスモジュールＮ３４００」〔住友バイエルウレタン(株)製〕、「デュラネートＥ−４０５−８０Ｔ」、「デュラネート２４Ａ−１００」、「デュラネートＴＳＥ−１００」〔旭化成工業(株)製〕、「タケネートＤ−１１０Ｎ」、「タケネートＤ−１２０Ｎ」、「タケネートＭ−６３１Ｎ」「ＭＴ−オレスターＮＰ１２００」〔以上三井武田ケミカル(株)製〕などの商品名により市販されているものを好適に使用することができる。
These isocyanate compounds include, for example, “Coronate HX”, “Coronate HL-S”, “Coronate 2234”, “Aquanate 200”, “Aquanate 210” (manufactured by Nippon Polyurethane Co., Ltd.), “Desmodur N3400” [ “Sumitomo Bayer Urethane Co., Ltd.”, “Duranate E-405-80T”, “Duranate 24A-100”, “Duranate TSE-100” [Asahi Kasei Kogyo Co., Ltd.], “Takenate D-110N”, “Takenate D” -120N "," Takenate M-631N "," MT-Olestar NP1200 "(manufactured by Mitsui Takeda Chemical Co., Ltd.) and the like can be suitably used.
これらポリイソシアネート化合物（D）の使用量は、前記アクリル系共重合体（Ａ）および（Ｂ）の反応性官能基の合計を１当量とした時、イソシアネート基として０．３〜１．２当量、特には０．５〜０．９当量の範囲であることが好ましく、また、必要に応じて ジブチル錫ラウリレート等の硬化触媒を使用してもよい。
The amount of these polyisocyanate compounds (D) used is 0.3 to 1.2 equivalents as isocyanate groups when the total of the reactive functional groups of the acrylic copolymers (A) and (B) is 1 equivalent. In particular, a range of 0.5 to 0.9 equivalent is preferable, and a curing catalyst such as dibutyltin laurate may be used as necessary.
本発明の光学部材表面保護フィルム用粘着剤組成物には、以上述べたアクリル系共重合体（Ａ）アクリル系共重合体（Ｂ）及びアルカリ金属塩（Ｃ）の他に、必要に応じて、表面保護フィルム用粘着剤組成物に配合される配合物、例えば、耐候性安定剤、タッキファイヤー、可塑剤、軟化剤、剥離助剤、染料、顔料、無機充填剤、界面活性剤、などを適宜配合することができる。
In addition to the acrylic copolymer (A) acrylic copolymer (B) and the alkali metal salt (C) described above, the pressure-sensitive adhesive composition for an optical member surface protective film of the present invention, if necessary. Formulations to be blended into the surface protective film pressure-sensitive adhesive composition, such as weather resistance stabilizer, tackifier, plasticizer, softener, peeling aid, dye, pigment, inorganic filler, surfactant, etc. It can mix | blend suitably.
中でも大面積での高速剥離用に使用する場合には、剥離助剤を配合することが好ましく、剥離力が小さく、更にジッピングを起こさず低速剥離における接着力に優れたシリコン化合物を剥離助剤として配合することは好ましい態様であり、中でもポリオキシアルキレン変性されたジメチルシリコン化合物を含有するのが好ましい。 Among them, when used for high-speed peeling in a large area, it is preferable to mix a peeling aid, and a peeling compound is used as a peeling aid, which has a small peeling force and does not cause zipping and has excellent adhesive strength in low-speed peeling. Mixing is a preferred embodiment, and among them, it is preferable to contain a polyoxyalkylene-modified dimethyl silicon compound.
上記ポリオキシアルキレン変性されたジメチルシリコン化合物としては、ジメチルシリコンの側鎖をポリオキシアルキレン基で置換した化合物、メチルシリコンの末端部分をポリオキシアルキレン基で置換した化合物、ジメチルシリコンの側鎖及び両末端をポリオキシアルキレン基で置換した化合物等が挙げられる。 Examples of the polyoxyalkylene-modified dimethyl silicon compound include compounds in which the side chain of dimethyl silicon is substituted with a polyoxyalkylene group, compounds in which the terminal portion of methyl silicon is substituted with a polyoxyalkylene group, side chains of dimethyl silicon and both Examples thereof include compounds in which the terminal is substituted with a polyoxyalkylene group.
ポリオキシアルキレン基としては、ポリオキシエチレン、ポリオキシプロピレン、ポリオキシブチレン及びこれらのブロック化合物が挙げられる。 Examples of the polyoxyalkylene group include polyoxyethylene, polyoxypropylene, polyoxybutylene, and block compounds thereof.
上記ポリオキシアルキレン変性されたシ゛メチルシリコン化合物（Ｂ）は、例えば「ＫＦ−３５１Ａ」、「ＫＦ−３５２Ａ」、「ＫＦ−３５３」、「ＫＦ−３５４Ｌ」、「ＫＦ−３５５Ａ」、「ＫＦ−６１５Ａ」、「ＫＦ−９４５」、「ＫＦ−６４０」、「ＫＦ−６４１」、「ＫＦ−６４２」、「ＫＦ−６４３」、「ＫＦ−６０２０」、「Ｘ−２２−６１９１」、「Ｘ−２２−４５１５」、「ＫＦ−６０１１」、「ＫＦ−６０１２」、「ＫＦ−６０１３」、「ＫＦ−６０１５」、「ＫＦ−６０１６」、「ＫＦ−６０１７」、「Ｘ−２２−４７４１」、「ＫＦ−１００２」、「Ｘ−２２−４９５２」、「Ｘ−２２−４２７２」、「Ｘ−２２−６２６６」、「ＫＦ−６００４」、「ＫＰ−３０１」、「ＫＰ−３２３」、「ＫＰ−３５４」、「ＫＰ−３５５」、「ＫＰ−３４１」、「ＫＰ−１１８」、「Ｆ−５０１」、「Ｘ−２２−６１９１」、「Ｘ−２２−３５０６」、「Ｘ−２２−３００４」、「ＫＦ−６００５」、「ＫＰ−１０１」、「ＫＦ−８８９」、「ＫＦ−６００３」、「Ｘ−２２−４５１５」、「Ｆ−３０３１」、「Ｘ−２４−１４３０」、「Ｘ−２２−４９９１」、「ＫＰ−２０８」、「ＫＦ−６００３」〔以上信越化学（株）製〕、「Ｌ−７２０」、「Ｌ−７６０４」、「Ｙ−７００６」、「ＢＹ−１６−２０１」、「ＦＺ−７７」、「ＦＺ−２１０１」、「ＦＺ−２１０４」、「ＦＺ−２１１０」、「ＦＺ−２１１８」、「ＦＺ−２１２０」、「ＦＺ−２１２２」、「ＦＺ−２１３０」、「ＦＺ−２１６１」、「ＦＺ−２１６２」、「ＦＺ−２１６３」、「ＦＺ−２１６４」、「ＦＺ−２１６６」、「ＦＺ−２１９１」、「ＦＺ−２１５４」、「ＦＺ−２２０３」、「ＦＺ−２２０７」、「ＦＺ−２２０８」、「Ｌ−７００１」、「Ｌ−７００２」、「ＳＦ−８４２７」、「ＳＦ−８４２８」、「ＳＨ−３７４９」、「ＳＨ−３７７３Ｍ」、「ＳＨ−８４００」、「ＦＺ−５６０９」、「ＦＺ−７００１」、「ＦＺ−７００２」〔東レ・ダウ（株）製〕、「ＴＳＦ−４４４０」、「ＴＳＦ−４４４１」、「ＴＳＦ−４４４５」、「ＴＳＦ−４４４６」、「ＴＳＦ−４４５０」、「ＴＳＦ−４４５２」、「ＴＳＦ−４４６０」〔モメンィブ・パフォーマンス（株）製〕などの商品名により市販されている。 Examples of the polyoxyalkylene-modified dimethyl silicon compound (B) include “KF-351A”, “KF-352A”, “KF-353”, “KF-354L”, “KF-355A”, “KF-615A”. ”,“ KF-945 ”,“ KF-640 ”,“ KF-641 ”,“ KF-642 ”,“ KF-643 ”,“ KF-6020 ”,“ X-22-6191 ”,“ X-22 ” -4515 "," KF-6011 "," KF-6012 "," KF-6013 "," KF-6015 "," KF-6016 "," KF-6017 "," X-22-4741 "," KF -1002 "," X-22-4952 "," X-22-4272 "," X-22-6266 "," KF-6004 "," KP-301 "," KP-323 "," KP-354 " "," KP 355 "," KP-341 "," KP-118 "," F-501 "," X-22-6191 "," X-22-3506 "," X-22-3004 "," KF-6005 " , “KP-101”, “KF-889”, “KF-6003”, “X-22-4515”, “F-3031”, “X-24-1430”, “X-22-4991”, “ KP-208 "," KF-6003 "(manufactured by Shin-Etsu Chemical Co., Ltd.)," L-720 "," L-7604 "," Y-7006 "," BY-16-201 "," FZ-77 " ”,“ FZ-2101 ”,“ FZ-2104 ”,“ FZ-2110 ”,“ FZ-2118 ”,“ FZ-2120 ”,“ FZ-2122 ”,“ FZ-2130 ”,“ FZ-2161 ”, "FZ-2162", "FZ-2163", "FZ-2 64 "," FZ-2166 "," FZ-2191 "," FZ-2154 "," FZ-2203 "," FZ-2207 "," FZ-2208 "," L-7001 "," L-7002 " , “SF-8427”, “SF-8428”, “SH-3749”, “SH-3773M”, “SH-8400”, “FZ-5609”, “FZ-7001”, “FZ-7002” [Toray Industries, Inc. -Dow Co., Ltd.], "TSF-4440", "TSF-4441", "TSF-4445", "TSF-4446", "TSF-4450", "TSF-4442", "TSF-4460" [ Momentive Performance Co., Ltd.).
また、目的に合わせ、ポリオキシアルキレン変性されたジメチルシリコン化合物以外に適宜シリコンオイルを組み合わせて配合しても良い。 In addition to the polyoxyalkylene-modified dimethylsilicon compound, silicone oil may be appropriately combined in accordance with the purpose.
上記ポリオキシアルキレン変性されたジメチルシリコン化合物が感圧接着剤組成物に含有される量は、該アクリル系共重合体（Ａ）１００重量部に対し０．０１〜２．０重量部であり、好ましくは０．０５〜１．０重量部であり、更に好ましくは０．１〜０．５重量部である。 The amount of the polyoxyalkylene-modified dimethylsilicone compound contained in the pressure-sensitive adhesive composition is 0.01 to 2.0 parts by weight with respect to 100 parts by weight of the acrylic copolymer (A), Preferably it is 0.05-1.0 weight part, More preferably, it is 0.1-0.5 weight part.
上記ポリオキシアルキレン変性されたジメチルシリコン化合物が感圧接着剤組成物に含有される量が上記下限値未満であると、保護フィルム表面が外的応力を受けて表面保護フィルムの感圧接着剤層の一部が破壊された場合に、表面保護フィルムを剥離した時に破壊された感圧接着剤層の一部が光学部材表面に残る不具合が発生する。また、上記ポリオキシアルキレン変性されたジメチルシリコン化合物が感圧接着剤組成物に含有される量が上記上限値を超えると、表面保護フィルムの接着性等が経時変化するとともに、光学部材の表面に過剰のジメチルシリコン化合物が残存して表面汚染を起こす。 When the amount of the polyoxyalkylene-modified dimethylsilicone compound contained in the pressure-sensitive adhesive composition is less than the lower limit, the surface of the protective film is subjected to external stress and the pressure-sensitive adhesive layer of the surface protective film If a part of the pressure-sensitive adhesive layer is broken, a part of the pressure-sensitive adhesive layer destroyed when the surface protective film is peeled off remains on the surface of the optical member. When the amount of the polyoxyalkylene-modified dimethylsilicon compound contained in the pressure-sensitive adhesive composition exceeds the upper limit, the adhesiveness of the surface protective film changes with time, and the surface of the optical member Excess dimethylsilicon compound remains and causes surface contamination.
かくして得られる本発明の光学部材表面保護フィルム用粘着剤組成物は、光学部材表面保護フィルムを作製するため、適宜の透明な表面保護基材の少なくとも一方の面に、従来公知の方法によって粘着剤層を形成するために用いられる。 The pressure-sensitive adhesive composition for an optical member surface protective film of the present invention thus obtained is used to produce an optical member surface protective film, and is prepared on at least one surface of an appropriate transparent surface protective substrate by a conventionally known method. Used to form a layer.
本発明の表面保護フィルムに用いられる基材としては、粘着剤が塗布できる基材であることが必要である。基材樹脂としては透視による光学部材の検査や管理の観点から、例えば、ポリエステル系樹脂、アセテート系樹脂、ポリエーテルサルホン系樹脂、ポリカーボネート系樹脂、ポリアミド系樹脂、ポリイミド系樹脂、ポリオレフィン系樹脂、アクリル系樹脂などからなるフィルムを挙げることができるが、表面保護性能からポリエステル系樹脂が好ましく、実用性を考慮すればポリエチレンテレフタレート樹脂が特に好ましい。 As a base material used for the surface protection film of this invention, it is required that it is a base material which can apply | coat an adhesive. From the viewpoint of inspection and management of optical members by fluoroscopy as the base resin, for example, polyester resin, acetate resin, polyether sulfone resin, polycarbonate resin, polyamide resin, polyimide resin, polyolefin resin, A film made of an acrylic resin can be exemplified, but a polyester resin is preferable from the viewpoint of surface protection performance, and a polyethylene terephthalate resin is particularly preferable in consideration of practicality.
基材の厚さは一般には５００μm以下、好ましくは５〜３００μm、さらに好ましくは１０〜２００μm程度の厚さを例示することができる。これらの基材に片面又は両面には、剥離時の帯電防止を目的に、帯電防止層が設けられていてもよい。また該基材の、粘着剤層が設けられる側の表面には、粘着剤層との密着性を向上させるためにコロナ放電処理等が施されていてもよい。 The thickness of the substrate is generally 500 μm or less, preferably 5 to 300 μm, more preferably about 10 to 200 μm. An antistatic layer may be provided on one or both surfaces of these base materials for the purpose of preventing antistatic during peeling. The surface of the substrate on the side where the pressure-sensitive adhesive layer is provided may be subjected to a corona discharge treatment or the like in order to improve the adhesion with the pressure-sensitive adhesive layer.
たとえば２０インチ以上の液晶表示画面に使用されるような大型の光学部材に対して十分な接着力を持ち（低速剥離の接着力が十分大きい）かつ高速剥離時に容易に剥離でき（高速剥離の接着力が大きくならない）かつなじみ性が良好である（切断した場合に切断端がめくり上がらない）ことが必要である。
すなわち、光学部材に対する２３℃での１８０度ピールの接着力は、剥離速度０．３ｍ／分（低速剥離）において接着力（剥離力）が０．０５Ｎ／２５ｍｍ以上、好ましくは０．０８Ｎ／２５ｍｍ以上であるのがよく、低速剥離の接着力が０．０５Ｎ／２５ｍｍ未満であるとめくれやずれが発生しやすいので好ましくない。
For example, it has sufficient adhesion to large optical members such as those used for LCD screens of 20 inches or more (adhesion for low-speed peeling is sufficiently large) and can be easily peeled off at high speed (adhesion for high-speed peeling) It is necessary that the force does not increase) and the conformability is good (the cut end does not turn up when cut).
That is, the adhesive force of 180 ° peel to the optical member at 23 ° C. is 0.05 N / 25 mm or more, preferably 0.08 N / 25 mm at a peeling speed of 0.3 m / min (low speed peeling). It is preferable that the adhesive force for low-speed peeling is less than 0.05 N / 25 mm because turning and shifting are likely to occur.
また、接着力が高くなると大面積における高速剥離の作業性が低下するので、剥離速度３０ｍ／分（高速剥離）において、接着力（剥離力）が１．５Ｎ／２５ｍｍ以上にならないこと、好ましくは１．２Ｎ／２５ｍｍより大きくならないことが好ましい。 Further, since the workability of high-speed peeling in a large area is reduced when the adhesive force is increased, the adhesive force (peeling force) does not become 1.5 N / 25 mm or more at a peeling speed of 30 m / min (high-speed peeling), preferably It is preferable not to be larger than 1.2 N / 25 mm.
さらに、剥離時の帯電が大きいと光学部材にダメージを与えるので、本発明の粘着剤組成物はアンチグレア偏光板に対する３０ｍ／分剥離時の剥離帯電圧が０．９ＫＶ以下であることが好ましく、０．５ＫＶ以下であればさらに好ましく０．３ＫＶ以下であれば特に好ましい。 Furthermore, since the optical member is damaged when the charge at the time of peeling is large, the pressure-sensitive adhesive composition of the present invention preferably has a peeling voltage of 0.9 KV or less at 30 m / min against the antiglare polarizing plate. More preferably, it is less than 0.5 KV, and particularly preferably less than 0.3 KV.
剥離の際のフィルム側の帯電を防止するために本発明の粘着剤組成物は表面抵抗値が１E+１３（Ω／□）以下、好ましくは１E+１１（Ω／□）以下であることが好ましい。 In order to prevent charging on the film side at the time of peeling, the pressure-sensitive adhesive composition of the present invention has a surface resistance value of 1E + 13 (Ω / □) or less, preferably 1E + 11 (Ω / □) or less. preferable.
基材上に形成される粘着剤層の厚さは、保護フィルムの求められる接着力や光学部材表面粗さなどに応じて適宜設定することができ、一般に１〜１００μｍ、好ましくは５〜５０μｍ、さらに好ましくは１５〜３０μｍ程度の厚さを例示することができる。 The thickness of the pressure-sensitive adhesive layer formed on the substrate can be appropriately set according to the adhesive force required for the protective film or the surface roughness of the optical member, and is generally 1 to 100 μm, preferably 5 to 50 μm. More preferably, a thickness of about 15 to 30 μm can be exemplified.
粘着剤層の形成方法としては、本発明の粘着剤組成物を、そのまま又は、必要に応じて適宜の溶媒で希釈し、これを表面保護ベースフィルムに直接塗布・乾燥して溶媒を除去する方法を採用することができる。また、先ずシリコーン樹脂等により離型処理が施された紙やポリエステルフィルム等の適宜のフィルムからなる剥離シート上に、本発明の粘着剤組成物を塗布し、加熱乾燥して粘着剤層を形成させ、次に該剥離シートの接着剤層側を表面保護ベースフィルムに圧接して該接着剤層を該保護フィルムに転写させることもできる。 As a method for forming the pressure-sensitive adhesive layer, the pressure-sensitive adhesive composition of the present invention is directly or as necessary diluted with an appropriate solvent, and this is directly applied to a surface protective base film and dried to remove the solvent. Can be adopted. First, the pressure-sensitive adhesive composition of the present invention is applied on a release sheet made of an appropriate film such as paper or polyester film that has been subjected to a release treatment with a silicone resin, and then dried by heating to form a pressure-sensitive adhesive layer. Then, the adhesive layer side of the release sheet can be pressed against the surface protective base film to transfer the adhesive layer to the protective film.
かくして得られる保護フィルムは、光学部材の表面に積層されて、その光学部材の表面が汚染されたり損傷したりしないよう保護し、該光学部材が液晶表示板などに加工される際には、該保護フィルムが光学部材に積層された状態のまま、打抜加工、検査、輸送、液晶表示板の組立などの各工程に供され、必要に応じて、オートクレーブ処理や高温エージング処理などの加熱加圧処理が施され、表面保護が不要となった段階で光学部材から剥離除去される。 The protective film thus obtained is laminated on the surface of the optical member to protect the surface of the optical member from being contaminated or damaged, and when the optical member is processed into a liquid crystal display panel or the like, While the protective film is laminated on the optical member, it is used in various processes such as punching, inspection, transportation, and assembly of the liquid crystal display panel. If necessary, heat and pressure such as autoclaving and high-temperature aging When the surface treatment is no longer necessary, the optical member is peeled off and removed.
以下に実施例及び比較例を挙げ、本発明の効果を具体的に説明するが、本発明はこれらの実施例に制限されるものではない。なお、実施例及び比較例において用いた、試験片の作成、並びに各種の試験方法及び評価方法は以下のとおりである。 EXAMPLES Examples and comparative examples will be described below to specifically describe the effects of the present invention, but the present invention is not limited to these examples. In addition, preparation of a test piece and various test methods and evaluation methods used in Examples and Comparative Examples are as follows.
（１）試験用粘着シートの作成
シリコーン系離型剤で表面処理された離型紙上に、乾燥後の塗工量が２０ｇ／ｍ2となるように、粘着剤組成物を塗布し、１００℃で６０秒間熱風循環式乾燥機にて乾燥して粘着剤層を形成した後、ポリエチレンテレフタレート（ＰＥＴ）フィルム〔商品名；Ｅ５００１；東洋紡績(株)製〕上に該粘着剤層面が接するように載置し、加圧ニップロールを通して圧着して貼り合わせた後、２３℃、５０％ＲＨで１０日間養生を行って試験用表面保護フィルムを得た。
(1) Preparation of test pressure-sensitive adhesive sheet A pressure-sensitive adhesive composition was applied on a release paper surface-treated with a silicone-based release agent so that the coating amount after drying was 20 g / m 2, and 100 ° C. After drying with a hot-air circulating dryer for 60 seconds to form an adhesive layer, the adhesive layer surface is in contact with a polyethylene terephthalate (PET) film [trade name; E5001; manufactured by Toyobo Co., Ltd.]. After mounting and pressure bonding through a pressure nip roll, the surfaces were cured at 23 ° C. and 50% RH for 10 days to obtain a test surface protective film.
（２）粘着剤層の外観
前(１)項により作製した試験用表面保護フィルムの粘着剤層が均一で透明なものであるか観察する。
○：粘着剤層が均一で透明である
△：粘着剤層は均一であるが、曇りが見られる
×：粘着剤層に欠陥が見られる
(2) Appearance of pressure-sensitive adhesive layer Before the appearance, observe whether the pressure-sensitive adhesive layer of the test surface protective film prepared according to the item (1) is uniform and transparent.
○: The pressure-sensitive adhesive layer is uniform and transparent. Δ: The pressure-sensitive adhesive layer is uniform but cloudy. ×: Defects are found in the pressure-sensitive adhesive layer.
(３) 接着力の測定
前(１)項により作製した試験用表面保護フィルムを２５ｍｍ×１５０ｍｍにカットしたのち、この表面保護フィルム片を、卓上ラミネート機を用いて、アンチグレア処理された偏光フィルム〔商品名；ＳＱ−１８５２ＡＰ−ＡＧ６；住友化学工業(株)製〕に圧着して試験サンプルとした。このサンプルを２３℃、５０％ＲＨの条件下で２４時間放置（コンディショニング処理）した後、１８０゜剥離における接着力を剥離速度０．３ｍ／分（低速剥離）及び３０ｍ／分（高速剥離）でそれぞれ測定した。
(3) Measurement of adhesive strength
After the surface protective film for test prepared in the preceding item (1) was cut to 25 mm × 150 mm, the surface protective film piece was subjected to anti-glare treatment using a desktop laminator [trade name: SQ-1852AP- AG6; manufactured by Sumitomo Chemical Co., Ltd.] was used as a test sample. After leaving this sample under conditions of 23 ° C. and 50% RH for 24 hours (conditioning treatment), the adhesive strength at 180 ° peeling was peeled off at a peeling speed of 0.3 m / min (low speed peeling) and 30 m / min (high speed peeling). Each was measured.
(４) 剥離後の偏光フィルムの表面状態の観察
前(３)項で試験した試験サンプルの剥離後の偏光フィルムの表面状態を観察した。
○：表面に糊残り等の異常は観察されない。
×：表面に糊残り等の異常が観察される。
(4) Before observation of surface state of polarizing film after peeling The surface state of the polarizing film after peeling of the test sample tested in the item (3) was observed.
○: Abnormalities such as adhesive residue on the surface are not observed.
X: Abnormalities such as adhesive residue are observed on the surface.
（５）剥離帯電圧測定
前(１)項により作製した試験用表面保護フィルムを２５ｍｍ×１５０ｍｍにカットしたのち、この表面保護フィルム片を、卓上ラミネート機を用いて、アンチグレア処理された偏光フィルム〔商品名；ＳＱ−１８５２ＡＰ−ＡＧ６；住友化学工業(株)製〕に圧着して試験サンプルとした。このサンプルを２３℃、５０％ＲＨの条件下で２４時間放置（コンディショニング処理）した後、１８０゜剥離、剥離速度３０ｍ／分（高速剥離条件）で剥離する。このときの発生する偏光板表面の電位を下図のとおり、所定の位置に固定してある電位測定機〔春日電機(株)製ＫＳＤ−０３０３〕にて測定した。測定は、２３℃×５０％ＲＨの環境下で行った。
(5) Before the stripping voltage measurement, the test surface protective film prepared according to the item (1) was cut into 25 mm × 150 mm, and then the surface protective film piece was antiglare-treated with a polarizing film [ Trade name: SQ-1852AP-AG6; manufactured by Sumitomo Chemical Co., Ltd.] was used as a test sample. This sample is allowed to stand for 24 hours under the conditions of 23 ° C. and 50% RH (conditioning treatment), and then peeled off at 180 ° and at a peeling speed of 30 m / min (high-speed peeling conditions). The potential of the polarizing plate surface generated at this time was measured with a potential measuring device (KSD-0303 manufactured by Kasuga Electric Co., Ltd.) fixed at a predetermined position as shown in the following figure. The measurement was performed in an environment of 23 ° C. × 50% RH.
（６）表面抵抗
得られた粘着シートの剥離紙を剥がし、粘着剤層表面の表面抵抗値を表面抵抗測定装置（(株)アドバンテスト：R１２７０４ RESISTIVITY CHAMBER）を用いて測定した。
(6) Surface resistance The release paper of the obtained pressure-sensitive adhesive sheet was peeled off, and the surface resistance value of the pressure-sensitive adhesive layer surface was measured using a surface resistance measurement device (Advantest Co., Ltd .: R12704 RESISTIVITY CHAMBER).
アクリル系共重合体（A）溶液の製造
製造例１
温度計、攪拌機、窒素導入管及び還流冷却器を備えた反応器内に、酢酸エチル２０重量部、トルエン１０重量部を入れ、また別の容器に、単量体(a1)として２-エチルヘキシルアクリレート（２ＥＨＡ）９５．０重量部、単量体(a2)として４-ヒドロキシブチルアクリレート（４ＨＢＡ）５．０重量部を入れ混合して単量体混合物とし、その中の２５％を反応容器中に加え、次いで該反応容器の空気を窒素ガスで置換した後、重合開始剤としてアゾビスブチロニトリル（以下ＡＩＢＮと言う）０．０２重量部を添加して、攪拌下に窒素雰囲気中で該反応容器内の混合物温度を７０℃に昇温させて初期反応を開始させた。初期反応がほぼ終了した後、残りの単量体混合物７５％、並びに酢酸エチル２０重量部、トルエン１０重量部及びＡＩＢＮ０．２重量部の混合物をそれぞれ逐次添加しながら約２時間反応させ、引き続いてさらに２時間反応させた。その後、トルエン２５重量部にＡＩＢＮ
０．２５重量部を溶解させた溶液を１時間かけて滴下し、さらに１．５時間反応させた。反応終了後、反応混合物をトルエン１２５重量部で希釈して、固形分３５重量％のアクリル系共重合体溶液Ａ-1を得た。
Production and production example 1 of acrylic copolymer (A) solution
In a reactor equipped with a thermometer, a stirrer, a nitrogen introduction tube and a reflux condenser, 20 parts by weight of ethyl acetate and 10 parts by weight of toluene are placed, and in another container, 2-ethylhexyl as a monomer (a 1 ). 95.0 parts by weight of acrylate (2EHA) and 5.0 parts by weight of 4-hydroxybutyl acrylate (4HBA) as monomer (a 2 ) are mixed to form a monomer mixture, 25% of which is contained in a reaction vessel Then, after replacing the air in the reaction vessel with nitrogen gas, 0.02 part by weight of azobisbutyronitrile (hereinafter referred to as AIBN) was added as a polymerization initiator, and the mixture was stirred in a nitrogen atmosphere. The temperature of the mixture in the reaction vessel was raised to 70 ° C. to initiate an initial reaction. After the initial reaction was almost completed, the remaining monomer mixture 75% and ethyl acetate 20 parts by weight, toluene 10 parts by weight and AIBN 0.2 part by weight were respectively reacted for about 2 hours, followed by subsequent reaction. The reaction was further continued for 2 hours. Then, AIBN was added to 25 parts by weight of toluene.
A solution having 0.25 parts by weight dissolved therein was added dropwise over 1 hour, and the mixture was further reacted for 1.5 hours. After completion of the reaction, the reaction mixture was diluted with 125 parts by weight of toluene to obtain an acrylic copolymer solution A-1 having a solid content of 35% by weight.
得られたアクリル系共重合体溶液の粘度は７３０ｍＰａ・ｓであり、またアクリル系共重合体は、ガラス転移温度（Ｔｇ）-７４℃であって、重量平均分子量（Ｍｗ）約５９万であった。 The viscosity of the obtained acrylic copolymer solution was 730 mPa · s, and the acrylic copolymer had a glass transition temperature (Tg) of −74 ° C. and a weight average molecular weight (Mw) of about 590,000. It was.
製造例２ 〜製造例５
単量体組成を表１に示す単量体組成に変更する以外は製造例１と同様にしてアクリル系共重合体溶液A-２〜A-５を製造した。得られたアクリル系共重合体溶液の粘度、固形分、ガラス転移点（Ｔｇ）、重量平均分子量（Ｍｗ）を表１に示す。
Production Example 2 to Production Example 5
Acrylic copolymer solutions A-2 to A-5 were produced in the same manner as in Production Example 1 except that the monomer composition was changed to the monomer composition shown in Table 1. Table 1 shows the viscosity, solid content, glass transition point (Tg), and weight average molecular weight (Mw) of the resulting acrylic copolymer solution.
製造例６ アルキレンオキサイド含有アクリル系共重合体 （B）の製造
攪拌羽根、温度計、窒素ガス導入管、冷却器、滴下ロートを備えた四つ口フラスコにt-BMA９０重量部、アルキレンオキサイド基含有モノマー メトキシポリエチレングリコールメタクリレート（アルキレンオキシド単位は４５）１０重量部、重合開始剤としてAIBN０．６重量部、酢酸エチル４１０重量部を仕込み、緩やかに攪拌しながら窒素ガスを導入し、フラスコ内の液温を７０℃
付近に保って６ 時間重合反応を行い、アルキレンオキサイド基含有アクリル系共重合体溶液B−１を調製した。前記アクリル系共重合体（B）の重量平均分子量は３．０ 万、ガラス転移温度（Ｔｇ）
は１５ ℃であった。
Production Example 6 Production of Alkylene Oxide-Containing Acrylic Copolymer (B) Four-necked flask equipped with stirring blade, thermometer, nitrogen gas inlet tube, cooler, dropping funnel, 90 parts by weight of t-BMA, containing alkylene oxide group Monomer Methoxypolyethylene glycol methacrylate (alkylene oxide unit is 45) 10 parts by weight, AIBN 0.6 part by weight as a polymerization initiator and ethyl acetate 410 parts by weight, nitrogen gas was introduced while gently stirring, and the liquid temperature in the flask 70 ° C
The polymerization reaction was carried out for 6 hours while maintaining the vicinity to prepare an alkylene oxide group-containing acrylic copolymer solution B-1. The acrylic copolymer (B) has a weight average molecular weight of 30,000 and a glass transition temperature (Tg).
Was 15 ° C.
製造例７〜製造例１２
単量体組成を表１に示す単量体組成に変更する以外は製造例６と同様にしてアクリル系共重合体溶液B−２〜B−６を製造した。また、Ｂ−７としては、ポリプロピレングリコール-ポリエチレングリコール-ポリプロピレングリコール共重合体（重量平均分子量：６０００、エチレンオキシド基含有率 ５０重量％）使用した。
得られたアクリル系共重合体溶液の粘度、固形分、ガラス転移点（Ｔｇ）、重量平均分子量（Ｍｗ）を表１に示す。
Production Example 7 to Production Example 12
Acrylic copolymer solutions B-2 to B-6 were produced in the same manner as in Production Example 6 except that the monomer composition was changed to the monomer composition shown in Table 1. As B-7, a polypropylene glycol-polyethylene glycol-polypropylene glycol copolymer (weight average molecular weight: 6000, ethylene oxide group content: 50% by weight) was used.
Table 1 shows the viscosity, solid content, glass transition point (Tg), and weight average molecular weight (Mw) of the resulting acrylic copolymer solution.
単量体組成を表１に示す単量体及びアルキレンオキサイド基含有モノマーの組成を表１に示すように変更する以外は製造例２と同様にしてアクリル系共重合体溶液B−２〜B−６ を製造した。得られたアクリル系共重合体溶液の粘度、固形分、ガラス転移点（Ｔｇ）、重量平均分子量（Ｍｗ）を表２に示す。 Acrylic copolymer solutions B-2 to B- were prepared in the same manner as in Production Example 2 except that the monomer composition and the alkylene oxide group-containing monomer composition were changed as shown in Table 1. 6 was produced. Table 2 shows the viscosity, solid content, glass transition point (Tg), and weight average molecular weight (Mw) of the obtained acrylic copolymer solution.
実施例１ 表面保護フィルム用粘着剤組成物の作製
攪拌羽根、温度計、冷却器、滴下ロートを備えた四つ口フラスコに前記アクリル系共重合体組成物（A−１）溶液（固形分３４．７重量％）、 １００重量部、 アルキレンオキサイド基含有アクリル系共重合体 （B-１）溶液（固形分２０．０重量％） ０．８７重量部、Ｌｉ（ＣＦ３ＳＯ２）２Ｎ（森田化学工業（株）製LiTFSI）０．０１７４重量部を仕込み、フラスコ内の液温を２ ５ ℃ 付近に保って４．０時間混合撹拌を行い、アクリル系共重合体混合溶液を得た。これにイソシアネート化合物（D）として商品名：アクアネート２１０〔HMDI型、固形分１００重量％、イソシアネート（ＮＣＯ）含有量１６．７重量％；日本ポリウレタン製〕２．４重量部（イソシアネートとして０．８当量）を添加し十分に攪拌して表３に示す光学部材表面保護フィルム用粘着剤組成物溶液を得た。 この粘着剤組成物は十分なポットライフを有するものであり、前記の試験用粘着シートの作成方法に従って試験用表面保護フィルムを作成し、前記の各種物性試験を行った。得られた結果を表４に示す。
Example 1 Preparation of pressure-sensitive adhesive composition for surface protective film The acrylic copolymer composition (A-1) solution (solid content 34) in a four-necked flask equipped with a stirring blade, a thermometer, a cooler, and a dropping funnel. 0.7% by weight), 100 parts by weight, alkylene oxide group-containing acrylic copolymer (B-1) solution (solid content 20.0% by weight) 0.87 parts by weight, Li (CF 3 SO 2 ) 2 N ( 0.017 parts by weight of LiTFSI manufactured by Morita Chemical Co., Ltd. was charged, and the mixture was stirred for 4.0 hours while maintaining the liquid temperature in the flask at around 25 ° C. to obtain an acrylic copolymer mixed solution. To this, as an isocyanate compound (D), trade name: Aquanate 210 [HMDI type, solid content 100% by weight, isocyanate (NCO) content 16.7% by weight; manufactured by Nippon Polyurethane] 2.4 parts by weight (0.2% as isocyanate) 8 equivalents) was added and sufficiently stirred to obtain a pressure-sensitive adhesive composition solution for an optical member surface protective film shown in Table 3. This pressure-sensitive adhesive composition has a sufficient pot life, and a test surface protective film was prepared according to the method for preparing the test pressure-sensitive adhesive sheet, and the above-described various physical property tests were performed. Table 4 shows the obtained results.
実施例２ 〜実施例１０
実施例1の配合条件の代わりに表２に示した各実施例の配合条件を使用する以外は、実施例１と同様にして表３に示すような表面保護フィルム用粘着剤組成物を作成した。 この粘着剤組成物を用い、前記の試験用表面保護フィルムの作成方法に従って試験用表面保護フィルムを作成し、前述した試験方法で各物性を測定した結果を表４に示す。
Example 2 to Example 10
A pressure-sensitive adhesive composition for a surface protective film as shown in Table 3 was prepared in the same manner as in Example 1 except that the blending conditions of each Example shown in Table 2 were used instead of the blending conditions of Example 1. . Using this pressure-sensitive adhesive composition, a test surface protective film was prepared according to the above-mentioned test surface protective film preparation method, and the physical properties measured by the test method described above are shown in Table 4.
比較例１〜比較例７
実施例1の配合条件の代わりに表２に示した各比較例の配合条件を使用する以外は、実施例１と同様にして表３に示すような表面保護フィルム用粘着剤組成物を作成した。 この粘着剤組成物を用い、前記の試験用表面保護フィルムの作成方法に従って試験用表面保護フィルムを作成し、前述した試験方法で各物性を測定した結果を表４に示す
Comparative Examples 1 to 7
A pressure-sensitive adhesive composition for a surface protective film as shown in Table 3 was prepared in the same manner as in Example 1 except that the mixing conditions of each comparative example shown in Table 2 were used instead of the mixing conditions of Example 1. . Using this pressure-sensitive adhesive composition, a test surface protective film was prepared according to the above-mentioned test surface protective film preparation method, and the physical properties measured by the test method described above are shown in Table 4.
Claims (8)
重量平均分子量０．３万〜１０万であり、ガラス転移温度（Tg）が−2０℃〜2０℃であって、分子内にアルキレンオキシド単位 ２０以上のアルキレンオキシド鎖を有するアルキレンオキシド鎖含有アクリル系共重合体（B）０．０５〜２．０重量部、
およびアルカリ金属塩（C）０．００５〜０．６重量部
（ただしアルカリ金属塩（C）の量はアクリル系共重合体（B）の量を超えない。）
を含む表面保護フィルム用アクリル系粘着剤組成物。 Acrylic copolymer having 0.1 to 10% by weight of a monomer having a hydroxyl group as a copolymerization component, a weight average molecular weight of 300,000 to 1,000,000, and a glass transition temperature (Tg) of −50 ° C. or lower. For 100 parts by weight of combined (A),
An alkylene oxide chain-containing acrylic system having a weight average molecular weight of 30,000 to 100,000, a glass transition temperature (Tg) of −20 ° C. to 20 ° C., and having 20 or more alkylene oxide chains in the molecule 0.05 to 2.0 parts by weight of copolymer (B),
And 0.005 to 0.6 parts by weight of alkali metal salt (C) (however, the amount of alkali metal salt (C) does not exceed the amount of acrylic copolymer (B)).
An acrylic pressure-sensitive adhesive composition for a surface protective film.
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| JP5422091B2 (en) * | 2003-12-26 | 2014-02-19 | 東洋インキＳｃホールディングス株式会社 | Antistatic acrylic adhesive |
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| JP5259940B2 (en) * | 2005-09-05 | 2013-08-07 | 日東電工株式会社 | Adhesive composition, adhesive sheet and surface protective film |
| JP2008069202A (en) * | 2006-09-12 | 2008-03-27 | Nippon Carbide Ind Co Inc | Pressure-sensitive adhesive composition for optical member surface protective film and optical member surface protective film |
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