JP2000121804A - Antireflection film - Google Patents
Antireflection filmInfo
- Publication number
- JP2000121804A JP2000121804A JP10288131A JP28813198A JP2000121804A JP 2000121804 A JP2000121804 A JP 2000121804A JP 10288131 A JP10288131 A JP 10288131A JP 28813198 A JP28813198 A JP 28813198A JP 2000121804 A JP2000121804 A JP 2000121804A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- antireflection
- hard coat
- film
- antireflection film
- 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.)
- Pending
Links
- 239000010410 layer Substances 0.000 claims description 129
- 239000000758 substrate Substances 0.000 claims description 24
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 14
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 13
- 230000003373 anti-fouling effect Effects 0.000 claims description 7
- 238000005268 plasma chemical vapour deposition Methods 0.000 claims description 5
- 239000012790 adhesive layer Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 30
- 239000011248 coating agent Substances 0.000 abstract description 18
- 238000000576 coating method Methods 0.000 abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002904 solvent Substances 0.000 abstract description 9
- 238000007598 dipping method Methods 0.000 abstract description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 238000007865 diluting Methods 0.000 abstract description 4
- 238000010030 laminating Methods 0.000 abstract description 4
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 3
- 238000011109 contamination Methods 0.000 abstract 4
- 230000003449 preventive effect Effects 0.000 abstract 3
- 238000005229 chemical vapour deposition Methods 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- 239000008199 coating composition Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 43
- 239000007789 gas Substances 0.000 description 38
- 208000028659 discharge Diseases 0.000 description 27
- 239000007787 solid Substances 0.000 description 26
- 239000000203 mixture Substances 0.000 description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 18
- -1 polysiloxane Polymers 0.000 description 14
- 239000011261 inert gas Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 239000002482 conductive additive Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229920002799 BoPET Polymers 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910004356 Ti Raw Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003989 dielectric material Substances 0.000 description 3
- 238000010891 electric arc Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 239000002519 antifouling agent Substances 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- SJBBXFLOLUTGCW-UHFFFAOYSA-N 1,3-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC(C(F)(F)F)=C1 SJBBXFLOLUTGCW-UHFFFAOYSA-N 0.000 description 1
- ZCCAOOJIWMTVGN-UHFFFAOYSA-N 1,6-diisocyanatohexane;[2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound O=C=NCCCCCCN=C=O.C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C ZCCAOOJIWMTVGN-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- WGKYSFRFMQHMOF-UHFFFAOYSA-N 3-bromo-5-methylpyridine-2-carbonitrile Chemical compound CC1=CN=C(C#N)C(Br)=C1 WGKYSFRFMQHMOF-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- QVHMSMOUDQXMRS-UHFFFAOYSA-N PPG n4 Chemical compound CC(O)COC(C)COC(C)COC(C)CO QVHMSMOUDQXMRS-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- IDCBOTIENDVCBQ-UHFFFAOYSA-N TEPP Chemical compound CCOP(=O)(OCC)OP(=O)(OCC)OCC IDCBOTIENDVCBQ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000010951 brass Substances 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
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- 239000003431 cross linking reagent Substances 0.000 description 1
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- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 238000007606 doctor blade method Methods 0.000 description 1
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- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
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- 239000006260 foam Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
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- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 229920000847 nonoxynol Polymers 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
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- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- 238000005192 partition Methods 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
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- 239000005297 pyrex Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
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- 239000010703 silicon Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- 230000008719 thickening Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
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- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、常圧で成膜、加工
された反射防止フィルムに関する。The present invention relates to an antireflection film formed and processed at normal pressure.
【０００２】[0002]
【従来の技術】自動車の計器類の窓ガラスに太陽光が反
射すると、反射光により計器の内容が読み取れ難いこと
が多い。そのため、計器類に使用されるガラス板、透明
樹脂板は、光の透過性を向上させると共に光の反射を少
なくする努力が払われている。反射防止性を賦与するた
めに反射防止層が設けられる。反射防止層を設ける方法
としては、従来より、表面に低屈折率の物質を蒸着した
り、スパッタリングする方法が取られたり、含フッ素重
合体などの低屈折率の物質の溶液を表面に塗布する方法
（例えば、特開平６−１１５０２３号公報）が提案され
ている。2. Description of the Related Art When sunlight is reflected on a window glass of an instrument of an automobile, it is often difficult to read the contents of the instrument due to the reflected light. For this reason, glass plates and transparent resin plates used for instruments have been making efforts to improve light transmittance and reduce light reflection. An anti-reflection layer is provided to provide anti-reflection properties. As a method for providing an anti-reflection layer, conventionally, a method of depositing a substance having a low refractive index on the surface, a method of sputtering, or applying a solution of a substance having a low refractive index such as a fluoropolymer to the surface is applied. A method (for example, Japanese Patent Application Laid-Open No. H6-115023) has been proposed.
【０００３】上記蒸着法やスパッタリング法は、低圧力
下のバッチ方式で行われ、高品質が求められるレンズ類
などの光学部品に適用されるに対して、含フッ素重合体
などの溶液を表面に塗布する溶液法は、大型ディスプレ
ーなどの保護パネルに利用されている。[0003] The vapor deposition method and the sputtering method are performed in a batch system under a low pressure, and are applied to optical parts such as lenses that require high quality. On the other hand, a solution such as a fluoropolymer is applied to the surface. The solution method for coating is used for protection panels such as large displays.
【０００４】従って、前者は、閉鎖系のバッチ方式であ
るため、小型の精密光学部品の処理に使用されるのに対
し、後者は、開放系の連続方式が取れるため、大型の平
滑なシート、板類の処理に適用される。しかし、大型の
ものは、大量の溶剤を必要とし、製造には細かい塵埃な
どを含まない高いクラスのクリーンルームで、精密塗
工、加熱乾燥、アニール、巻き取り、裁断などの設備が
必要となるため、原料及び設備共にコストが大きなもの
となる。[0004] Accordingly, the former is a closed batch system and is used for processing small precision optical components, while the latter is an open continuous system and can be used for large smooth sheets, Applied to the processing of boards. However, large ones require a large amount of solvent and require high-precision coating, heat drying, annealing, winding, cutting, and other equipment in a high-class clean room that does not contain fine dust. In addition, the cost of both raw materials and equipment increases.
【０００５】しかしながら、上記蒸着法やスパッタリン
グ法では、例えば、シート・フィルム基材上に、反射防
止層を有するシート・フィルムを長尺のロール状物とし
て製造することはできなかった。However, in the above-mentioned vapor deposition method and sputtering method, for example, a sheet / film having an anti-reflection layer on a sheet / film base material cannot be produced as a long roll-shaped material.
【０００６】また、透明材料に反射防止性を賦与させて
も、表面が帯電して塵埃が付着すれば、表面に被覆した
低屈折率の物質に光が透過する前に、塵埃によって光が
乱反射されたり、吸収されたりするため、光の透過性が
減少して、反射防止膜を設けた意味がなくなってしまう
という問題点があった。Even if the transparent material is provided with an antireflection property, if the surface is charged and dust adheres, the light is diffusely reflected by the dust before the light passes through the low refractive index material coated on the surface. This is problematic in that the light transmittance is reduced due to being absorbed or absorbed, and the meaning of providing an antireflection film is lost.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、上記問題点
を解決するためのものであって、基材上に常圧プラズマ
ＣＶＤ法により形成された反射防止層を有する反射防止
フィルムを長尺のロール状物として提供することを目的
とする。SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide an antireflection film having an antireflection layer formed on a substrate by a normal pressure plasma CVD method. It is intended to be provided as a roll.
【０００８】[0008]
【課題を解決するための手段】本願の請求項１に記載の
発明（以下、第１発明という）の反射防止フィルムは、
基材の片面に、ハードコート層、反射防止層及び防汚層
がこの順に積層されてなることを特徴とする。Means for Solving the Problems The antireflection film according to the invention described in claim 1 of the present application (hereinafter referred to as the first invention) comprises:
A hard coat layer, an antireflection layer and an antifouling layer are laminated on one surface of the substrate in this order.
【０００９】本願の請求項２に記載の発明（以下、第２
発明という）の反射防止フィルムは、基材の片面に、導
電層及び反射防止層がこの順に積層されてなることを特
徴とする。The invention described in claim 2 of the present application (hereinafter referred to as “second
The antireflection film of the invention) is characterized in that a conductive layer and an antireflection layer are laminated in this order on one surface of a substrate.
【００１０】以下、本発明の反射防止フィルムについて
説明する。第１発明の反射防止フィルムは、基材の片面
に、ハードコート層、反射防止層及び防汚層がこの順に
積層されたものである。Hereinafter, the antireflection film of the present invention will be described. The antireflection film of the first invention is obtained by laminating a hard coat layer, an antireflection layer and an antifouling layer in this order on one surface of a substrate.
【００１１】上記ハードコート層は、例えば、後述の基
材上にハードコート組成物をマイクログラビアコーター
等で塗工し、紫外線硬化させることによって形成するこ
とができる。上記ハードコート層の膜厚は２〜２０μｍ
となるように塗工速度を調節することが好ましい。さら
に、基材とハードコート層との密着性を高めるために、
基材の表面にコロナ放電処理が施されてもよい。The above-mentioned hard coat layer can be formed, for example, by applying a hard coat composition on a base material described later with a micro gravure coater or the like and curing it with ultraviolet rays. The thickness of the hard coat layer is 2 to 20 μm
It is preferable to adjust the coating speed so that Furthermore, in order to improve the adhesion between the substrate and the hard coat layer,
The surface of the substrate may be subjected to a corona discharge treatment.
【００１２】上記ハードコート組成物として、好ましく
は多官能アクリレートとシリカ粒子及び／又はポリシロ
キサンとを混合したものが挙げられる。The hard coat composition preferably includes a mixture of a polyfunctional acrylate and silica particles and / or polysiloxane.
【００１３】上記多官能アクリレートとしては、例え
ば、ジペンタエリスリトールヘキサ（メタ）アクリレー
ト、ジペンタエリスリトールペンタ（メタ）アクリレー
ト、ジペンタエリスリトール（メタ）テトラアクリレー
ト、ジペンタエリスリトールトリ（メタ）アクリレー
ト、トリメチロールプロパントリ（メタ）アクリレート
等が挙げられる。また、これらの多官能アクリレートを
変性したものも利用することができ、これらは単独で用
いられてもよく、２種以上が併用されてもよい。Examples of the polyfunctional acrylate include dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol (meth) tetraacrylate, dipentaerythritol tri (meth) acrylate, and trimethylol. And propane tri (meth) acrylate. Further, those obtained by modifying these polyfunctional acrylates can also be used, and these may be used alone or in combination of two or more.
【００１４】上記シリカ粒子としては、汎用のものが使
用できるが、粒径が小さくなるとハードコート組成物の
粘度が高くなるため塗工が困難になり、粒径が大きくな
ると塗工後のヘイズ値が下がり透明性が低下するので、
粒径０．１〜３μｍが好ましく、より好ましくは０．２
〜０．７μｍである。As the above silica particles, general-purpose silica particles can be used. However, when the particle size is small, the viscosity of the hard coat composition becomes high, so that the coating becomes difficult, and when the particle size is large, the haze value after coating becomes large. And transparency decreases.
The particle size is preferably from 0.1 to 3 μm, more preferably from 0.2 to 3 μm.
０．７0.7 μm.
【００１５】上記ポリシロキサンとしては、以下の
（Ｉ）、（II）及び(III) で表される化合物が用いられ
る。式中、ｍ、ｎは自然数であり、ｍ≧０、ｎ≧０、１
００≧ｍ＋ｎ≧１０が好ましく、より好ましくは５０≧
ｍ＋ｎ≧１５である。ｍ＋ｎ＜１０であると硬度が低く
なり、ハードコート性能が劣る。また、１００＜ｍ＋ｎ
であると塗料が高粘度化するため塗工に問題が生じる。As the polysiloxane, compounds represented by the following (I), (II) and (III) are used. In the formula, m and n are natural numbers, and m ≧ 0, n ≧ 0, 1
00 ≧ m + n ≧ 10 is preferred, and more preferably 50 ≧
m + n ≧ 15. If m + n <10, the hardness will be low and the hard coat performance will be poor. Also, 100 <m + n
If this is the case, the coating material will have a high viscosity, causing problems in coating.
【００１６】[0016]
【化１】 Embedded image
【００１７】上記ハードコート組成物において、シリカ
粒子又はポリシロキサンの配合量は、上記多官能アクリ
レート１００重量部に対して１〜４０重量部が好まし
く、より好ましくは３〜２０重量部である。配合量が、
１重量部未満では表面硬度が低く密着性が向上せず、４
０重量部を超えると硬化後のハードコート層にクラック
が発生し、密着性が低下する。In the hard coat composition, the amount of the silica particles or polysiloxane is preferably 1 to 40 parts by weight, more preferably 3 to 20 parts by weight, based on 100 parts by weight of the polyfunctional acrylate. The amount is
When the amount is less than 1 part by weight, the surface hardness is low and the adhesion is not improved.
If the amount exceeds 0 parts by weight, cracks occur in the hard coat layer after curing, and the adhesiveness is reduced.
【００１８】上記ハードコート組成物の粘度を調整する
ために、非重合性の希釈溶媒を使用してもよい。非重合
性の希釈溶媒としては、例えば、トルエン、キシレン、
酢酸エチル、酢酸ブチル、メチルセルソルブ、エチルセ
ルソルブ、エチルセルソルブアセテート、イソプロピル
アルコール、メチルエチルケトン等が挙げられ、これら
は単独で用いられてもよく、２種以上が併用されてもよ
い。In order to adjust the viscosity of the hard coat composition, a non-polymerizable diluting solvent may be used. As the non-polymerizable diluting solvent, for example, toluene, xylene,
Examples thereof include ethyl acetate, butyl acetate, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, isopropyl alcohol, and methyl ethyl ketone, and these may be used alone or in combination of two or more.
【００１９】また、本発明では市販のハードコート剤を
使用することもできる。この具体例としては、例えば、
後述の反射防止層との密着性を高めた、ＥＸＦ３７に
ウレタンを添加したもの、又は、ＥＸＦ３７にシリコ
ーン系成分及びウレタンを添加したものを用いることが
好ましい。In the present invention, a commercially available hard coat agent can be used. As a specific example, for example,
It is preferable to use a material obtained by adding urethane to EXF37 or a material obtained by adding a silicone-based component and urethane to EXF37, which has improved adhesion to an antireflection layer described later.
【００２０】上記反射防止層としては、ＴｉＯ2 層上と
ＳｉＯ2 層との積層体を用いることが好ましい。上記積
層体は、ハードコート層上に屈折率の高いＴｉＯ2 層
（屈折率：約１．８〜２．１）が形成され、該ＴｉＯ2
層上に屈折率の低いＳｉＯ2 層（屈折率：約１．４〜
１．５）が形成された２層積層体；さらに、この２層積
層体上に、ＴｉＯ2 層上及びＳｉＯ2 層がこの順序で形
成された４層積層体が好ましい。このような２層積層体
又は４層積層体の反射防止層を設けることにより、特定
波長の光の反射率を低くすることができる。As the antireflection layer, it is preferable to use a laminate of a TiO 2 layer and a SiO 2 layer. The laminate has a high refractive index TiO 2 layer on the hard coat layer (refractive index: about 1.8-2.1) is formed, said TiO 2
An SiO 2 layer having a low refractive index (refractive index: about 1.4 to
1.5) formed two-layer laminate; a four-layer laminate in which a TiO 2 layer and a SiO 2 layer are formed in this order on this two- layer laminate is preferable. By providing such a two-layered or four-layered antireflection layer, the reflectance of light having a specific wavelength can be reduced.
【００２１】上記反射防止層の膜厚をｄ、屈折率をｎ、
入射光の波長をλとすると、反射防止層の膜厚とその屈
折率との間でｎｄ＝λ／４なる関係式が成立する。反射
防止層の屈折率が基材の屈折率より小さい場合は、上記
関係式が成立する条件では反射率が最小となる。従っ
て、得られる反射防止層の屈折率ｎが分かっていれば、
膜厚ｄは反射防止層の製造における成膜速度とその処理
時間で決定でき、特定の入射光の波長λ（単色光）に対
して反射率を最小にすることができる。The thickness of the antireflection layer is d, the refractive index is n,
Assuming that the wavelength of the incident light is λ, a relational expression of nd = λ / 4 is established between the thickness of the antireflection layer and its refractive index. When the refractive index of the antireflection layer is smaller than the refractive index of the base material, the reflectance becomes minimum under the conditions where the above relational expression is satisfied. Therefore, if the refractive index n of the obtained antireflection layer is known,
The film thickness d can be determined by the film formation speed and the processing time in the production of the antireflection layer, and the reflectance can be minimized with respect to the specific incident light wavelength λ (monochromatic light).
【００２２】上記反射防止層が、例えばＳｉＯ2 層から
形成され、屈折率が１．４２である場合は、可視光線中
の５５０ｎｍの波長の入射光に対して、反射率を最小に
する反射防止層の膜厚は９７ｎｍとなる。反射防止効果
を期待する可視光線の波長領域は、５５０ｎｍを中心と
して４００〜７００ｎｍの範囲にあるので、反射防止層
の膜厚が波長５５０ｎｍに対応できる膜厚を中心に±３
０％の範囲に設定されれば、可視光線に対する反射防止
効果が十分に期待される。When the antireflection layer is formed of, for example, an SiO 2 layer and has a refractive index of 1.42, the antireflection layer minimizes the reflectance with respect to incident light having a wavelength of 550 nm in visible light. The thickness of the layer is 97 nm. Since the wavelength region of visible light for which an antireflection effect is expected is in the range of 400 to 700 nm around 550 nm, the thickness of the antireflection layer is ± 3 around the film thickness capable of coping with the wavelength of 550 nm.
If it is set in the range of 0%, the antireflection effect on visible light can be sufficiently expected.
【００２３】２層以上の薄膜で反射防止層を形成する場
合は、最上層（表面層）を低屈折率材料のλ／４膜とな
るようにし、基材上から高屈折率材料〜低屈折率材料の
順に配置することが好ましい。ここで、表面から２層目
以降の膜厚は、屈折率との兼ね合いになるが、λ／２膜
又はλ／４膜近辺の厚さとなる。これにより、単層の反
射防止層よりも低反射の波長領域を広げることができ
る。但し、層数を増やすと光の透過率が低下するので、
４層以下が好ましい。When the antireflection layer is formed of two or more thin films, the uppermost layer (surface layer) is formed of a λ / 4 film of a low-refractive-index material, and a high-refractive-index material to a low-refractive-index material is formed on a substrate. It is preferable to arrange them in the order of the rate materials. Here, the film thickness of the second and subsequent layers from the surface depends on the refractive index, but is a thickness near the λ / 2 film or λ / 4 film. This makes it possible to broaden the wavelength range of low reflection compared to a single-layer antireflection layer. However, if the number of layers is increased, the light transmittance will decrease.
Four or less layers are preferred.
【００２４】上記ＳｉＯ2 層上及びＴｉＯ2 層は、常圧
プラズマＣＶＤ法によって成膜されるものが好ましい。The above-mentioned SiO 2 layer and the TiO 2 layer are preferably formed by normal pressure plasma CVD.
【００２５】上記ＴｉＯ2 層は、Ｔｉ原料を常圧プラズ
マＣＶＤ法によって気化させ、キャリアガス（Ａｒ単独
ガス又はＯ2 ガスとの混合ガス）と混合した後、常圧プ
ラズマによりハードコート層上又はすでに積層されたＳ
ｉＯ2 層上に成膜することによって形成される。上記Ｓ
ｉＯ2 層は、Ｓｉ原料を常圧プラズマＣＶＤ法によって
気化させ、キャリアガス（ＡｒもしくはＮ2 の単独ガス
又はこれらの混合ガス；これらのガスとＯ2 ガスとの混
合ガス）と混合した後、常圧プラズマによりハードコー
ト層上又はすでに積層されたＴｉＯ2 層上に成膜するこ
とによって形成される。The TiO 2 layer is formed by vaporizing a Ti raw material by a normal pressure plasma CVD method and mixing it with a carrier gas (a single gas of Ar or a mixed gas with an O 2 gas). Already stacked S
It is formed by forming a film on the iO 2 layer. The above S
The iO 2 layer is formed by evaporating the Si raw material by a normal pressure plasma CVD method and mixing it with a carrier gas (a single gas of Ar or N 2 or a mixed gas thereof; a mixed gas of these gases and O 2 gas). It is formed by forming a film on a hard coat layer or an already laminated TiO 2 layer by normal pressure plasma.
【００２６】上記Ｓｉ原料としては、例えば、テトラエ
トキシシラン等が挙げられ、上記Ｔｉ原料としては、例
えば、テトライソプロポキシチタン等が挙げられる。Examples of the Si raw material include tetraethoxysilane and the like, and examples of the Ti raw material include tetraisopropoxytitanium and the like.
【００２７】上記反射防止層は、一対の対向電極を有
し、当該電極の対向面の少なくとも一方に固体誘電体が
設置されている装置を用いて形成される。プラズマが発
生する部位は、上記電極の一方に固体誘電体を設置した
場合は、固体誘電体と電極の間、上記電極の双方に固体
誘電体を設置した場合は、固体誘電体同士の間の空間で
ある。The antireflection layer has a pair of opposed electrodes, and is formed using a device in which a solid dielectric is provided on at least one of the opposed surfaces of the electrodes. The portion where plasma is generated is between the solid dielectric and the electrode when a solid dielectric is installed on one of the electrodes, and between the solid dielectrics when the solid dielectric is installed on both of the electrodes. Space.
【００２８】上記電極としては、銅、アルミニウム等の
金属単体；ステンレス、真鍮等の合金；金属間化合物等
からなるものが挙げられる。上記対向電極は、電界集中
によるアーク放電の発生を避けるために、対向電極間の
距離が略一定となる構造であることが好ましい。この条
件を満たす電極構造としては、平行平板型、円筒対向平
板型、球対向平板型、双曲面対向平板型、同軸円筒型構
造等が挙げられる。Examples of the above-mentioned electrodes include those composed of a single metal such as copper and aluminum; alloys such as stainless steel and brass; and intermetallic compounds. It is preferable that the counter electrode has a structure in which the distance between the counter electrodes is substantially constant in order to avoid occurrence of arc discharge due to electric field concentration. Examples of an electrode structure that satisfies this condition include a parallel plate type, a cylindrical opposed plate type, a spherical opposed plate type, a hyperboloid opposed plate type, and a coaxial cylindrical structure.
【００２９】上記固体誘電体は、上記電極の対向面の一
方又は双方に設置する。この際、固体誘電体と設置され
る側の電極が密着し、且つ、接する電極の対向面を完全
に覆うようにすることが好ましい。固体誘電体によって
覆われずに電極同士が直接対向する部位があると、そこ
からアーク放電が生じるためである。The solid dielectric is provided on one or both of the opposing surfaces of the electrode. At this time, it is preferable that the electrode on the side on which the solid dielectric is placed is in close contact with the electrode, and that the opposing surface of the contacting electrode is completely covered. This is because if there is a portion where the electrodes directly face each other without being covered by the solid dielectric, an arc discharge occurs therefrom.
【００３０】上記固体誘電体としては、ポリテトラフル
オロエチレン、ポリエチレンテレフタレート等のプラス
チック；ガラス；二酸化珪素、酸化アルミニウム（Ａｌ
2 Ｏ 3 ）、酸化ジルコニウム（ＺｒＯ2 ）、酸化チタン
（ＴｉＯ2 ）等の金属酸化物；チタン酸バリウム等の複
酸化物などが挙げられる。As the solid dielectric, polytetrafur
Plus of ethylene, polyethylene terephthalate, etc.
Tic; glass; silicon dioxide, aluminum oxide (Al
TwoO Three), Zirconium oxide (ZrO)Two), Titanium oxide
(TiOTwoMetal oxides such as barium titanate)
Oxides and the like.
【００３１】上記固体誘電体の形状は、シート状であっ
てもフィルム状であってもよいが、厚みが０．０５〜４
ｍｍであることが好ましい。厚すぎると放電プラズマを
発生するのに高電圧を要し、薄すぎると電圧印加時に絶
縁破壊が起こりアーク放電が発生するためである。The solid dielectric may be in the form of a sheet or a film.
mm. If the thickness is too large, a high voltage is required to generate discharge plasma. If the thickness is too small, dielectric breakdown occurs when a voltage is applied, and arc discharge occurs.
【００３２】上記電極間の距離は、固体誘電体の厚さ、
印加電圧の大きさ、プラズマを利用する目的等を考慮し
て決定される。上記電極の一方に固体誘電体を設置した
場合の固体誘電体と電極の最短距離、又は、上記電極の
双方に固体誘電体を設置した場合の固体誘電体同士の最
短距離は、いずれの場合も１〜５０ｍｍであることが好
ましい。最短距離が１ｍｍ未満の場合は、反射防止層を
製造するには、放電プラズマ発生部の間隔が不充分であ
り、５０ｍｍを超えると、均一な放電プラズマを発生さ
せることが難しい。The distance between the electrodes depends on the thickness of the solid dielectric,
It is determined in consideration of the magnitude of the applied voltage, the purpose of utilizing the plasma, and the like. The shortest distance between the solid dielectric and the electrode when the solid dielectric is installed on one of the electrodes, or the shortest distance between the solid dielectrics when the solid dielectric is installed on both of the electrodes, in any case Preferably it is 1 to 50 mm. When the shortest distance is less than 1 mm, the interval between the discharge plasma generating portions is insufficient for producing an anti-reflection layer, and when it exceeds 50 mm, it is difficult to generate uniform discharge plasma.
【００３３】上記反射防止層の形成方法は、以上説明し
たように、固有の放電プラズマの発生方法により対向電
極間に発生させたプラズマを利用するものであり、対向
電極間、又は、一方の電極の対向面に固体誘電体を設置
する場合には、その固体誘電体と他方の電極の間、もし
くは双方の電極の対向面に固体誘電体を設置する場合に
は、その固体誘電体の間に、反射防止層を形成する基材
が配置される。As described above, the method for forming the anti-reflection layer utilizes the plasma generated between the opposed electrodes by a unique method for generating the discharge plasma, and is used between the opposed electrodes or one of the electrodes. When a solid dielectric is installed on the opposite surface of the solid dielectric, between the solid dielectric and the other electrode, or between the solid dielectric when the solid dielectric is installed on the opposite surface of both electrodes. And a base material for forming an anti-reflection layer.
【００３４】ここで常圧とは、１００〜８００Ｔｏｒｒ
の圧力下をいい、特に圧力調整が容易で、装置が簡便に
なる７００〜７８０Ｔｏｒｒの範囲が好ましい。Here, the normal pressure is 100 to 800 Torr.
The pressure is preferably in the range of 700 to 780 Torr in which pressure adjustment is easy and the apparatus is simple.
【００３５】上記防汚層は、フッ素系シランカップリン
グ剤を、スピンコーター、ディッピング装置、マイクロ
グラビアコーター等の塗工装置によって、上記反射防止
層上に塗工、乾燥することにより形成される。尚、スピ
ンコーター、ディッピング装置では連続処理が行えずバ
ッチ処理になる。The antifouling layer is formed by applying a fluorine-based silane coupling agent on the antireflection layer using a coating apparatus such as a spin coater, a dipping apparatus, or a microgravure coater, and drying. It should be noted that continuous processing cannot be performed with a spin coater or dipping apparatus, and batch processing is performed.
【００３６】上記フッ素系シランカップリング剤の市販
品としては、例えば、信越化学社製コート剤「ＫＰ−８
０１Ｍ」〔CF3(CF2)n C2H4Si(NH2)3〕、東芝シリコン社
製〔CF3(CF2)7C2H4Si(OCH3)3の１００％溶液〕等が挙げ
られる。上記コート剤「ＫＰ−８０１Ｍ」は溶剤ＴＦＢ
〔成分：１，３−ビス（トリフロロメチル）ベンゼン、
セントラル硝子社製〕で希釈して使用される。Commercially available fluorine-based silane coupling agents include, for example, a coating agent “KP-8” manufactured by Shin-Etsu Chemical Co., Ltd.
01M "[CF 3 (CF 2 ) n C 2 H 4 Si (NH 2 ) 3 ], Toshiba Silicon Corp. [100% solution of CF 3 (CF 2 ) 7 C 2 H 4 Si (OCH 3 ) 3 ], etc. Is mentioned. The coating agent “KP-801M” is a solvent TFB
[Ingredient: 1,3-bis (trifluoromethyl) benzene,
Central Glass Co., Ltd.].
【００３７】上記基材としては、透明性を有する有機材
料、無機材料、複合材料から構成され、例えば、透明塩
化ビニル樹脂、ポリスチレン、ポリメチルメタクリレー
ト、ポリメタクリルブチレート、スチレン−メチルメタ
クリレート共重合体、スチレン−アクリロニトリル共重
合体、ポリエチレンテレフタレート、ポリカーボネー
ト、テレフタル酸−ビスフェノールＡの縮合体、シリコ
ーン樹脂、トリアセチルセルロースなどの透明性樹脂；
各種ガラス、セラミックなどが挙げられ、これらの積層
体であってもよい。The substrate is composed of a transparent organic material, an inorganic material, or a composite material. For example, a transparent vinyl chloride resin, polystyrene, polymethyl methacrylate, polymethacryl butyrate, styrene-methyl methacrylate copolymer Styrene-acrylonitrile copolymer, polyethylene terephthalate, polycarbonate, terephthalic acid-bisphenol A condensate, silicone resin, transparent resin such as triacetyl cellulose;
Various types of glass, ceramics, and the like may be mentioned, and a laminate of these may be used.
【００３８】上記基材の形状としては、シート状、フィ
ルム状等が挙げられるが、特に限定されず、様々な形状
をした立体形状物であってもよい。また、表面がＡＧ
（Antiglare)処理されたものであってもよく、トリアセ
チルセルロースの場合はケン化処理が施されたものであ
ってもよい。Examples of the shape of the base material include a sheet shape and a film shape, but are not particularly limited, and may be a three-dimensional object having various shapes. The surface is AG
(Antiglare) treatment may be used, and in the case of triacetyl cellulose, saponification treatment may be applied.
【００３９】上記防汚層は、例えば、ハードコート層上
に防汚剤を溶剤によって希釈したものを、スピンコータ
ー、ディッピング装置、マイクログラビアコーター等に
よって塗工することに形成することができる。上記スピ
ンコーター、ディッピング装置を使用する場合は、連続
処理ができずバッチ処理となる。The antifouling layer can be formed, for example, by coating a hard coat layer obtained by diluting an antifouling agent with a solvent using a spin coater, a dipping device, a microgravure coater, or the like. When the above spin coater and dipping apparatus are used, continuous processing cannot be performed and batch processing is performed.
【００４０】第２発明の反射防止フィルムは、基材の片
面に導電層及び反射防止層がこの順に積層されたもので
ある。The antireflection film of the second invention is obtained by laminating a conductive layer and an antireflection layer on one side of a substrate in this order.
【００４１】上記導電層には、例えば、紫外線、レーザ
ー光線、β線、γ線等のエネルギー線の照射によって硬
化して、透明な皮膜を形成する光硬化性組成物が用いら
れる。光硬化性導電性組成物は、例えば、多官能性（メ
タ）アクリレート化合物、導電性添加剤、（メタ）アク
リル酸アルキルエステル系重合体、光重合開始剤等から
なる組成物を意味し、通常、適切な粘度を有する塗工液
となる。For the conductive layer, a photocurable composition which forms a transparent film by being cured by irradiation with energy rays such as ultraviolet rays, laser beams, β rays, and γ rays is used. The photocurable conductive composition means, for example, a composition comprising a polyfunctional (meth) acrylate compound, a conductive additive, a (meth) alkyl acrylate-based polymer, a photopolymerization initiator, and the like. A coating liquid having an appropriate viscosity is obtained.
【００４２】上記多官能性（メタ）アクリレート化合物
としては、例えば、エチレングリコールジ（メタ）アク
リレート、ノナエチレングリコールジ（メタ）アクリレ
ート、テトラプロピレングリコールジ（メタ）アクリレ
ート、ペンタエリスリトールトリ（メタ）アクリレー
ト、トリメチロールプロパントリ（メタ）アクリレー
ト、グリセロールトリ（メタ）アクリレート、トリス−
（２−ヒドロキシエチル）−イソシアヌル酸エステル
（メタ）アクリレート、２，２−ビス〔４−（アクリロ
キシジエトキシ）フェニル〕プロパン、３−フェノキシ
−２−プロパノイルアクリレート、ペンタエリスリトー
ルトリアクリレートヘキサメチレンジイソシアネートな
どが挙げられる。Examples of the polyfunctional (meth) acrylate compound include ethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, and pentaerythritol tri (meth) acrylate. , Trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, tris-
(2-hydroxyethyl) -isocyanuric acid ester (meth) acrylate, 2,2-bis [4- (acryloxydiethoxy) phenyl] propane, 3-phenoxy-2-propanoyl acrylate, pentaerythritol triacrylate hexamethylene diisocyanate And the like.
【００４３】上記導電性添加剤としては、透明性を著し
く阻害しない限り、通常の有機、無機の導電性添加剤が
使用でき、透明性を重視する場合は、導電性添加剤の粒
子径は可視光線の半波長より十分小さいことが必要であ
る。導電性添加剤を具体的に例示すれば、銀、銅、ニッ
ケル、酸化錫、酸化アンチモン含有酸化錫等の無機系導
電体の超微粒子；アニリン系重合体、ピロール系重合
体、チオフェン系重合体等の有機系導電性体が挙げられ
る。As the above-mentioned conductive additive, ordinary organic and inorganic conductive additives can be used as long as the transparency is not significantly impaired. When importance is placed on transparency, the particle size of the conductive additive is visible. It must be well below the half wavelength of the light beam. Specific examples of the conductive additive include ultrafine particles of an inorganic conductive material such as silver, copper, nickel, tin oxide and antimony oxide-containing tin oxide; aniline polymer, pyrrole polymer, and thiophene polymer. And other organic conductive materials.
【００４４】上記光硬化性導電性組成物において、導電
性添加剤の添加量は、無機系導電体の場合、多官能性
（メタ）アクリレート化合物１００重量部に対し、１０
０〜５００重量部が好ましい。１００重量部未満の場合
は、塗工・硬化膜である導電層の帯電防止性が低く、５
００重量部を超えると、透明性が悪くなる。又、有機系
導電性体の場合、多官能性（メタ）アクリレート化合物
１００重量部に対し、０．１〜３０重量部が好ましい。
０．１重量部未満の場合は、得られる導電層の帯電防止
性が低く、３０重量部を超えると透明性が悪くなる。In the photocurable conductive composition, the amount of the conductive additive is 10 parts by weight based on 100 parts by weight of the polyfunctional (meth) acrylate compound in the case of an inorganic conductive material.
0 to 500 parts by weight is preferred. If the amount is less than 100 parts by weight, the antistatic property of the conductive layer which is a coated / cured film is low, and
If it exceeds 00 parts by weight, the transparency will be poor. In the case of an organic conductive material, the amount is preferably 0.1 to 30 parts by weight based on 100 parts by weight of the polyfunctional (meth) acrylate compound.
When the amount is less than 0.1 part by weight, the antistatic property of the obtained conductive layer is low, and when it exceeds 30 parts by weight, the transparency is deteriorated.
【００４５】上記（メタ）アクリル酸アルキルエステル
系重合体は、（メタ）アクリル酸アルキルエステルの単
独又は共重合体を意味し、導電性添加剤の分散剤として
用いられる。具体的に例示すれば、メチル（メタ）アク
リレート、エチル（メタ）アクリレート、ブチル（メ
タ）アクリレートなどの単独重合体又は共重合体が挙げ
られる。The above-mentioned (meth) acrylic acid alkyl ester-based polymer means a homopolymer or a copolymer of (meth) acrylic acid alkyl ester, and is used as a dispersant for a conductive additive. Specific examples include a homopolymer or copolymer such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate.
【００４６】上記光硬化性導電性組成物において、（メ
タ）アクリル酸アルキルエステル系重合体の添加量は、
多官能性（メタ）アクリレート化合物１００重量部に対
し、１〜１００重量部が好ましい。１重量部未満の場合
は、導電性添加剤の分散効果が少なく、充分な増粘効果
が得られず、塗工性が不充分となる。又、１００重量部
を超えると、粘度が高すぎて塗工性が悪くなり、得られ
る導電層の耐摩耗性が不充分となる。In the above-mentioned photocurable conductive composition, the amount of the alkyl (meth) acrylate polymer is
The amount is preferably 1 to 100 parts by weight based on 100 parts by weight of the polyfunctional (meth) acrylate compound. If the amount is less than 1 part by weight, the effect of dispersing the conductive additive is small, a sufficient thickening effect cannot be obtained, and the coating property becomes insufficient. On the other hand, if it exceeds 100 parts by weight, the viscosity is too high and the coatability is deteriorated, and the abrasion resistance of the obtained conductive layer becomes insufficient.
【００４７】上記光重合開始剤としては、特に限定され
るものではなく、紫外線等の照射により重合開始剤が生
成する光増感剤が使用され、例えば、ベンソイン系、ベ
ンゾフェノン系、アントラセン系のものなどが挙げられ
る。The photopolymerization initiator is not particularly limited, and a photosensitizer which generates a polymerization initiator upon irradiation with ultraviolet rays or the like is used. Examples thereof include benzoin-based, benzophenone-based, and anthracene-based ones. And the like.
【００４８】上記光硬化性導電性組成物には、上記構成
材料以外に、必要に応じて、適宜、有機溶剤、紫外線吸
収剤、酸化防止剤、重合禁止剤などが添加されてもよ
い。[0048] In addition to the above-mentioned constituent materials, an organic solvent, an ultraviolet absorber, an antioxidant, a polymerization inhibitor and the like may be appropriately added to the photocurable conductive composition as required.
【００４９】基材としては、第１発明と同様のものが用
いられる。上記基材に上記光硬化性導電性組成物を塗工
する際には、通常、スプレー法、バーコート法、ドクタ
ーブレード法、ロールコート法、ディッピング法等が採
用される。上記光硬化性導電性組成物に溶剤が添加され
ている場合は、通常、乾燥工程が加えられる。As the base material, the same one as in the first invention is used. When the photocurable conductive composition is applied to the substrate, a spray method, a bar coating method, a doctor blade method, a roll coating method, a dipping method, or the like is usually employed. When a solvent is added to the photocurable conductive composition, a drying step is usually added.
【００５０】上記光硬化性導電性組成物によって形成さ
れる導電層の厚さは、０．５〜５μｍが好ましい。厚さ
が、０．５μｍ未満では導電性が不十分であるため実用
的な帯電防止効果が得られ難く、５μｍを超えると全光
線透過率が低下する。The thickness of the conductive layer formed of the photocurable conductive composition is preferably 0.5 to 5 μm. When the thickness is less than 0.5 μm, the conductivity is insufficient, so that a practical antistatic effect is hardly obtained. When the thickness exceeds 5 μm, the total light transmittance decreases.
【００５１】上記光硬化性導電性組成物の硬化に用いら
れるエネルギー線源としては、例えば、高圧水銀ラン
プ、ハロゲンランプ、キセノンランプ、窒素レーザー、
電子線加速装置、放射性元素などの線源が使用される。
エネルギー線源の照射量は、紫外線波長３６５ｎｍでの
積算露光量として、５０〜５０００ｍＪ／ｃｍ2 が好ま
しい。照射量が、５０ｍＪ／ｃｍ2 未満の場合は、硬化
が不十分となるため、導電層の耐摩耗性や硬度が低下す
る。また、５０００ｍＪ／ｃｍ2 を超えると、導電層が
着色して透明性が低下する。Examples of the energy ray source used for curing the photocurable conductive composition include a high-pressure mercury lamp, a halogen lamp, a xenon lamp, a nitrogen laser,
An electron beam accelerator or a radiation source such as a radioactive element is used.
The irradiation amount of the energy ray source is preferably from 50 to 5000 mJ / cm 2 as an integrated exposure amount at an ultraviolet wavelength of 365 nm. When the irradiation amount is less than 50 mJ / cm 2 , the curing becomes insufficient, so that the wear resistance and hardness of the conductive layer decrease. If it exceeds 5,000 mJ / cm 2 , the conductive layer will be colored and the transparency will be reduced.
【００５２】第２発明の反射防止フィルムは、上記導電
層上に反射防止層が設けられたものである。上記反射防
止層は、第１発明と同様の原料を用いて第１発明と同様
の方法により形成される。[0052] The antireflection film of the second invention has an antireflection layer provided on the conductive layer. The antireflection layer is formed using the same raw materials as in the first invention and by the same method as in the first invention.
【００５３】本発明の反射防止フィルムにおいて、基材
のもう一方の面（導電層の非積層側）に粘着剤層が設け
られてもよい。上記粘着剤としては、基材や偏光板等の
光学部品を強固に接着でき、しかも高温、高湿の条件下
におかれても発泡しないものが好ましく、例えば、アク
リル系粘着剤が好適に用いられる。In the antireflection film of the present invention, a pressure-sensitive adhesive layer may be provided on the other surface of the substrate (on the non-laminated side of the conductive layer). As the pressure-sensitive adhesive, those capable of firmly adhering optical components such as a substrate and a polarizing plate, and which do not foam even under high-temperature, high-humidity conditions are preferable. For example, an acrylic pressure-sensitive adhesive is preferably used. Can be
【００５４】上記アクリル系粘着剤としては、例えば、
アクリル（メタ）アクリレートを主成分とする、重量平
均分子量（Ｍｗ）５０万以下、 Ｍｗ／Ｍｎ（数平均分
子量）＝４以下であるアクリル系ポリマー１００重量
部、ジメチルシリコーンオイル又は側鎖の一部を他の有
機基に置換した変性シリコーンオイルからなる消泡剤
０．０１〜５重量部、メチルハイドロジェンシリコーン
オイルからなる再剥離剤０．０１〜５重量部、及び、架
橋剤０．００１〜５重量部からなるものが好ましい。ま
た、アクリル系粘着剤の市販品としては、例えば綜研化
学社製「ＳＫダイン１３５８」が使用可能である。As the acrylic pressure-sensitive adhesive, for example,
Acrylic (meth) acrylate as a main component, 100 parts by weight of an acrylic polymer having a weight average molecular weight (Mw) of 500,000 or less and Mw / Mn (number average molecular weight) of 4 or less, dimethyl silicone oil or part of a side chain 0.01 to 5 parts by weight of a defoaming agent composed of a modified silicone oil in which is substituted by another organic group, 0.01 to 5 parts by weight of a re-stripping agent composed of a methyl hydrogen silicone oil, and 0.001 to 1 part by weight of a crosslinking agent Those comprising 5 parts by weight are preferred. As a commercially available acrylic pressure-sensitive adhesive, for example, "SK Dyne 1358" manufactured by Soken Chemical Co., Ltd. can be used.
【００５５】上記粘着剤層は、例えば、上記アクリル系
粘着剤を基材に直接塗工して形成してもよく、予め粘着
剤層を離型紙上に設けた後、ラミネータ等によって基材
に積層して形成してもよい。The pressure-sensitive adhesive layer may be formed, for example, by directly applying the above-mentioned acrylic pressure-sensitive adhesive to a base material. After the pressure-sensitive adhesive layer is provided on release paper in advance, the base material is applied to the base material by a laminator or the like. They may be formed by lamination.
【００５６】[0056]
【発明の実施の形態】以下、実施例を掲げて、本発明の
反射防止膜の製造方法を更に詳しく説明するが、本発明
は、これらの実施例のみに限定されるものではない。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the method for producing an antireflection film of the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
【００５７】（実施例１）透明なトリアセテートフィル
ム基材（コニカ社製、１００μｍ厚）の片面に、マイク
ログラビアコーターによってハードコート剤（ＥＸＦ３
７、シリコーン系成分及びウレタンを含有する）を塗工
し、紫外線硬化させてハードコート層（５μｍ厚）を形
成する工程；次いで、このハードコート層上に、ＴｉＯ
2 層（１８０Å厚）及びＳｉＯ2 層（２６０Å厚）をこ
の順に成膜して、２層積層体からなる反射防止層を形成
する工程；上記反射防止層上に、防汚剤（信越化学社製
コート剤「ＫＰ−８０１Ｍ」を溶剤ＴＦＢに溶解した
０．１％固形分濃度溶液）をマイクログラビアコーター
によって塗工して防汚層（２０ｎｍ厚）を形成する工程
を連続して行った後、ロール状に巻取って長尺の反射防
止フィルムを得た。(Example 1) A hard coat agent (EXF3) was coated on one side of a transparent triacetate film substrate (manufactured by Konica Corporation, 100 μm thick) using a microgravure coater.
7, containing a silicone-based component and urethane) and curing with ultraviolet rays to form a hard coat layer (5 μm thick);
A step of forming a two- layer (180 ° thick) and a SiO 2 layer (260 ° thick) in this order to form an antireflection layer composed of a two-layer laminate; an antifouling agent (Shin-Etsu Chemical Co., Ltd.) After a step of applying a coating agent “KP-801M” in a solvent TFB to form a 0.1% solid concentration solution in a solvent TFB by a microgravure coater to form an antifouling layer (20 nm thick), The film was wound into a roll to obtain a long antireflection film.
【００５８】上記反射防止層の製造に図１に示した放電
プラズマ装置を使用した。この装置に於いては下部電極
５上に固体誘電体６が設置されており、固体誘電体６と
上部電極４（直径８０ｍｍの管に直径１ｍｍの穴が５ｍ
ｍ間隔で配設されている）の間の空間に放電プラズマが
発生する。容器２（パイレックスガラス容器、容量８リ
ットル）、ガス導入管８、ガス排出口１０及びガス排気
口１１を備えており、Ｔｉ原料（テトライソプロポキシ
チタン）ガスを導入管８から放電プラズマ発生空間３に
供給し、基材７の上面にＴｉＯ2 からなる反射防止層を
形成した。次いで、Ｓｉ原料（テトラエトキシシラン）
ガスを導入管８から放電プラズマ発生空間３に供給し、
同様にしてＳｉＯ2 からなる反射防止層を形成した。基
材の両面に処理を施したい場合は、放電プラズマ発生空
間３に基材を浮かせて設置すればよい。The discharge plasma apparatus shown in FIG. 1 was used for manufacturing the antireflection layer. In this apparatus, a solid dielectric 6 is provided on a lower electrode 5 and a solid dielectric 6 and an upper electrode 4 (a 1 mm diameter hole is formed in a tube of 80 mm diameter by 5 m).
(disposed at m intervals), discharge plasma is generated. A container 2 (pyrex glass container, capacity 8 liters), a gas inlet tube 8, a gas outlet 10 and a gas outlet 11 are provided, and a Ti raw material (tetraisopropoxytitanium) gas is discharged from the inlet tube 8 into the discharge plasma generation space 3. To form an anti-reflection layer made of TiO 2 on the upper surface of the substrate 7. Next, Si raw material (tetraethoxysilane)
The gas is supplied from the introduction pipe 8 to the discharge plasma generation space 3,
Similarly, an antireflection layer made of SiO 2 was formed. If it is desired to treat both surfaces of the base material, the base material may be set up in the discharge plasma generation space 3.
【００５９】上記Ｔｉ原料ガス及びＳｉ原料ガスはプラ
ズマ発生空間に均一に供給されることが好ましい。Ｔｉ
原料ガス又はＳｉ原料ガスと不活性ガスの混合気体中で
処理を行う場合、不活性ガスは処理用ガスに比較して軽
いので、供給時に不均一になることを避けるような装置
の工夫がされていることが好ましく、特に面積の大きな
基材を処理する場合は、不均一になり易いので注意を要
する。It is preferable that the Ti source gas and the Si source gas are uniformly supplied to the plasma generation space. Ti
When processing in a raw material gas or a mixed gas of a Si raw material gas and an inert gas, since the inert gas is lighter than the processing gas, a device has been devised so as to avoid non-uniformity during supply. In particular, when a substrate having a large area is treated, care must be taken since the substrate tends to be non-uniform.
【００６０】図１の装置に示した例では、ガス導入管８
が多孔構造をもつ上部電極４に連結されており、Ｔｉ原
料ガス又はＳｉ原料ガスは該電極４の孔を通して基材７
上方のプラズマ発生空間３に供給される。不活性ガス
は、これとは別の不活性ガス導入管９から環状に配置さ
れた多数の小孔９１から供給される。不活性ガスを均一
に供給することが可能であれば、このような構造に限定
されず、不活性ガスを撹拌又は高速で吹き付ける等の手
段を用いてもよい。In the example shown in the apparatus of FIG.
Are connected to the upper electrode 4 having a porous structure, and the Ti raw material gas or the Si raw material gas
It is supplied to the upper plasma generation space 3. The inert gas is supplied from a number of small holes 91 arranged annularly from another inert gas introduction pipe 9. The structure is not limited to such a structure as long as the inert gas can be supplied uniformly, and a means such as stirring or blowing the inert gas at a high speed may be used.
【００６１】上記容器２の材質は、樹脂、ガラス等が挙
げられるが、特に限定されない。電極と絶縁のとれた構
造になっていれば、ステンレス、アルミニウム等の金属
を用いることもできる。The material of the container 2 includes, for example, resin and glass, but is not particularly limited. Metals such as stainless steel and aluminum can also be used as long as they have a structure insulated from the electrodes.
【００６２】上記放電プラズマ処理は、基材を加熱また
は冷却して行ってもよいが、室温下で充分可能である。
上記放電プラズマ処理に要する時間は、印加電圧、Ｔｉ
原料ガス又はＳｉ原料ガスの種類及び混合気体中の割合
等を考慮して、反射防止層の膜厚が、式ｎｄ＝λ／４の
関係を満たすように決定される。ここで、ｄは反射防止
層の厚さ、λは入射光の波長、ｎは反射防止層の屈折率
をそれぞれ表す。The discharge plasma treatment may be performed by heating or cooling the substrate, but is sufficiently possible at room temperature.
The time required for the discharge plasma treatment is as follows: applied voltage, Ti
The thickness of the antireflection layer is determined so as to satisfy the relationship of nd = λ / 4 in consideration of the type of the source gas or the Si source gas, the ratio in the mixed gas, and the like. Here, d represents the thickness of the antireflection layer, λ represents the wavelength of the incident light, and n represents the refractive index of the antireflection layer.
【００６３】（実施例２）反射防止層として、ＴｉＯ2
層（１８０Å厚）及びＳｉＯ2 層（２６０Å厚）の２層
積層体の上に、さらにＴｉＯ2 層（１４１０Å厚）及び
ＳｉＯ2 層（８８０Å厚）からなる積層体を設けた４層
積層体を使用したこと以外は、実施例１と同様にして長
尺の反射防止フィルムを得た。Example 2 TiO 2 was used as an anti-reflection layer.
On the 2-layer laminate of layer (180 Å thick) and an SiO 2 layer (260 Å thick), a further TiO 2 layer (1410A thick) and an SiO 2 layer (880A thick) 4-layer laminate of the laminated body is provided consisting of Except having used, it carried out similarly to Example 1, and obtained the long antireflection film.
【００６４】上記実施例１及び２で得られた反射防止フ
ィルムにつき、分光光度計（日立製作所製「Ｕ−４００
０」）を使用して、波長５５０ｎｍ（緑色光）の光で反
射率を測定し図２に示した。The antireflection film obtained in Examples 1 and 2 was used with a spectrophotometer (“U-400” manufactured by Hitachi, Ltd.).
0 "), the reflectance was measured with light having a wavelength of 550 nm (green light), and is shown in FIG.
【００６５】（実施例３）導電性添加剤（三菱マテリア
ル社製「Ｔ−１」）３００重量部、ポリメチルメタクリ
レート（旭化学社製「デルペットＬＰ−1 」）５０重量
部、光重合開始剤（日本化薬社製「カヤキュアーＤＥＴ
Ｘ」）０．１重量部、光重合促進剤（日本化薬社製「カ
ヤキュアーＥＰＡ」）０．１重量部、メチルエチルケト
ン２００重量部、及び、シクロヘキサノン８００重量部
をアトライターを用いて８時間撹拌分散した後、ジペン
タエリスリトールヘキサアクリレート（日本化薬社製
「ＤＰＨＡ）１００重量部を添加して、アトライターを
用いて３０分間撹拌分散して、光硬化性導電性組成物を
調製した。透明アクリル樹脂板（２ｍｍ厚）に上記光硬
化性導電性組成物をバーコーターを用いて、乾燥後の膜
厚が２μｍとなるように塗工した後、高圧水銀ランプに
より１０００ｍＪ／ｃｍ2 の紫外線を照射して塗膜を硬
化させ、導電層を形成した。(Example 3) 300 parts by weight of a conductive additive ("T-1" manufactured by Mitsubishi Materials Corporation), 50 parts by weight of polymethyl methacrylate ("Delpet LP-1" manufactured by Asahi Chemical Co., Ltd.), photopolymerization started (Kayacure DET manufactured by Nippon Kayaku Co., Ltd.)
X ") 0.1 parts by weight, 0.1 parts by weight of a photopolymerization accelerator (" Kayacure EPA "manufactured by Nippon Kayaku Co., Ltd.), 200 parts by weight of methyl ethyl ketone, and 800 parts by weight of cyclohexanone are stirred for 8 hours using an attritor. After the dispersion, 100 parts by weight of dipentaerythritol hexaacrylate (“DPHA” manufactured by Nippon Kayaku Co., Ltd.) was added, and the mixture was stirred and dispersed using an attritor for 30 minutes to prepare a photocurable conductive composition. After applying the above-mentioned photocurable conductive composition to an acrylic resin plate (2 mm thick) using a bar coater so that the film thickness after drying becomes 2 μm, ultraviolet light of 1000 mJ / cm 2 is applied by a high-pressure mercury lamp. The coating was cured by irradiation to form a conductive layer.
【００６６】図１に示した放電プラズマ処理装置におい
て、下部電極５（直径１４０ｍｍ、表面を酸化ジルコニ
ウムの固体誘電体６で被覆したもの）の上に、上記導電
層を設けた透明アクリル樹脂板基材７を配置し、該基材
７表面から２ｍｍ上方に上部電極４を配置して、下記の
条件で反射防止層を作製した。油回転ポンプ（図示しな
い）で容器２内が０．１Ｔｏｒｒになるまで排気した
後、容器内が７６０Ｔｏｒｒになるまでアルゴンガスを
不活性ガス導入管９から導入した。次いで、上部電極４
に接続した（反応）ガス導入管８から流量１０ｓｃｃｍ
のテトラエトキシシラン、流量１０ｓｃｃｍの酸素と流
量９８０ｓｃｃｍの窒素との混合気体を導入した。該混
合気体を１分間導入した後、上部電極４と下部電極５の
間に波高値１６ｋＶ、周波数８ｋＨｚのパルス電界を印
加し、４０秒間放電して、ＳｉＯ2 からなる反射防止層
を作製した。In the discharge plasma processing apparatus shown in FIG. 1, a transparent acrylic resin plate base having the conductive layer provided on a lower electrode 5 (140 mm in diameter, the surface of which is coated with a solid dielectric 6 of zirconium oxide) is used. The material 7 was arranged, and the upper electrode 4 was arranged 2 mm above the surface of the substrate 7 to prepare an antireflection layer under the following conditions. After the inside of the vessel 2 was evacuated to 0.1 Torr by an oil rotary pump (not shown), argon gas was introduced from the inert gas introduction pipe 9 until the inside of the vessel reached 760 Torr. Next, the upper electrode 4
10 sccm from the (reaction) gas inlet tube 8 connected to
And a mixed gas of oxygen at a flow rate of 10 sccm and nitrogen at a flow rate of 980 sccm. After the mixed gas was introduced for one minute, a pulse electric field having a peak value of 16 kV and a frequency of 8 kHz was applied between the upper electrode 4 and the lower electrode 5 and discharged for 40 seconds to produce an antireflection layer made of SiO 2 .
【００６７】（実施例４）ポリエチレンテレフタレート
フィルム基材（帝人社製「テトロンフィルムＨＰ７」、
２ｍｍ厚、以下ＰＥＴという））の上に、上記光硬化製
導電性組成物をマイクログラビアコーターを用いて、乾
燥後の膜厚が２μｍとなるように塗工した後、高圧水銀
ランプを用い１０００ｍＪ／ｃｍ2 の紫外線を照射して
光硬化導電層を硬化させ、導電層を形成した。(Example 4) Polyethylene terephthalate film substrate ("Tetron film HP7" manufactured by Teijin Limited)
2 mm thick, hereinafter referred to as PET)), the photocurable conductive composition is applied using a microgravure coater so that the film thickness after drying becomes 2 μm, and then 1000 mJ using a high-pressure mercury lamp. The photocurable conductive layer was cured by irradiating ultraviolet rays of / cm 2 to form a conductive layer.
【００６８】図３に示した連続処理用放電プラズマ処理
装置（容量８リットルのステンレス製容器２５を有す
る）を用いて、以下に示した操作によりＰＥＴフィルム
基材の導電層上に反射防止層を形成した。図３に示すよ
うに、上記連続処理用放電プラズマ処理装置において、
略円筒状の下部電極２１と局面を有する上部電極２２と
が略等間隔で対向して配置されており、上部電極２２と
下部電極２１との表面には固体誘電体がそれぞれ装着さ
れて、放電面３１及び３２となされている。放電面３１
と３２との間には放電空間３３が形成されている。上記
下部電極２１は接地されており、印加電源（図示しな
い）から放電面３１と３２との間にパルス電圧が印加さ
れ、放電空間３３でプラズマが発生する。Using the discharge plasma processing apparatus for continuous processing shown in FIG. 3 (having a stainless steel container 25 having a capacity of 8 liters), an anti-reflection layer was formed on the conductive layer of the PET film substrate by the following operation. Formed. As shown in FIG. 3, in the discharge plasma processing apparatus for continuous processing,
A substantially cylindrical lower electrode 21 and an upper electrode 22 having a surface are opposed to each other at substantially equal intervals, and solid dielectrics are mounted on the surfaces of the upper electrode 22 and the lower electrode 21, respectively. Surfaces 31 and 32 are provided. Discharge surface 31
And 32, a discharge space 33 is formed. The lower electrode 21 is grounded, a pulse voltage is applied between the discharge surfaces 31 and 32 from an applied power supply (not shown), and plasma is generated in the discharge space 33.
【００６９】上記導電層を有するＰＥＴフィルムの捲重
体を巻き出しロール８０にセットし、該ＰＥＴフィルム
４０を導入口４２、上部電極２２と下部電極２１との間
３３、排出口４３の順で連続処理用放電プラズマ処理装
置で通過させ、巻き取りロール８１に固定した。次い
で、導入口４２及び排出口４３を閉じ、油回転ポンプ
（図示しない）で装置内が７６０Ｔｏｒｒになるまでア
ルゴンガスを、不活性ガス導入管１６から導入した。The wound body of the PET film having the conductive layer was set on an unwinding roll 80, and the PET film 40 was continuously placed in the order of the inlet 42, the gap 33 between the upper electrode 22 and the lower electrode 21, and the outlet 43. It was passed through a processing discharge plasma processing apparatus and fixed to a take-up roll 81. Next, the inlet port 42 and the outlet port 43 were closed, and argon gas was introduced from the inert gas inlet pipe 16 with an oil rotary pump (not shown) until the inside of the apparatus reached 760 Torr.
【００７０】さらに、一方がボンベ６１に接続し、他方
が上部電極２２に接続したガス導入管１６から流量１０
ｓｃｃｍの気化した希釈反応ガス（テトライソロポキシ
チタン２０重量％を含むイソプロピルアルコール溶
液）、及び、流量７０ｓｃｃｍの酸素と流量９２０ｓｃ
ｃｍの窒素との混合気体を放電空間３３に導入した。該
混合気体を１分間導入した後、上部電極２２と下部電極
２１との間に１２ｋＶ、８ｋＨｚのパルス電圧を印加
し、２０秒間放電して導電層上に厚さ２８ｎｍのＴｉＯ
2 からなる反射防止層を連続的に作製した。放電空間３
３を通過した混合気体は不活性ガス排気管１７から排気
される。Further, one of the flow rates is controlled by a gas introduction pipe 16 connected to the cylinder 61 and the other to the upper electrode 22.
sccm vaporized diluted reaction gas (isopropyl alcohol solution containing 20 wt% tetraisolopoxytitanium), 70 sccm oxygen and 920 sc flow
cm of a mixed gas with nitrogen was introduced into the discharge space 33. After the mixed gas was introduced for 1 minute, a pulse voltage of 12 kV and 8 kHz was applied between the upper electrode 22 and the lower electrode 21 and discharged for 20 seconds to form a TiO layer having a thickness of 28 nm on the conductive layer.
An antireflection layer consisting of 2 was continuously produced. Discharge space 3
The mixed gas passing through 3 is exhausted from the inert gas exhaust pipe 17.
【００７１】上記で得られたＴｉＯ2 からなる反射防止
膜上に、上記と同様の連続処理用放電プラズマ処理装置
を用いて、油回転ポンプ（図示しない）で装置内が０．
０１Ｔｏｒｒになるまで排気した後、装置内が７６０Ｔ
ｏｒｒになるまでアルゴンガスを不活性ガス導入管から
導入した。次いで、ガス導入管１６から流量１０ｓｃｃ
ｍのエトキシシラン、及び、流量２００ｓｃｃｍの酸素
と流量７９０ｓｃｃｍの窒素との混合気体を導入した。
該混合気体を１分間導入した後、ロール電極１と曲面電
極２との間に１６ｋＶ、８ｋＨｚのパルス電圧を印加
し、２０秒間放電してＴｉＯ2 反射防止層上に厚さ２２
ｎｍのＳｉＯ2 からなる反射防止層を連続的に作製し
た。以下同様にして、さらに厚さ８４ｎｍのＴｉＯ2 か
らなる反射防止層及び厚さ９５ｎｍのＳｉＯ2 からなる
反射防止層を順次積層して４層からなる反射防止層を形
成し、反射防止フィルムを作製した。On the anti-reflection film made of TiO 2 obtained above, using a discharge plasma processing apparatus for continuous processing similar to the above, the inside of the apparatus was turned to 0.1 mm by an oil rotary pump (not shown).
After exhausting until the pressure reaches 01 Torr, the inside of the
Ar gas was introduced from an inert gas inlet tube until the pressure reached orr. Next, a flow rate of 10 scc from the gas introduction pipe 16
m of ethoxysilane and a mixed gas of oxygen at a flow rate of 200 sccm and nitrogen at a flow rate of 790 sccm were introduced.
After the mixed gas was introduced for 1 minute, a pulse voltage of 16 kV and 8 kHz was applied between the roll electrode 1 and the curved electrode 2 and discharged for 20 seconds to form a layer having a thickness of 22 Å on the TiO 2 antireflection layer.
An anti-reflection layer made of nm 2 SiO 2 was continuously produced. Similarly, an antireflection layer made of TiO 2 having a thickness of 84 nm and an antireflection layer made of SiO 2 having a thickness of 95 nm are sequentially laminated to form an antireflection layer consisting of four layers, thereby producing an antireflection film. did.
【００７２】（比較例１）導電層を全く設けなかったこ
と以外は、実施例３と同様にして反射防止フィルムを作
製した。Comparative Example 1 An anti-reflection film was produced in the same manner as in Example 3 except that no conductive layer was provided.
【００７３】（比較例２）反射防止層を全く設けなかっ
たこと以外は、実施例４と同様にして反射防止フィルム
を作製した。Comparative Example 2 An antireflection film was produced in the same manner as in Example 4 except that no antireflection layer was provided.
【００７４】上記実施例３，４及び比較例１，２で得ら
れた反射防止フィルムにつき、下記項目の評価を行っ
た。 （１）表面固有抵抗 ＡＳＴＭ Ｄ２５７に準拠して表面固有抵抗を測定し、
表１に示した。 （２）反射率 分光光度計（日立製作所製「Ｕ−４０００」）を使用し
て、波長４００〜７００ｎｍの波長範囲における光の反
射率を測定し、図４に示した。また、波長５５０ｎｍ
（緑色光）の光の反射率を表１に示した。The antireflection films obtained in Examples 3 and 4 and Comparative Examples 1 and 2 were evaluated for the following items. (1) Surface resistivity The surface resistivity is measured in accordance with ASTM D257,
The results are shown in Table 1. (2) Reflectance The reflectance of light in a wavelength range of 400 to 700 nm was measured using a spectrophotometer (“U-4000” manufactured by Hitachi, Ltd.), and the results are shown in FIG. In addition, a wavelength of 550 nm
Table 1 shows the reflectance of (green light) light.
【００７５】[0075]
【表１】 [Table 1]
【００７６】[0076]
【発明の効果】本発明の反射防止フィルムは、上述の構
成であり、連続的に生産されることにより、透明性が優
れると共に、基材上にハードコート層、反射防止層及び
防汚層を有する長尺物として提供される。また、本反射
防止フィルムは、透明性が優れると共に導電層を有する
ことにより塵埃が付着し難いので、自動車計器・精密機
器の窓、クリーンルームの間仕切り板、コンピューター
のディスプレイ等に好適に利用される。The antireflection film of the present invention has the above-mentioned structure, and is produced continuously, thereby being excellent in transparency and having a hard coat layer, an antireflection layer and an antifouling layer on a substrate. It is provided as a long object having. In addition, the antireflection film has excellent transparency and has a conductive layer, so that it is difficult for dust to adhere thereto. Therefore, the antireflection film is suitably used for windows of automobile instruments and precision instruments, partition boards for clean rooms, displays of computers, and the like.
【図１】放電プラズマ処理装置の概要を示す模式図であ
る。FIG. 1 is a schematic diagram showing an outline of a discharge plasma processing apparatus.
【図２】実施例１及び２の反射防止シートの反射率測定
結果を示した曲線である。FIG. 2 is a curve showing reflectance measurement results of the antireflection sheets of Examples 1 and 2.
【図３】連続処理用放電プラズマ処理装置の概要を示す
模式図である。FIG. 3 is a schematic diagram showing an outline of a discharge plasma processing apparatus for continuous processing.
【図４】実施例３，４及び比較例１，２の反射防止シー
トの反射率測定結果を示した曲線である。FIG. 4 is a curve showing the reflectance measurement results of the antireflection sheets of Examples 3 and 4 and Comparative Examples 1 and 2.
２ 容器 ３ 放電プラズマ発生空間 ４ 上部電極 ５ 下部電極 ６ 固体誘電体 ７ 基材 ８ ガス導入管 １６ 不活性ガス導入管 １７ 不活性ガス排気管 ２１ 下部電極 ２２ 上部電極 ３１，３２ 放電面 ３３ 放電空間 ４０ ＰＥＴフィルム ４２ 導入口 ４３ 排出口 2 container 3 discharge plasma generation space 4 upper electrode 5 lower electrode 6 solid dielectric 7 base material 8 gas introduction tube 16 inert gas introduction tube 17 inert gas exhaust tube 21 lower electrode 22 upper electrode 31, 32 discharge surface 33 discharge space 40 PET film 42 Inlet 43 Outlet
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｂ０５Ｄ 7/04 Ｂ０５Ｄ 7/04 Ｂ３２Ｂ 7/02 １０３ Ｂ３２Ｂ 7/02 １０３ 9/00 9/00 Ａ Ｂ６０Ｋ 37/00 Ｂ６０Ｋ 37/00 Ｆ Ｃ０９Ｊ 7/02 Ｃ０９Ｊ 7/02 Ｚ Ｇ０２Ｂ 1/10 Ｇ０２Ｂ 1/10 Ｚ ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) B05D 7/04 B05D 7/04 B32B 7/02 103 B32B 7/02 103 9/00 9/00 A B60K 37 / 00 B60K 37/00 F C09J 7/02 C09J 7 / 02Z G02B 1/10 G02B 1 / 10Z
Claims (5)
止層及び防汚層がこの順に積層されてなることを特徴と
する反射防止フィルム。1. An anti-reflection film comprising a hard coat layer, an anti-reflection layer and an anti-fouling layer laminated on one surface of a substrate in this order.
この順に積層されてなることを特徴とする反射防止フィ
ルム。2. An anti-reflection film, comprising a conductive layer and an anti-reflection layer laminated on one surface of a substrate in this order.
層の積層体によって構成されることを特徴とする請求項
１又は２記載の反射防止フィルム。3. An anti-reflection layer comprising a SiO 2 layer and a TiO 2 layer.
The antireflection film according to claim 1, wherein the antireflection film is formed of a layered body.
より形成されてなることを特徴とする請求項１〜３のい
ずれか１項に記載の反射防止フィルム。4. The anti-reflection film according to claim 1, wherein the anti-reflection layer is formed by a normal pressure plasma CVD method.
れてなることを特徴とする請求項１〜４のいずれか１項
に記載の反射防止フィルム。5. The antireflection film according to claim 1, wherein an adhesive layer is provided on the other surface of the substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10288131A JP2000121804A (en) | 1998-10-09 | 1998-10-09 | Antireflection film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10288131A JP2000121804A (en) | 1998-10-09 | 1998-10-09 | Antireflection film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000121804A true JP2000121804A (en) | 2000-04-28 |
Family
ID=17726222
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10288131A Pending JP2000121804A (en) | 1998-10-09 | 1998-10-09 | Antireflection film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000121804A (en) |
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| US7281491B2 (en) | 2002-06-11 | 2007-10-16 | Konica Corporation | Dielectric-coated electrode, plasma discharge treatment apparatus and method for forming thin film |
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| JP4496726B2 (en) * | 2002-07-05 | 2010-07-07 | 日油株式会社 | Low refractive index layer for anti-reflective material, anti-reflective material provided therewith, and use thereof |
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