JP2023021736A - Resin composition for water-repellent lens protective film and method for protecting water-repellent lens - Google Patents
Resin composition for water-repellent lens protective film and method for protecting water-repellent lens Download PDFInfo
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- JP2023021736A JP2023021736A JP2021126788A JP2021126788A JP2023021736A JP 2023021736 A JP2023021736 A JP 2023021736A JP 2021126788 A JP2021126788 A JP 2021126788A JP 2021126788 A JP2021126788 A JP 2021126788A JP 2023021736 A JP2023021736 A JP 2023021736A
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- Prior art keywords
- water
- component
- protective film
- lens
- repellent
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- 230000001681 protective effect Effects 0.000 title claims abstract description 63
- 239000005871 repellent Substances 0.000 title claims abstract description 62
- 239000011342 resin composition Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 29
- 239000003999 initiator Substances 0.000 claims abstract description 23
- -1 thiol compound Chemical class 0.000 claims abstract description 22
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 18
- 239000011737 fluorine Substances 0.000 claims abstract description 18
- 229920001400 block copolymer Polymers 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 238000012545 processing Methods 0.000 abstract description 22
- 239000000463 material Substances 0.000 abstract description 8
- 230000003373 anti-fouling effect Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 206010040844 Skin exfoliation Diseases 0.000 description 11
- 230000003075 superhydrophobic effect Effects 0.000 description 10
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 9
- 238000010186 staining Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 6
- 239000002390 adhesive tape Substances 0.000 description 6
- 230000001588 bifunctional effect Effects 0.000 description 6
- 239000003085 diluting agent Substances 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000002093 peripheral effect Effects 0.000 description 5
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 4
- 150000008365 aromatic ketones Chemical class 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- 239000003550 marker Substances 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 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
- 239000000178 monomer Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
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- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- IMQFZQVZKBIPCQ-UHFFFAOYSA-N 2,2-bis(3-sulfanylpropanoyloxymethyl)butyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(CC)(COC(=O)CCS)COC(=O)CCS IMQFZQVZKBIPCQ-UHFFFAOYSA-N 0.000 description 2
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 2
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 2
- PCKZAVNWRLEHIP-UHFFFAOYSA-N 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropanoyl)phenyl]methyl]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1CC1=CC=C(C(=O)C(C)(C)O)C=C1 PCKZAVNWRLEHIP-UHFFFAOYSA-N 0.000 description 2
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- YYVYAPXYZVYDHN-UHFFFAOYSA-N 9,10-phenanthroquinone Chemical compound C1=CC=C2C(=O)C(=O)C3=CC=CC=C3C2=C1 YYVYAPXYZVYDHN-UHFFFAOYSA-N 0.000 description 2
- MJVAVZPDRWSRRC-UHFFFAOYSA-N Menadione Chemical compound C1=CC=C2C(=O)C(C)=CC(=O)C2=C1 MJVAVZPDRWSRRC-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- SEEVRZDUPHZSOX-WPWMEQJKSA-N [(e)-1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethylideneamino] acetate Chemical compound C=1C=C2N(CC)C3=CC=C(C(\C)=N\OC(C)=O)C=C3C2=CC=1C(=O)C1=CC=CC=C1C SEEVRZDUPHZSOX-WPWMEQJKSA-N 0.000 description 2
- YAAUVJUJVBJRSQ-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2-[[3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propoxy]methyl]-2-(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS YAAUVJUJVBJRSQ-UHFFFAOYSA-N 0.000 description 2
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003759 ester based solvent Substances 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- QGZHYFIQDSBZCB-UHFFFAOYSA-N (2-ethylphenyl)-(2,4,6-trimethylbenzoyl)phosphinic acid Chemical compound CCC1=CC=CC=C1P(O)(=O)C(=O)C1=C(C)C=C(C)C=C1C QGZHYFIQDSBZCB-UHFFFAOYSA-N 0.000 description 1
- WNILQWYHQCFQDH-UHFFFAOYSA-N (2-oxooctylideneamino) 1-(4-phenylsulfanylphenyl)cyclohexa-2,4-diene-1-carboxylate Chemical compound C=1C=C(SC=2C=CC=CC=2)C=CC=1C1(C(=O)ON=CC(=O)CCCCCC)CC=CC=C1 WNILQWYHQCFQDH-UHFFFAOYSA-N 0.000 description 1
- XHXSXTIIDBZEKB-UHFFFAOYSA-N 1,2,3,4,5,6,7,8-octamethylanthracene-9,10-dione Chemical compound CC1=C(C)C(C)=C2C(=O)C3=C(C)C(C)=C(C)C(C)=C3C(=O)C2=C1C XHXSXTIIDBZEKB-UHFFFAOYSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- KIJPZYXCIHZVGP-UHFFFAOYSA-N 2,3-dimethylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=C(C)C(C)=C2 KIJPZYXCIHZVGP-UHFFFAOYSA-N 0.000 description 1
- LZWVPGJPVCYAOC-UHFFFAOYSA-N 2,3-diphenylanthracene-9,10-dione Chemical compound C=1C=CC=CC=1C=1C=C2C(=O)C3=CC=CC=C3C(=O)C2=CC=1C1=CC=CC=C1 LZWVPGJPVCYAOC-UHFFFAOYSA-N 0.000 description 1
- UCSGWEMRGIONEW-UHFFFAOYSA-N 2-(2-chlorophenyl)-4,5-bis(2-methoxyphenyl)-1h-imidazole Chemical class COC1=CC=CC=C1C1=C(C=2C(=CC=CC=2)OC)NC(C=2C(=CC=CC=2)Cl)=N1 UCSGWEMRGIONEW-UHFFFAOYSA-N 0.000 description 1
- UIHRWPYOTGCOJP-UHFFFAOYSA-N 2-(2-fluorophenyl)-4,5-diphenyl-1h-imidazole Chemical class FC1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 UIHRWPYOTGCOJP-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- SNFCQJAJPFWBDJ-UHFFFAOYSA-N 2-(4-methoxyphenyl)-4,5-diphenyl-1h-imidazole Chemical class C1=CC(OC)=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 SNFCQJAJPFWBDJ-UHFFFAOYSA-N 0.000 description 1
- BXYWKXBAMJYTKP-UHFFFAOYSA-N 2-[2-[2-[2-(3-sulfanylpropanoyloxy)ethoxy]ethoxy]ethoxy]ethyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCCOCCOCCOCCOC(=O)CCS BXYWKXBAMJYTKP-UHFFFAOYSA-N 0.000 description 1
- LLOXZCFOAUCDAE-UHFFFAOYSA-N 2-diphenylphosphorylbenzene-1,4-diol Chemical compound OC1=CC=C(O)C(P(=O)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 LLOXZCFOAUCDAE-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- AXYQEGMSGMXGGK-UHFFFAOYSA-N 2-phenoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(=O)C(C=1C=CC=CC=1)OC1=CC=CC=C1 AXYQEGMSGMXGGK-UHFFFAOYSA-N 0.000 description 1
- NTZCFGZBDDCNHI-UHFFFAOYSA-N 2-phenylanthracene-9,10-dione Chemical compound C=1C=C2C(=O)C3=CC=CC=C3C(=O)C2=CC=1C1=CC=CC=C1 NTZCFGZBDDCNHI-UHFFFAOYSA-N 0.000 description 1
- YTPSFXZMJKMUJE-UHFFFAOYSA-N 2-tert-butylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(C(C)(C)C)=CC=C3C(=O)C2=C1 YTPSFXZMJKMUJE-UHFFFAOYSA-N 0.000 description 1
- FYXPKOPFEGFWHG-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)-phenylphosphoryl]phenol Chemical compound C1=CC(O)=CC=C1P(=O)(C=1C=CC(O)=CC=1)C1=CC=CC=C1 FYXPKOPFEGFWHG-UHFFFAOYSA-N 0.000 description 1
- LMBQOLBVWODAFG-UHFFFAOYSA-N 4-bis(4-hydroxyphenyl)phosphorylphenol Chemical compound C1=CC(O)=CC=C1P(=O)(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 LMBQOLBVWODAFG-UHFFFAOYSA-N 0.000 description 1
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- QFUAZGOBONNJEI-UHFFFAOYSA-N 4-diphenylphosphorylphenol Chemical compound C1=CC(O)=CC=C1P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 QFUAZGOBONNJEI-UHFFFAOYSA-N 0.000 description 1
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- 230000006750 UV protection Effects 0.000 description 1
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 description 1
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- HECGKCOICWUUJU-UHFFFAOYSA-N bis(diphenylphosphanylmethyl)-phenylphosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CP(C=1C=CC=CC=1)CP(C=1C=CC=CC=1)C1=CC=CC=C1 HECGKCOICWUUJU-UHFFFAOYSA-N 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
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- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
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- YDMWUMUNUXUYKT-UHFFFAOYSA-N ethyl [(1-oxo-1-phenylpropan-2-ylidene)amino] carbonate Chemical compound CCOC(=O)ON=C(C)C(=O)C1=CC=CC=C1 YDMWUMUNUXUYKT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003887 surface segregation Methods 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
- 238000010998 test method Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は撥水レンズの周縁加工時にレンズ表面を保護するための撥水レンズ保護膜用樹脂組成物に関する。また、撥水レンズの周縁加工時に、加工装置にレンズを保持するために撥水レンズを保護する方法に関する。 TECHNICAL FIELD The present invention relates to a resin composition for a water-repellent lens protective film for protecting the lens surface during peripheral processing of the water-repellent lens. The present invention also relates to a method for protecting a water-repellent lens so as to hold the lens in a processing device during peripheral processing of the water-repellent lens.
眼鏡レンズは眼鏡フレームの枠形状に合うよう加工装置を用いて周縁を加工する。この加工装置は、一対のレンズチャック軸に眼鏡レンズを保持し、レンズチャック軸の回転によりレンズが回転され、砥石等の加工具がレンズに押し当てられることにより、レンズを所望の形状に加工する機械である。その際、眼鏡レンズには両面テープで冶具を貼り付け、その冶具を介してレンズチャック軸に保持される。 The spectacle lens is processed by using a processing device so as to match the frame shape of the spectacle frame. In this processing device, a spectacle lens is held by a pair of lens chuck shafts, the lens is rotated by the rotation of the lens chuck shafts, and a processing tool such as a grindstone is pressed against the lens, thereby processing the lens into a desired shape. Machine. At that time, a jig is attached to the spectacle lens with double-sided tape, and the lens chuck shaft holds the spectacle lens via the jig.
近年、水や油など汚れが付着しにくい撥水・撥油物質がレンズ表面にコーティングされた撥水レンズが多く使用されている。これらの撥水レンズはその表面が滑りやすいため、撥水処理が施されていないレンズと同様の加工法では両面テープの粘着力が不足し、レンズチャック軸の回転角度に対してレンズの回転角度がずれてしまう、いわゆる軸ずれが発生する問題があった。この軸ずれを防ぐ方法として、レンズ表面に一時的に保護膜を設ける手法が知られている。この手法では、レンズ表面に冶具固定用の両面テープ及びレンズ表面と良好な接着性を有する保護層を形成することで、レンズ加工時の軸ずれを防止できる。また、加工後はレンズから保護膜を容易に剥がすことができる。 In recent years, water-repellent lenses coated with a water-repellent/oil-repellent substance to which dirt such as water and oil are less likely to adhere have been widely used. Since the surface of these water-repellent lenses is slippery, if the same processing method is used for lenses that are not water-repellent, the adhesive strength of the double-sided tape will be insufficient, and the rotation angle of the lens relative to the rotation angle of the lens chuck axis will be reduced. There is a problem that the so-called axis misalignment occurs. A method of temporarily providing a protective film on the lens surface is known as a method of preventing this axial displacement. In this method, a double-faced tape for fixing jigs and a protective layer having good adhesion to the lens surface are formed on the lens surface, thereby preventing misalignment during lens processing. Moreover, after processing, the protective film can be easily peeled off from the lens.
上記の保護膜を形成するための組成物には、撥水レンズ表面に均一に塗工可能であること（塗工性）が求められる。加えて、本組成物から得られる保護膜には、加工時は撥水レンズから剥離せず、加工後は容易に剥離可能という適度な密着性を有すること（密着性）、保護膜剥離後にレンズの撥水性に影響を与えないこと（非汚染性）も必要とされる。尚、レンズに保護膜を形成後、周縁加工を行うまでには数ヶ月の期間が空く場合もあるため、保護膜には長期間保管を行っても密着性や非汚染性が変わらないことも求められる。 The composition for forming the above protective film is required to be able to be uniformly applied to the surface of the water-repellent lens (coatability). In addition, the protective film obtained from this composition should have appropriate adhesion (adhesion) so that it does not peel off from the water-repellent lens during processing and can be easily peeled off after processing. It is also required not to affect the water repellency of the coating (non-staining property). After the protective film is formed on the lens, it may take several months before the peripheral processing is performed. Desired.
このような組成物として、特許文献１には、撥水・撥油性能を有する防汚膜が形成されたプラスチック眼鏡レンズの表面に、一時的に保護膜を形成するための材料として、アクリル樹脂を有機溶剤に溶解した組成物が記載されている。 As such a composition, in Patent Document 1, an acrylic resin is used as a material for temporarily forming a protective film on the surface of a plastic spectacle lens on which an antifouling film having water and oil repellency is formed. is dissolved in an organic solvent.
また、特許文献２には被着体から硬化物を剥離させる際に適度な剥離強度を有する保護膜を形成可能な材料として、アクリルオリゴマー、アクリルモノマー、チオール化合物及び光開始剤を組み合わせた組成物が記載されている。 In addition, Patent Document 2 describes a composition in which an acrylic oligomer, an acrylic monomer, a thiol compound and a photoinitiator are combined as a material capable of forming a protective film having an appropriate peel strength when the cured product is peeled off from the adherend. is described.
しかしながら、最近はコーティング表面の水滴の接触角が１５０°以上となる、いわゆる超撥水と呼ばれる撥水処理が増えており、このような処理が施された超撥水レンズに対しては、特許文献１及び特許文献２に記載の発明では、塗工性、密着性及び非汚染性を並立できないという課題があった。 Recently, however, there has been an increase in the number of water-repellent treatments called super-water-repellent, in which the contact angle of water droplets on the coating surface is 150° or more. The inventions described in Document 1 and Patent Document 2 have the problem that coatability, adhesion and non-staining properties cannot be achieved at the same time.
本発明は前記の従来技術に鑑みてなされたものであり、その目的は、特に防汚性の高い超撥水レンズであっても均一に塗工可能であり、且つ、加工時は撥水レンズから剥離せず、加工後には容易に剥離可能な適度な密着性を有するとともに、剥離時の硬化膜の破断が生じない強靭性を有し、剥離後に基材の撥水性に影響を与えない保護膜を形成可能な樹脂組成物と、撥水レンズに保護膜を形成することで加工時のレンズの軸ずれを防止し、所望の形状へ加工できる方法を提供することである。 The present invention has been made in view of the prior art described above, and its object is to enable uniform coating even on super water-repellent lenses with particularly high antifouling properties, and to provide a water-repellent lens during processing. It does not peel off from the substrate and has moderate adhesion that allows it to be easily peeled off after processing. It also has toughness so that the cured film does not break when peeled off, and does not affect the water repellency of the substrate after peeling. To provide a resin composition capable of forming a film, and a method for forming a protective film on a water-repellent lens so as to prevent misalignment of the lens during processing and to process the lens into a desired shape.
本発明は（Ａ）重量平均分子量が２５０～３０，０００である多官能（メタ）アクリレートと、（Ｂ）多官能チオール化合物と、（Ｃ）光重合開始剤と、（Ｄ）重量平均分子量が２５，０００～１００，０００でありフッ素系セグメントと非フッ素系セグメントからなるブロック共重合体を含有する樹脂組成物であって、前記（Ａ）成分１００質量部中に、（Ｂ）成分を０．５～３０質量部、（Ｃ）成分を０．１～２５質量部、（Ｄ）成分を０．１～２５質量部含むことを特徴とする、撥水レンズ保護膜用樹脂組成物である。 The present invention comprises (A) a polyfunctional (meth)acrylate having a weight average molecular weight of 250 to 30,000, (B) a polyfunctional thiol compound, (C) a photopolymerization initiator, and (D) a weight average molecular weight of 25,000 to 100,000 and containing a block copolymer consisting of fluorine-based segments and non-fluorine-based segments, wherein 0 parts by mass of component (B) is contained in 100 parts by mass of component (A). .5 to 30 parts by mass, 0.1 to 25 parts by mass of component (C), and 0.1 to 25 parts by mass of component (D). .
また、本発明は撥水レンズに上記保護膜用樹脂組成物を塗布、硬化して得られる硬化膜を保護層として設けることにより、撥水レンズを保護する方法である。 The present invention also provides a method for protecting a water-repellent lens by providing a cured film obtained by coating and curing the above resin composition for a protective film on the water-repellent lens as a protective layer.
本発明の撥水レンズ保護膜用樹脂組成物は、特に防汚性が高く、表面への塗工が困難な超撥水レンズであっても均一に塗工可能である。加えて、本発明の撥水レンズ保護膜用樹脂組成物を硬化して得られる硬化膜は、撥水レンズに対して適度な密着力を有することから加工時の軸ずれを防止でき、保護膜を剥離した際に残渣なく容易に剥がすことができる。 The resin composition for a water-repellent lens protective film of the present invention has particularly high antifouling properties, and can be uniformly coated even on super-water-repellent lenses that are difficult to coat on the surface. In addition, the cured film obtained by curing the resin composition for a protective film for a water-repellent lens of the present invention has an appropriate adhesive strength to the water-repellent lens, so that it is possible to prevent misalignment of the axis during processing. can be easily removed without leaving any residue.
以下に本発明について詳しく説明する。なお、本発明において「（メタ）アクリレート」とは、アクリレートとメタクリレートの双方を含む総称を意味する。また、本発明において数値範囲を示す「○○～××」とは、別途記載が無い限り、その下限値（「○○」）や上限値（「××」）を含む概念である。すなわち、正確には「○○以上××以下」を意味する。 The present invention will be described in detail below. In the present invention, "(meth)acrylate" means a generic term including both acrylate and methacrylate. In the present invention, "○○ to XX", which indicates a numerical range, is a concept including its lower limit ("○○") and upper limit ("XX") unless otherwise specified. That is, it means "more than XX and less than XX" exactly.
本発明の撥水レンズ保護膜用樹脂組成物は、下記（Ａ）、（Ｂ）、（Ｃ）及び（Ｄ）成分を必須成分として含有する硬化性樹脂組成物である。
＜（Ａ）成分：多官能（メタ）アクリレート＞
（Ａ）多官能（メタ）アクリレートは、重量平均分子量（Ｍｗ）が２５０～３０，０００であり、分子内に（メタ）アクリロイル基を２個以上有する化合物であれば特に限定されず、公知の材料を用いることができる。尚、（Ａ）成分は、１種のみを単独で用いてもよく、２種以上を組み合わせて用いても良い。
The resin composition for a water-repellent lens protective film of the present invention is a curable resin composition containing the following components (A), (B), (C) and (D) as essential components.
<(A) component: polyfunctional (meth)acrylate>
(A) The polyfunctional (meth)acrylate is not particularly limited as long as it is a compound having a weight average molecular weight (Mw) of 250 to 30,000 and having two or more (meth)acryloyl groups in the molecule. materials can be used. In addition, (A) component may be used individually by 1 type, and may be used in combination of 2 or more types.
（Ａ）多官能（メタ）アクリレートの好ましい例として以下の一般式（式１）で表される化合物が挙げられる。
式中のａは、好ましくは２～３０である。
Ｒ１は、炭素数２～３００の炭化水素基若しくはエーテル酸素（－Ｏ－）およびヒドロキシル基（－ＯＨ）からなる群より選択される少なくとも１種を含む炭素数２～３００の炭化水素基、イソシアヌレート環若しくはイソシアヌレート環と炭化水素基若しくは炭素数２～２０の炭化水素基のみからなる基、又は、炭素数２～２５０の炭化水素基若しくはエーテル酸素（－Ｏ－）およびヒドロキシル基（－ＯＨ）からなる群より選択される少なくとも１種を含む炭素数２～２５０の炭化水素基である。Ｒ２は、水素原子またはメチル基である。
In the formula, a is preferably 2-30.
R 1 is a hydrocarbon group having 2 to 300 carbon atoms or a hydrocarbon group having 2 to 300 carbon atoms containing at least one selected from the group consisting of ether oxygen (-O-) and hydroxyl group (-OH); An isocyanurate ring or a group consisting of an isocyanurate ring and a hydrocarbon group or a hydrocarbon group having 2 to 20 carbon atoms, or a hydrocarbon group having 2 to 250 carbon atoms or an ether oxygen (-O-) and a hydroxyl group (- OH) is a hydrocarbon group having 2 to 250 carbon atoms containing at least one selected from the group consisting of: R2 is a hydrogen atom or a methyl group.
（Ａ）多官能（メタ）アクリレートの具体例としては、トリメチロールプロパントリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールヘキサアクリレート等の多官能（メタ）アクリレートモノマーや、エポキシ基を有する化合物と（メタ）アクリル酸の反応によって得られるエポキシ変性（メタ）アクリレート、ジイソシアネート化合物とジオール化合物と水酸基を有する（メタ）アクリレート化合物との反応によって得られるウレタン（メタ）アクリレート等の多官能（メタ）アクリレートオリゴマー等が挙げられる。 (A) Specific examples of polyfunctional (meth)acrylates include polyfunctional (meth)acrylate monomers such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate; ) Polyfunctional (meth)acrylate oligomers such as epoxy-modified (meth)acrylate obtained by reaction of acrylic acid, urethane (meth)acrylate obtained by reaction of diisocyanate compound, diol compound and hydroxyl group-containing (meth)acrylate compound, etc. is mentioned.
これらの中でもウレタン（メタ）アクリレートを用いることが好ましい。柔軟なウレタン結合を有する化合物を用いることで、硬化膜と撥水レンズとの密着力が向上し、加工時の軸ずれを抑制することができる。加えて、硬化膜の強靭性が向上し、剥離時の硬化膜の破断を抑制できる。 Among these, it is preferable to use urethane (meth)acrylate. By using a compound having a flexible urethane bond, the adhesion between the cured film and the water-repellent lens is improved, and misalignment during processing can be suppressed. In addition, the toughness of the cured film is improved, and breakage of the cured film during peeling can be suppressed.
ウレタン（メタ）アクリレートの具体例としては、ＵＮ－３５２（官能基数：２、Ｍｗ：３，０００）、ＵＮ－３３３（官能基数：２、Ｍｗ：３，０００）、ＵＮ－３５３（官能基数：２、Ｍｗ：５，０００）、ＵＮ－１２５５（官能基数：２、Ｍｗ：８，０００）、ＵＮ－６２００（官能基数：２、Ｍｗ：６，５００）、ＵＮ－６２０１（官能基数：２、Ｍｗ：１，６００）、ＵＮ－９０００ＰＥＰ（官能基数：２、Ｍｗ：５，０００）、ＵＮ－９２００Ａ（官能基数：２、Ｍｗ：１５，０００）、ＵＮ－３３２０ＨＡ（官能基数：６、Ｍｗ：１，５００）、ＵＮ－９０４（官能基数：１０、Ｍｗ：４，９００）、ＵＮ－９５３（官能基数：２０、Ｍｗ：１４，０００～４０，０００）、ＵＮ－９５４（官能基数：６、Ｍｗ：４，５００）、ＵＮ－６３０５（官能基数：２、Ｍｗ：２７，０００）、Ｈ－２１９（官能基数：９、Ｍｗ：２５，０００～５０，０００）（以上はいずれも商品名、根上工業株式会社製）、ＥＢＥＣＲＹＬ２３０（官能基数：２、Ｍｗ：５，０００）、ＥＢＥＣＲＹＬ９２６０（官能基数：３、Ｍｗ：１，５００）、ＥＢＥＣＲＹＬ４６６６（官能基数：４、Ｍｗ：１，１００）（以上はいずれも商品名、ダイセル・オルネクス株式会社製）、ＵＸ－４１０１（官能基数：２、Ｍｗ：６，５００）、ＵＸ－６１０１（官能基数：２、Ｍｗ：６，５００）（以上はいずれも商品名、日本化薬工業株式会社製）等が挙げられる。 Specific examples of urethane (meth)acrylates include UN-352 (number of functional groups: 2, Mw: 3,000), UN-333 (number of functional groups: 2, Mw: 3,000), UN-353 (number of functional groups: 2, Mw: 5,000), UN-1255 (number of functional groups: 2, Mw: 8,000), UN-6200 (number of functional groups: 2, Mw: 6,500), UN-6201 (number of functional groups: 2, Mw: 1,600), UN-9000PEP (number of functional groups: 2, Mw: 5,000), UN-9200A (number of functional groups: 2, Mw: 15,000), UN-3320HA (number of functional groups: 6, Mw: 1,500), UN-904 (number of functional groups: 10, Mw: 4,900), UN-953 (number of functional groups: 20, Mw: 14,000 to 40,000), UN-954 (number of functional groups: 6, Mw: 4,500), UN-6305 (number of functional groups: 2, Mw: 27,000), H-219 (number of functional groups: 9, Mw: 25,000 to 50,000) (all of the above are trade names, Neagari Kogyo Co., Ltd.), EBECRYL230 (number of functional groups: 2, Mw: 5,000), EBECRYL9260 (number of functional groups: 3, Mw: 1,500), EBECRYL4666 (number of functional groups: 4, Mw: 1,100) (above are all trade names, manufactured by Daicel Allnex Co., Ltd.), UX-4101 (number of functional groups: 2, Mw: 6,500), UX-6101 (number of functional groups: 2, Mw: 6,500) (all of the above product name, manufactured by Nippon Kayaku Kogyo Co., Ltd.) and the like.
（Ａ）多官能（メタ）アクリレートの重量平均分子量は２５０～３０，０００であることが好ましく、より好ましくは５００～１５，０００である。重量平均分子量が２５０未満であると、硬化膜と撥水レンズとの密着力が低下し、３０，０００を超えると、硬化膜の強靭性が不十分となり、剥離時に硬化膜が破断するため、撥水レンズから硬化膜を剥離する際の作業性が低下する。 (A) The polyfunctional (meth)acrylate preferably has a weight average molecular weight of 250 to 30,000, more preferably 500 to 15,000. If the weight-average molecular weight is less than 250, the adhesive strength between the cured film and the water-repellent lens is reduced. Workability is reduced when the cured film is peeled off from the water-repellent lens.
なお、本明細書において、重量平均分子量は、東ソー（株）製ゲルパーミエーションクロマトグラフィー装置ＨＬＣ－８２２０ＧＰＣを用いて、カラムとして東ソー（株）製ＴＳＫｇｅｌ ＨＺＭ－Ｍを用い、ＴＨＦを溶離液とし、ＲＩ検出器により測定してポリスチレン換算により求めた。 In the present specification, the weight average molecular weight is measured using a gel permeation chromatography device HLC-8220GPC manufactured by Tosoh Corporation, using TSKgel HZM-M manufactured by Tosoh Corporation as a column, using THF as an eluent, It was measured with an RI detector and calculated by polystyrene conversion.
（Ａ）多官能（メタ）アクリレートの分子内の（メタ）アクリロイル基の数（官能基数）は、２以上であれば特に制限されないが、例えば、２～３０である。上限値として、好ましくは２０以下であり、より好ましくは１５以下であり、さらに好ましくは１０以下であり、特に好ましくは８以下である。 (A) The number of (meth)acryloyl groups in the molecule of the polyfunctional (meth)acrylate (number of functional groups) is not particularly limited as long as it is 2 or more, and is, for example, 2-30. The upper limit is preferably 20 or less, more preferably 15 or less, still more preferably 10 or less, and particularly preferably 8 or less.
（Ａ）多官能（メタ）アクリレートの含有量は、（Ａ）～（Ｄ）成分全量を基準として、７０～９７質量％であることが好ましく、より好ましくは７５～９５質量％である。（Ａ）成分の含有量が７０質量％以上の場合、硬化膜の強靭性が向上し、剥離時の硬化膜の破断を抑制するため、撥水レンズから硬化膜を剥離する際の作業性が向上する。９７質量％以下の場合、硬化膜と撥水レンズとの密着力が適度に調整され、硬化膜を剥離することが容易となる。 (A) The content of polyfunctional (meth)acrylate is preferably 70 to 97% by mass, more preferably 75 to 95% by mass, based on the total amount of components (A) to (D). When the content of component (A) is 70% by mass or more, the toughness of the cured film is improved, and breakage of the cured film during peeling is suppressed. improves. When the content is 97% by mass or less, the adhesion between the cured film and the water-repellent lens is appropriately adjusted, and the cured film can be easily peeled off.
＜（Ｂ）成分：多官能チオール化合物＞
（Ｂ）成分である多官能チオール化合物は、分子内にチオール基（－ＳＨ基）を２個以上有する化合物であれば特に限定されず、公知の材料を用いることができる。尚、（Ｂ）成分は、１種のみを単独で用いてもよく、２種以上を組み合わせて用いても良い。
<(B) component: polyfunctional thiol compound>
The polyfunctional thiol compound as component (B) is not particularly limited as long as it has two or more thiol groups (--SH groups) in the molecule, and known materials can be used. In addition, (B) component may be used individually by 1 type, and may be used in combination of 2 or more types.
（Ｂ）多官能チオール化合物の具体例としては、トリメチロールプロパントリス（３－メルカプトプロピオネート）、トリス－［（３－メルカプトプロピオニルオキシ）－エチル］－イソシアヌレート、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）、テトラエチレングリコールビス（３－メルカプトプロピオネート）、ジペンタエリスリトールヘキサキス（３－メルカプトプロピオネート）等が挙げられる。 (B) Specific examples of polyfunctional thiol compounds include trimethylolpropane tris (3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritol tetrakis (3-mercapto propionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate) and the like.
（Ｂ）多官能チオール化合物の含有量は、前記（Ａ）成分１００質量部に対して０．５～３０質量部であることが好ましく、より好ましくは１．０～２５質量部である。（Ｂ）成分の含有量が前記（Ａ）成分１００質量部に対して０．５質量部未満であると、硬化膜と撥水レンズとの密着力が過剰となり、硬化膜を剥離することが困難となり、３０質量部を超えると、硬化膜の強靭性が不十分となり、剥離時に硬化膜が破断するため、撥水レンズから硬化膜を剥離する際の作業性が低下する。 The content of the polyfunctional thiol compound (B) is preferably 0.5 to 30 parts by mass, more preferably 1.0 to 25 parts by mass, per 100 parts by mass of the component (A). If the content of component (B) is less than 0.5 parts by mass with respect to 100 parts by mass of component (A), the adhesion between the cured film and the water-repellent lens becomes excessive, and the cured film may be peeled off. If it exceeds 30 parts by mass, the toughness of the cured film will be insufficient, and the cured film will break when peeled off, resulting in reduced workability when peeling the cured film from the water-repellent lens.
（Ａ）成分由来の（メタ）アクリロキシ基に対する（Ｂ）成分由来のチオール基の比率（以下、（Ｂ）／（Ａ）官能基比）は、０．０５～５．０であることが好ましく、より好ましくは０．１０～３．０である。（Ｂ）／（Ａ）官能基比が０．０５未満であると、硬化膜と撥水レンズとの密着力が過剰となり、硬化膜を剥離することが困難であり、５．０を超えると、硬化膜の強靭性が不十分となり、剥離時に硬化膜が破断するため、撥水レンズから硬化膜を剥離する際の作業性が低下する。 The ratio of thiol groups derived from component (B) to (meth)acryloxy groups derived from component (A) (hereinafter referred to as (B)/(A) functional group ratio) is preferably 0.05 to 5.0. , more preferably 0.10 to 3.0. When the (B)/(A) functional group ratio is less than 0.05, the adhesion between the cured film and the water-repellent lens becomes excessive, making it difficult to peel off the cured film. In addition, the toughness of the cured film becomes insufficient, and the cured film breaks when peeled off, resulting in a decrease in workability when the cured film is peeled off from the water-repellent lens.
＜（Ｃ）成分：光重合開始剤＞
（Ｃ）成分である光重合開始剤は、特に限定されず、公知の材料を用いることができる。尚、（Ｃ）成分は、１種のみを単独で用いてもよく、２種以上を組み合わせて用いても良い。
<(C) Component: Photoinitiator>
The photopolymerization initiator that is the component (C) is not particularly limited, and known materials can be used. In addition, (C) component may be used individually by 1 type, and may be used in combination of 2 or more types.
（Ｃ）光重合開始剤の具体例としては、アシルホスフィンオキサイド系、オキシムエステル系、芳香族ケトン系、キノン系、アルキルフェノン系、イミダゾール系、アクリジン系、フェニルグリシン系の光重合開始剤等が挙げられる。 (C) Specific examples of the photopolymerization initiator include acylphosphine oxide-based, oxime ester-based, aromatic ketone-based, quinone-based, alkylphenone-based, imidazole-based, acridine-based, and phenylglycine-based photopolymerization initiators. mentioned.
（アシルホスフィンオキサイド系光重合開始剤）
アシルホスフィンオキサイド系光重合開始剤は、アシルホスフィンオキサイド基（＞Ｐ（＝Ｏ）－Ｃ（＝Ｏ）－基）を有するものであり、具体例としては、（２，６－ジメトキシベンゾイル）－２，４，６－ペンチルホスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）－フェニルホスフィンオキサイド、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド（「ＩＲＧＡＣＵＲＥ－ＴＰＯ」（ＢＡＳＦ社製））、エチル－２，４，６－トリメチルベンゾイルフェニルホスフィネイト、ビス（２，４，６－トリメチルベンゾイル）－フェニルホスフィンオキサイド（「ＩＲＧＡＣＵＲＥ－８１９」（ＢＡＳＦ社製））、（２，５－ジヒドロキシフェニル）ジフェニルホスフィンオキサイド、（ｐ－ヒドロキシフェニル）ジフェニルホスフィンオキサイド、ビス（ｐ－ヒドロキシフェニル）フェニルホスフィンオキサイド、トリス（ｐ－ヒドロキシフェニル）ホスフィンオキサイド等が挙げられる。
(Acylphosphine oxide photopolymerization initiator)
The acylphosphine oxide photopolymerization initiator has an acylphosphine oxide group (>P(=O)-C(=O)-group), and specific examples include (2,6-dimethoxybenzoyl)- 2,4,6-pentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (“IRGACURE-TPO” (manufactured by BASF)), Ethyl-2,4,6-trimethylbenzoylphenylphosphinate, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (“IRGACURE-819” (manufactured by BASF)), (2,5-dihydroxyphenyl ) diphenylphosphine oxide, (p-hydroxyphenyl)diphenylphosphine oxide, bis(p-hydroxyphenyl)phenylphosphine oxide, tris(p-hydroxyphenyl)phosphine oxide and the like.
（オキシムエステル系光重合開始剤）
オキシムエステル系光重合開始剤は、オキシムエステル結合を有する光重合開始剤であり、具体例としては、１，２－オクタンジオン－１－［４－（フェニルチオ）フェニル］－２－（Ｏ－ベンゾイルオキシム）（商品名：ＯＸＥ－０１、ＢＡＳＦ社製）、１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］エタノン１－（Ｏ－アセチルオキシム）（商品名：ＯＸＥ－０２、ＢＡＳＦ社製）、１－フェニル－１，２－プロパンジオン－２－［Ｏ－（エトキシカルボニル）オキシム］（商品名：Ｑｕａｎｔａｃｕｒｅ－ＰＤＯ、日本化薬株式会社製）等が挙げられる。
(Oxime ester photopolymerization initiator)
The oxime ester photopolymerization initiator is a photopolymerization initiator having an oxime ester bond, and specific examples include 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyl oxime) (trade name: OXE-01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime) (trademark Name: OXE-02, manufactured by BASF), 1-phenyl-1,2-propanedione-2-[O-(ethoxycarbonyl)oxime] (trade name: Quantacure-PDO, manufactured by Nippon Kayaku Co., Ltd.), etc. mentioned.
（芳香族ケトン系光重合開始剤）
芳香族ケトン系光重合開始剤の具体例としては、ベンゾフェノン、Ｎ，Ｎ’－テトラメチル－４，４’－ジアミノベンゾフェノン（ミヒラーケトン）、Ｎ，Ｎ’－テトラエチル－４，４’－ジアミノベンゾフェノン、４－メトキシ－４’－ジメチルアミノベンゾフェノン、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン（「ＩＲＧＡＣＵＲＥ－６５１」（ＢＡＳＦ社製））、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタン－１－オン（「ＩＲＧＡＣＵＲＥ－３６９」（ＢＡＳＦ社製））、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルフォリノ－プロパン－１－オン（「ＩＲＧＡＣＵＲＥ－９０７」（ＢＡＳＦ社製））等が挙げられる。
(Aromatic ketone-based photopolymerization initiator)
Specific examples of aromatic ketone-based photopolymerization initiators include benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one ("IRGACURE-651" (manufactured by BASF)), 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl)-butan-1-one ("IRGACURE-369" (manufactured by BASF)), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propane-1- ON (“IRGACURE-907” (manufactured by BASF)) and the like.
（キノン系光重合開始剤）
キノン系光重合開始剤の具体例としては、２－エチルアントラキノン、フェナントレンキノン、２－ｔ－ブチルアントラキノン、オクタメチルアントラキノン、１，２－ベンズアントラキノン、２，３－ベンズアントラキノン、２－フェニルアントラキノン、２，３－ジフェニルアントラキノン、１－クロロアントラキノン、２－メチルアントラキノン、１，４－ナフトキノン、９，１０－フェナントラキノン、２－メチル－１，４－ナフトキノン、２，３－ジメチルアントラキノン等が挙げられる。
(Quinone photopolymerization initiator)
Specific examples of quinone photopolymerization initiators include 2-ethylanthraquinone, phenanthrenequinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, etc. mentioned.
（アルキルフェノン系光重合開始剤）
アルキルフェノン系光重合開始剤の具体例としては、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインフェニルエーテル等のベンゾイン系化合物、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン（「ＩＲＧＡＣＵＲＥ－６５１」（ＢＡＳＦ社製））、１－ヒドロキシ－シクロヘキシル－フェニル－ケトン（「ＩＲＧＡＣＵＲＥ－１８４」（ＢＡＳＦ社製））、２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン（「ＩＲＧＡＣＵＲＥ－１１７３」（ＢＡＳＦ社製））、１－［４－（２－ヒドロキシエトキシ）－フェニル］－２－ヒドロキシ－２－メチル－１－プロパン－１－オン（「ＩＲＧＡＣＵＲＥ－２９５９」（ＢＡＳＦ社製））、２－ヒロドキシ－１－｛４－［４－（２－ヒドロキシ－２－メチル－プロピオニル）－ベンジル］フェニル｝－２－メチル－プロパン－１－オン（「ＩＲＧＡＣＵＲＥ－１２７」（ＢＡＳＦ社製））等が挙げられる。
(Alkylphenone photopolymerization initiator)
Specific examples of alkylphenone-based photopolymerization initiators include benzoin-based compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin phenyl ether, and 2,2-dimethoxy-1,2-diphenylethane-1. -one (“IRGACURE-651” (manufactured by BASF)), 1-hydroxy-cyclohexyl-phenyl-ketone (“IRGACURE-184” (manufactured by BASF)), 2-hydroxy-2-methyl-1-phenyl-propane -1-one (“IRGACURE-1173” (manufactured by BASF)), 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (“IRGACURE -2959" (manufactured by BASF)), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one ("IRGACURE-127" (manufactured by BASF)) and the like.
（イミダゾール系光重合開始剤）
イミダゾール系光重合開始剤の具体例としては、２，４，５－トリアリールイミダゾール二量体が例示され、より詳細には、２－（２－クロロフェニル）－１－〔２－（２－クロロフェニル）－４，５－ジフェニル－１，３－ジアゾール－２－イル〕－４，５－ジフェニルイミダゾール等の２－（ｏ－クロロフェニル）－４，５－ジフェニルイミダゾール二量体、２－（ｏ－クロロフェニル）－４，５－ジ（メトキシフェニル）イミダゾール二量体、２－（ｏ－フルオロフェニル）－４，５－ジフェニルイミダゾール二量体、２－（ｏ－メトキシフェニル）－４，５－ジフェニルイミダゾール二量体、２－（ｐ－メトキシフェニル）－４，５－ジフェニルイミダゾール二量体等が挙げられる。
(Imidazole-based photopolymerization initiator)
Specific examples of imidazole-based photopolymerization initiators include 2,4,5-triarylimidazole dimers, more specifically, 2-(2-chlorophenyl)-1-[2-(2-chlorophenyl 2-(o-chlorophenyl)-4,5-diphenylimidazole dimers such as )-4,5-diphenyl-1,3-diazol-2-yl]-4,5-diphenylimidazole, 2-(o- Chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenyl Examples include imidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, and the like.
これらの中でも各種光源を用いた際の硬化性の観点から、芳香族ケトン系光重合開始剤を用いることが好ましい。 Among these, it is preferable to use an aromatic ketone-based photopolymerization initiator from the viewpoint of curability when using various light sources.
（Ｃ）光重合開始剤の含有量は、前記（Ａ）成分１００質量部に対して０．１～２５質量部であることが好ましく、より好ましくは０．５～２０質量部である。（Ｃ）成分の含有量が前記（Ａ）成分１００質量部に対して０．１質量部未満であると、硬化不足となり、硬化膜と撥水レンズとの密着力低下や硬化膜の強靭性低下が生じるとともに、保護膜を剥離した際に未硬化成分の残渣により基材の撥水性が低下する。また、（Ｃ）成分の含有量が前記（Ａ）成分１００質量部に対して２５質量部を超えると、光重合開始剤が過剰となり、保護膜を剥離した際に光重合開始剤の残渣により基材の撥水性が低下する。 The content of (C) photopolymerization initiator is preferably 0.1 to 25 parts by mass, more preferably 0.5 to 20 parts by mass, per 100 parts by mass of component (A). If the content of component (C) is less than 0.1 part by mass with respect to 100 parts by mass of component (A), curing will be insufficient, resulting in reduced adhesion between the cured film and the water-repellent lens and toughness of the cured film. When the protective film is peeled off, the residue of the uncured component lowers the water repellency of the substrate. Further, when the content of component (C) exceeds 25 parts by mass with respect to 100 parts by mass of component (A), the photopolymerization initiator becomes excessive, and when the protective film is peeled off, the residue of the photopolymerization initiator causes The water repellency of the base material is lowered.
＜（Ｄ）成分：フッ素系セグメントと非フッ素系セグメントからなるブロック共重合体＞
（Ｄ）成分であるフッ素系セグメントと非フッ素系セグメントからなるブロック共重合体は、公知の材料を用いることができる。尚、（Ｄ）成分は、１種のみを単独で用いてもよく、２種以上を組み合わせて用いても良い。
<(D) Component: Block Copolymer Consisting of Fluorinated Segment and Non-Fluorinated Segment>
Known materials can be used for the block copolymer consisting of a fluorine-based segment and a non-fluorine-based segment, which is the component (D). In addition, (D) component may be used individually by 1 type, and may be used in combination of 2 or more types.
（Ｄ）フッ素系セグメントと非フッ素系セグメントからなるブロック共重合体の具体例としては、エチレン性不飽和化合物のブロック共重合体が挙げられる。フッ素系セグメントと非フッ素系セグメントからなるブロック共重合体を用いることで、撥水レンズに保護膜形成用樹脂組成物を塗布した際に（Ｄ）成分が表面偏析し易くなり、撥水レンズへの塗工性を高めることができる。また、表面偏析性が高まることにより、塗膜内部の（Ａ）多官能（メタ）アクリレートと（Ｂ）多官能チオール化合物の硬化反応を（Ｄ）成分が阻害し難くなるため、より強靭性に優れた硬化膜が得られる。 (D) Specific examples of block copolymers composed of fluorine-based segments and non-fluorine-based segments include block copolymers of ethylenically unsaturated compounds. By using a block copolymer consisting of a fluorine-based segment and a non-fluorine-based segment, when the resin composition for forming a protective film is applied to the water-repellent lens, the component (D) is easily segregated on the surface, and the water-repellent lens becomes can improve the coatability of. In addition, by increasing the surface segregation, it becomes difficult for the component (D) to inhibit the curing reaction between the (A) polyfunctional (meth)acrylate and (B) the polyfunctional thiol compound inside the coating film, resulting in a tougher coating. An excellent cured film is obtained.
（Ｄ）フッ素系セグメントと非フッ素系セグメントからなるブロック共重合体の市販品としては、モディパーＦ２０６、モディパーＦ２４６、モディパーＦ３６３６（以上はいずれも商品名、日油株式会社製）等が挙げられる。 (D) Examples of commercially available block copolymers composed of fluorine-based segments and non-fluorine-based segments include MODIPER F206, MODIPER F246, and MODIPER F3636 (all trade names, manufactured by NOF Corporation).
（Ｄ）フッ素系セグメントと非フッ素系セグメントからなるブロック共重合体の重量平均分子量は２５，０００～１００，０００が好ましく、より好ましくは３０，０００～８０，０００である。重量平均分子量が２５，０００未満であると、保護膜を剥離した際に界面活性剤の残渣により基材の撥水性が低下し、１００，０００を超えると、撥水レンズへの塗工性が低下する。なお、重量平均分子量の測定方法は、（Ａ）多官能（メタ）アクリレートの重量平均分子量の測定方法と同一である。 (D) The block copolymer consisting of fluorine-based segments and non-fluorine-based segments preferably has a weight average molecular weight of 25,000 to 100,000, more preferably 30,000 to 80,000. If the weight-average molecular weight is less than 25,000, the water repellency of the substrate is lowered due to the residue of the surfactant when the protective film is peeled off. descend. The method for measuring the weight average molecular weight is the same as the method for measuring the weight average molecular weight of (A) polyfunctional (meth)acrylate.
（Ｄ）フッ素系セグメントと非フッ素系セグメントからなるブロック共重合体の含有量は、前記（Ａ）成分１００質量部に対して０．１～２５質量部であることが好ましく、より好ましくは０．５～２０質量部、特に好ましくは１．０～１５質量部である。（Ｄ）成分の含有量が前記（Ａ）成分１００質量部に対して０．１質量部未満であると、撥水レンズへの塗工性が不足し、２５質量部を超えると、保護膜を剥離した際に界面活性剤の残渣により基材の撥水性が低下する。 (D) The content of the block copolymer consisting of fluorine-based segments and non-fluorine-based segments is preferably 0.1 to 25 parts by mass, more preferably 0 parts by mass, per 100 parts by mass of component (A). .5 to 20 parts by weight, particularly preferably 1.0 to 15 parts by weight. If the content of component (D) is less than 0.1 parts by mass based on 100 parts by mass of component (A), the coating properties on the water-repellent lens will be insufficient. When the is peeled off, the water repellency of the substrate is lowered due to the residue of the surfactant.
＜希釈剤＞
本発明の撥水レンズ保護膜用樹脂組成物は、反応系を均一にし、塗工を容易にするために有機溶媒や反応性希釈剤で希釈して使用してもよい。そのような有機溶媒としては、アルコール系溶剤、芳香族炭化水素系溶剤、エーテル系溶剤、エステル系溶剤及びエーテルエステル系溶剤、ケトン系溶剤等が挙げられる。反応性希釈剤としてはビニル基、アクリロイル基、メタクリロイル基等を有する、単官能性の光重合性単量体を用いることができる。これらのうち、アクリロイル基又はメタクリロイル基を有する（メタ）アクリレート化合物が好ましく、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ｎ－ヘキシル（メタ）アクリレート、ステアリル（メタ）アクリレート等が挙げられる。希釈剤の配合量は本発明の特性を損なわない範囲において任意に調整すれば良い。
<Diluent>
The resin composition for a water-repellent lens protective film of the present invention may be diluted with an organic solvent or a reactive diluent before use in order to homogenize the reaction system and facilitate coating. Examples of such organic solvents include alcohol-based solvents, aromatic hydrocarbon-based solvents, ether-based solvents, ester-based solvents, ether-ester-based solvents, and ketone-based solvents. A monofunctional photopolymerizable monomer having a vinyl group, an acryloyl group, a methacryloyl group, or the like can be used as the reactive diluent. Among these, (meth)acrylate compounds having an acryloyl group or a methacryloyl group are preferred, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, tert -Butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, n-hexyl (meth)acrylate, stearyl (meth)acrylate and the like. The blending amount of the diluent may be arbitrarily adjusted within a range that does not impair the characteristics of the present invention.
本発明の撥水レンズ保護膜用樹脂組成物には、本発明の特性を損なわない範囲において顔料、染料などの着色剤、安定剤、難燃剤、有機充填剤、可塑剤、酸化防止剤、消泡剤、カップリング剤、レオロジーコントロール剤等の添加剤を適量配合しても良い。 The resin composition for a water-repellent lens protective film of the present invention contains coloring agents such as pigments and dyes, stabilizers, flame retardants, organic fillers, plasticizers, antioxidants, and anti-oxidants as long as the properties of the present invention are not impaired. Additives such as foaming agents, coupling agents, and rheology control agents may be added in appropriate amounts.
＜保護膜の形成＞
本発明の撥水レンズ保護膜用樹脂組成物を用いて保護膜を形成する方法は特に制限されないが、例えば、ディップコート、スプレーコート、スピンコートなどの方法を挙げることができる。本発明の撥水レンズ保護膜用樹脂組成物を用いて形成される保護膜の厚みは、特に制限されないが、レンズの周縁加工時の軸ずれ防止や、加工及び保管時の傷つき防止の観点から、１０μｍ以上である方が好ましい。一方、塗膜の厚みは、レンズ中心を特定する際位置ずれが生じないように、１００μｍ以下であることが好ましい。
<Formation of protective film>
The method for forming a protective film using the resin composition for a water-repellent lens protective film of the present invention is not particularly limited, and examples thereof include methods such as dip coating, spray coating, and spin coating. The thickness of the protective film formed using the resin composition for a water-repellent lens protective film of the present invention is not particularly limited, but from the viewpoints of preventing misalignment during peripheral processing of the lens and preventing damage during processing and storage. , is preferably 10 μm or more. On the other hand, the thickness of the coating film is preferably 100 μm or less so as not to cause misalignment when specifying the lens center.
本発明の撥水レンズ保護膜用樹脂組成物を塗布した後に、基材上に塗布された当該組成物を紫外線などの活性エネルギー線を照射して保護膜を得ることができる。活性エネルギー線照射工程で用いられる光源としては、例えばＵＶ－ＬＥＤ（紫外線ＬＥＤ）、低圧水銀灯、高圧水銀灯、超高圧水銀灯、メタルハライドランプ、カーボンアーク、キセノンアーク、気体レーザー、固体レーザー、電子線照射装置などが挙げられる。
中でも従来のＵＶランプ等と比較して消費電力が大幅に少なく、光源から発生する熱量がＵＶランプと比較して特に少ないＵＶ－ＬＥＤが好ましく、さらにはそのピーク照度が可視光に近い３９５ｎｍ以上であるＵＶ－ＬＥＤを用いることで紫外線照射時の撥水レンズへの影響を抑制し、撥水層におけるクラックの発生を抑制することが出来る。
After coating the resin composition for a water-repellent lens protective film of the present invention, the composition coated on the substrate is irradiated with active energy rays such as ultraviolet rays to obtain a protective film. Examples of light sources used in the active energy ray irradiation process include UV-LEDs (ultraviolet LEDs), low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, carbon arcs, xenon arcs, gas lasers, solid-state lasers, and electron beam irradiation devices. etc.
Among them, UV-LED, which consumes significantly less power than conventional UV lamps, etc., and emits particularly little heat from the light source compared to UV lamps, is preferable. By using a certain UV-LED, it is possible to suppress the influence of UV irradiation on the water-repellent lens and suppress the occurrence of cracks in the water-repellent layer.
＜（Ａ）成分：多官能（メタ）アクリレート＞
Ａ－１：エチレンオキシド変性ビスフェノールＡジメタクリレート（ブレンマーＰＤＢＥ－２００Ａ 日油株式会社製：２官能、重量平均分子量５４１）
Ａ－２： ウレタンアクリレート（アートレジンＵＮ－３３３ 根上工業社製：２官能、重量平均分子量３，０００）
Ａ－３： ポリエーテル系ウレタンアクリレート（アートレジンＵＮ－１２５５ 根上工業社製：２官能、重量平均分子量８，０００）
Ａ－４： ポリカーボネート系ウレタンアクリレート（アートレジンＵＮ－９２００Ａ 根上工業社製：２官能、重量平均分子量１５，０００）
Ａ－５： 脂肪族ウレタンアクリレート（ＥＢＥＣＲＹＬ４６６６ ダイセル・オルネクス社製：４官能、重量平均分子量１，１００）
Ａ’－１：エチレングリコールジメタクリレート（ライトエステルＥＧ 共栄社化学株式会社製：２官能、重量平均分子量１９８）
Ａ’－２：ウレタンアクリレート（紫光ＵＶ－３７００Ｂ 三菱ケミカル株式会社製：２官能、重量平均分子量３８，０００）
<(A) component: polyfunctional (meth)acrylate>
A-1: Ethylene oxide-modified bisphenol A dimethacrylate (Blenmer PDBE-200A manufactured by NOF Corporation: bifunctional, weight average molecular weight 541)
A-2: Urethane acrylate (Artresin UN-333, manufactured by Negami Kogyo Co., Ltd.: bifunctional, weight average molecular weight 3,000)
A-3: Polyether-based urethane acrylate (Artresin UN-1255, manufactured by Negami Kogyo Co., Ltd.: bifunctional, weight average molecular weight 8,000)
A-4: Polycarbonate-based urethane acrylate (Artresin UN-9200A, manufactured by Negami Kogyo Co., Ltd.: bifunctional, weight average molecular weight 15,000)
A-5: Aliphatic urethane acrylate (EBECRYL4666 manufactured by Daicel Allnex Co., Ltd.: tetrafunctional, weight average molecular weight 1,100)
A'-1: Ethylene glycol dimethacrylate (light ester EG manufactured by Kyoeisha Chemical Co., Ltd.: bifunctional, weight average molecular weight 198)
A'-2: Urethane acrylate (Shikou UV-3700B, manufactured by Mitsubishi Chemical Corporation: bifunctional, weight average molecular weight 38,000)
＜（Ｂ）成分：多官能チオール化合物＞
Ｂ－１：ジペンタエリスリトールヘキサキス（３－メルカプトプロピオネート）（ＤＰＭＰ ＳＣ有機化学株式会社製：６官能、重量平均分子量７８３）
Ｂ－２：トリメチロールプロパントリス（３－メルカプトプロピオネート）（ＴＭＭＰ ＳＣ有機化学株式会社製：３官能、重量平均分子量３９９）
<(B) component: polyfunctional thiol compound>
B-1: Dipentaerythritol hexakis (3-mercaptopropionate) (manufactured by DPMP SC Organic Chemical Co., Ltd.: hexafunctional, weight average molecular weight 783)
B-2: Trimethylolpropane tris (3-mercaptopropionate) (manufactured by TMMP SC Organic Chemical Co., Ltd.: trifunctional, weight average molecular weight 399)
＜（Ｃ）成分：光重合開始剤＞
Ｃ－１：２，２－ジメトキシー２－フェニルアセトフェノン（ＯＭＮＩＲＡＤ６５１ ＩＧＭ社製）
<(C) Component: Photoinitiator>
C-1: 2,2-dimethoxy-2-phenylacetophenone (OMNIRAD651 manufactured by IGM)
＜（Ｄ）成分：フッ素系セグメントと非フッ素系セグメントからなるブロック共重合体＞
Ｄ－１：フッ素系ブロックコポリマー（モディパーＦ２０６ 日油株式会社製、重量平均分子量３８，０００）
Ｄ－２：フッ素系ブロックコポリマー（モディパーＦ２４６ 日油株式会社製、重量平均分子量２５，０００）
Ｄ－３：フッ素系ブロックコポリマー（モディパーＦ３６３６ 日油株式会社製、重量平均分子量７７，０００）
Ｄ’－１：ポリエーテル変性シリコーンオイル（ＤＯＷＳＩＬ Ｌ－７００１ ダウ・東レ株式会社）
<(D) Component: Block Copolymer Consisting of Fluorinated Segment and Non-Fluorinated Segment>
D-1: Fluorinated block copolymer (Modiper F206 manufactured by NOF Corporation, weight average molecular weight 38,000)
D-2: Fluorinated block copolymer (MODIPER F246 manufactured by NOF Corporation, weight average molecular weight 25,000)
D-3: Fluorinated block copolymer (MODIPER F3636 manufactured by NOF Corporation, weight average molecular weight 77,000)
D'-1: Polyether-modified silicone oil (DOWSIL L-7001 Dow Toray Industries, Inc.)
＜希釈剤＞
ＭＥＫ：メチルエチルケトン
ＩＰＡＣ：イソプロピルアセテート
ＢＡ：ブチルアクリレート
<Diluent>
MEK: methyl ethyl ketone IPAC: isopropyl acetate BA: butyl acrylate
表１～３に示す配合比で（Ａ）～（Ｄ）成分及び希釈剤を混合容器へ投入し、室温（２３℃）、紫外線カット下でスリーワンモーターを用いて均一になるまで撹拌することで、撥水レンズ保護膜用樹脂組成物のサンプルを得た。得られた実施例及び比較例の各撥水レンズ保護膜用樹脂組成物に対して以下の塗工性、密着性（保持力、剥離性、強靭性）及び非汚染性の評価を行った。その結果を表１～３に示す。 The components (A) to (D) and the diluent are added to the mixing container at the compounding ratios shown in Tables 1 to 3, and stirred until uniform using a three-one motor at room temperature (23 ° C.) under UV protection. , a sample of a resin composition for a water-repellent lens protective film was obtained. The obtained resin compositions for water-repellent lens protective films of Examples and Comparative Examples were evaluated for coatability, adhesion (holding power, peelability, toughness) and non-staining properties as follows. The results are shown in Tables 1-3.
[超撥水レンズへの保護膜形成]
評価には純水の接触角が１５０°以上となる超撥水層を備えたプラスチックレンズ（直径７５ｍｍ）を用いた。この超撥水レンズに対し、実施例及び比較例の撥水レンズ保護膜用樹脂組成物をディップコート法により硬化後膜厚が２０μｍとなるようにコートした。コート後、室温（２３℃）、紫外線がカットされた空間で１０分間静置し乾燥させ、ＬＥＤ紫外線照射装置（ウシオ電機株式会社製Ｕｎｉｊｅｔ Ｅ１１０ＩＩＨＤ―３９５）を用い、照度５００ｍＷ／ｃｍ２になるようレンズとの距離を調節して片面ずつ照射した。尚、超撥水レンズの接触角は、対象レンズ表面に純水１μＬの液滴を接触させ、その時のレンズと液滴のなす角度により算出した。
[Formation of protective film on superhydrophobic lens]
For the evaluation, a plastic lens (diameter 75 mm) provided with a superhydrophobic layer having a pure water contact angle of 150° or more was used. This super water-repellent lens was coated with the resin compositions for a water-repellent lens protective film of Examples and Comparative Examples by a dip coating method so that the film thickness after curing was 20 μm. After coating, it is allowed to stand for 10 minutes at room temperature (23 ° C.) in a space where ultraviolet rays are cut off, and dried using an LED ultraviolet irradiation device (Unijet E110IIHD-395 manufactured by Ushio Inc.) so that the illuminance is 500 mW / cm 2 . The distance to the lens was adjusted to irradiate one side at a time. The contact angle of the superhydrophobic lens was calculated from the angle formed by the lens and the droplet when a droplet of 1 μL of pure water was brought into contact with the surface of the objective lens.
［塗工性評価］
前述したディップコート法により超撥水レンズへ撥水レンズ保護膜用樹脂組成物をコートし、硬化させた。ハジキが見られた場合、レンズ端部からコートされていない部分の最大の幅をハジキの大きさとして計測し、以下の通り評価した。尚、塗工性はハジキの大きさが１０ｍｍ以下を合格とした。
◎：ハジキ無し。
○：端部からコートできていない部分が５ｍｍ以下である。
△：端部からコートできていない部分が５ｍｍより大きく１０ｍｍ以下である。
×：端部からコートできていない部分が１０ｍｍより大きい。
[Evaluation of coatability]
The superhydrophobic lens was coated with the resin composition for a water-repellent lens protective film by the above-described dip coating method and cured. When cissing was observed, the maximum width of the uncoated portion from the edge of the lens was measured as the size of cissing and evaluated as follows. As regards the coatability, the size of repellency of 10 mm or less was regarded as acceptable.
A: No cissing.
◯: The portion not coated from the edge is 5 mm or less.
Δ: The portion not coated from the edge is greater than 5 mm and 10 mm or less.
x: The part which cannot be coated from the edge is larger than 10 mm.
［保持力評価］
レンズの周縁加工時の軸ずれ評価として、超撥水レンズへ形成した保護膜の保持力を評価した。保持力評価はＪＩＳ－Ｚ０２３７に準拠し、荷重を変更して行った。温度：２３℃、相対湿度：５０％環境下で３ヶ月保管した保護膜形成済み超撥水レンズの中心部に幅２４ｍｍ、長さ１３０ｍｍの粘着テープ（ニチバン社製ＣＴ４０５ＡＰ－２４）を貼り付ける（図１参照）。この時、粘着テープ上とレンズ凹部の中心部で重なるよう油性ペンで印をつける。粘着テープのレンズに貼り付けた端部と反対側の端部に重さ１４．７Ｎの荷重をかけ、１０分間後に凸面と凹面の印にずれが生じた距離を測定した（図２参照）。得られた測定結果について以下の通り評価した。尚、保持力測定結果は２．０ｍｍ以下を合格とした。
◎：保持力測定結果が０．０ｍｍである。
○：保持力測定結果が０．０ｍｍより大きく、０．５ｍｍ以下である。
△：保持力測定結果が０．５ｍｍより大きく２．０ｍｍ以下である。
×：保持力測定結果が２．０ｍｍより大きい。
[Holding power evaluation]
As an evaluation of axial misalignment during peripheral processing of the lens, the holding power of the protective film formed on the superhydrophobic lens was evaluated. The holding power evaluation was performed by changing the load according to JIS-Z0237. An adhesive tape (CT405AP-24 manufactured by Nichiban Co., Ltd.) with a width of 24 mm and a length of 130 mm is attached to the center of a super water-repellent lens with a protective film formed on it that has been stored for 3 months under an environment of temperature: 23°C and relative humidity: 50% ( See Figure 1). At this time, mark with a permanent marker so that the adhesive tape overlaps with the center of the concave portion of the lens. A load of 14.7 N was applied to the end of the adhesive tape opposite to the end attached to the lens, and after 10 minutes, the distance by which the marks on the convex and concave surfaces were displaced was measured (see FIG. 2). The obtained measurement results were evaluated as follows. A holding force measurement result of 2.0 mm or less was regarded as acceptable.
A: The holding force measurement result is 0.0 mm.
○: The holding force measurement result is greater than 0.0 mm and 0.5 mm or less.
Δ: The holding force measurement result is greater than 0.5 mm and 2.0 mm or less.
x: The holding force measurement result is larger than 2.0 mm.
［剥離性］
温度：２３℃、相対湿度：５０％環境下で３ヶ月保管した保護膜形成済み超撥水レンズの端部に粘着テープ（ニチバン社製ＣＴ４０５ＡＰ－２４）を貼り付けた後、手でテープを剥離した。同位置で粘着テープの貼付・剥離を繰り返し、保護膜が剥離するまでに必要なテープの剥離回数を確認し、以下の通り評価した。尚、剥離性は〇又は△を合格とした。
〇：１回のテープ剥離で保護膜を剥離できる。
△：２～５回のテープ剥離で保護膜を剥離できる。
×：５回以上のテープ剥離を行っても保護膜を剥離できない。
[Peelability]
An adhesive tape (CT405AP-24 manufactured by Nichiban Co., Ltd.) was affixed to the end of a super water-repellent lens with a protective film formed thereon, which had been stored for 3 months under an environment of temperature: 23°C and relative humidity: 50%, and then the tape was peeled off by hand. bottom. The adhesion and peeling of the adhesive tape were repeated at the same position, and the number of peelings of the tape required until the protective film was peeled off was confirmed and evaluated as follows. For peelability, ◯ or Δ was regarded as acceptable.
◯: The protective film can be peeled off by one tape peeling.
Δ: The protective film can be peeled off by tape peeling 2 to 5 times.
x: The protective film cannot be peeled off even if the tape is peeled off 5 times or more.
［強靭性］
温度：２３℃、相対湿度：５０％環境下で３ヶ月保管した保護膜形成済み超撥水レンズの端部に粘着テープ（ニチバン社製ＣＴ４０５ＡＰ－２４）を貼り付けた後、手でテープを剥離した。剥離した保護膜の形状を確認し、以下の通り、評価した。尚、強靭性は〇又は△を合格とした。
〇：保護膜に亀裂がない。
△：保護膜に３０ｍｍ未満の亀裂がある。
×：保護膜が破断し、１回のテープ剥離では保護膜を剥離できない。
[Toughness]
An adhesive tape (CT405AP-24 manufactured by Nichiban Co., Ltd.) was affixed to the end of a super water-repellent lens with a protective film formed thereon, which had been stored for 3 months under an environment of temperature: 23°C and relative humidity: 50%, and then the tape was peeled off by hand. bottom. The shape of the peeled protective film was confirmed and evaluated as follows. For the toughness, ◯ or △ was regarded as a pass.
O: No cracks in the protective film.
Δ: The protective film has cracks of less than 30 mm.
x: The protective film was broken, and the protective film could not be peeled off by one tape peeling.
［非汚染性］
温度：２３℃、相対湿度：５０％環境下で３ヶ月保管した保護膜形成済み超撥水レンズから保護膜を剥離した後、レンズに対し油性マジック（寺西化学工業社製マジックインキ（黒））でレンズに線を引いた際のインクのハジキを観察し、以下の通り評価した。尚、保護膜を形成する前のレンズ表面は油性マジックのインクをはじくが、レンズ表面に汚染物質が残っていると撥水性が低下する。尚、非汚染性は〇又は△を合格とした。
〇：直線で描いたインクが点状になる。
△：直線で描いたインクが細い線状になる。
×：直線で描いたインクにハジキが見られない。
[Non-staining]
Temperature: 23 ° C., Relative humidity: 50% After peeling off the protective film from the protective film-formed super water-repellent lens stored for 3 months, the lens was applied with an oil-based marker (marker ink (black) manufactured by Teranishi Kagaku Kogyo Co., Ltd.). When a line was drawn on the lens with , repelling of the ink was observed and evaluated as follows. Although the lens surface before the protective film is formed repels oil-based marker ink, the water repellency decreases if contaminants remain on the lens surface. For the non-staining property, ◯ or △ was regarded as acceptable.
◯: The ink drawn with a straight line becomes dot-like.
Δ: The ink drawn with a straight line becomes a thin line.
x: No cissing is observed in ink drawn in a straight line.
表１、２の結果から、実施例１～１９の樹脂組成物はいずれも超撥水レンズに対する塗工性が良好であった。また、実施例１～１９の樹脂組成物を硬化させて得られた保護膜は温度：２３℃、相対湿度：５０％環境下で３ヶ月保管後においても、超撥水レンズに対する適度な密着性を有しており、保持力、剥離性及び強靭性が高いレベルで並立されていた。さらに、保護膜剥離後の超撥水レンズの撥水性低下も抑えられており、非汚染性にも優れていた。 From the results in Tables 1 and 2, all of the resin compositions of Examples 1 to 19 had good coatability for super water-repellent lenses. In addition, the protective films obtained by curing the resin compositions of Examples 1 to 19 had moderate adhesion to the superhydrophobic lens even after being stored for 3 months in an environment at a temperature of 23°C and a relative humidity of 50%. It had a high level of holding power, peelability and toughness. Furthermore, the decrease in water repellency of the superhydrophobic lens after peeling off the protective film was suppressed, and the non-staining property was also excellent.
一方、表３の結果から、比較例１、２では、（Ａ）成分の重量平均分子量が過小、又は過大であるため、得られた保護膜の超撥水レンズに対する保持力、或いは強靭性が不足していた。比較例３、４では、（Ｂ）成分の含有量が過少、又は過多であるため、得られた保護膜の超撥水レンズからの剥離性、或いは強靭性が不足していた。比較例５では、（Ｃ）成分の含有量が過少であるため、得られた保護膜の超撥水レンズに対する保持力、強靭性及び非汚染性が不足していた。比較例６では、（Ｃ）成分の含有量が過多であるため、得られた保護膜の非汚染性が不足していた。比較例７、９、１０では、（Ｄ）成分の含有量が過少、（Ｄ）成分としてシリコン系界面活性剤を使用、或いは（Ｄ）成分を含有していないため、超撥水レンズへの塗布性が不足していた。比較例８では（Ｄ）成分の含有量が過多であるため、得られた保護膜の非汚染性が不足していた。 On the other hand, from the results in Table 3, in Comparative Examples 1 and 2, the weight-average molecular weight of the component (A) was too small or too large, so that the resulting protective film had poor holding power or toughness for the superhydrophobic lens. was lacking. In Comparative Examples 3 and 4, the content of the component (B) was too little or too much, so that the resulting protective film lacked releasability from the superhydrophobic lens or lacked toughness. In Comparative Example 5, since the content of component (C) was too small, the obtained protective film lacked holding power, toughness, and non-staining properties for superhydrophobic lenses. In Comparative Example 6, since the content of the component (C) was excessive, the non-staining property of the obtained protective film was insufficient. In Comparative Examples 7, 9, and 10, the content of the component (D) was too small, the silicone-based surfactant was used as the component (D), or the component (D) was not contained. The coatability was insufficient. In Comparative Example 8, since the content of the component (D) was excessive, the non-staining property of the obtained protective film was insufficient.
Claims (2)
前記（Ａ）成分１００質量部に対して、（Ｂ）成分を０．５～３０質量部、（Ｃ）成分を０．１～２５質量部、（Ｄ）成分を０．１～２５質量部含むことを特徴とする、撥水レンズ保護膜用樹脂組成物。
（Ａ）成分：重量平均分子量が２５０～３０，０００である多官能（メタ）アクリレート
（Ｂ）成分：多官能チオール化合物
（Ｃ）成分：光重合開始剤
（Ｄ）成分：重量平均分子量が２５，０００～１００，０００であり、フッ素系セグメントと非フッ素系セグメントからなるブロック共重合体 A resin composition characterized by containing the following components (A) to (D),
Per 100 parts by mass of component (A), 0.5 to 30 parts by mass of component (B), 0.1 to 25 parts by mass of component (C), and 0.1 to 25 parts by mass of component (D) A resin composition for a water-repellent lens protective film, comprising:
(A) component: polyfunctional (meth) acrylate having a weight average molecular weight of 250 to 30,000 (B) component: polyfunctional thiol compound (C) component: photopolymerization initiator (D) component: weight average molecular weight of 25 ,000 to 100,000 and a block copolymer consisting of a fluorine-based segment and a non-fluorine-based segment
A method for protecting a water-repellent lens by providing a protective film formed by coating and curing the resin composition for a water-repellent lens protective film according to claim 1 on the water-repellent lens.
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| JP2021126788A JP2023021736A (en) | 2021-08-02 | 2021-08-02 | Resin composition for water-repellent lens protective film and method for protecting water-repellent lens |
| PCT/JP2021/036003 WO2022071446A1 (en) | 2020-09-30 | 2021-09-29 | Resin composition for water-repellent lens protective films, and method for protecting water-repellent lens |
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| JP2021126788A JP2023021736A (en) | 2021-08-02 | 2021-08-02 | Resin composition for water-repellent lens protective film and method for protecting water-repellent lens |
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