TW201641577A - Active energy ray-curable resin composition and article - Google Patents
Active energy ray-curable resin composition and article Download PDFInfo
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- TW201641577A TW201641577A TW105109149A TW105109149A TW201641577A TW 201641577 A TW201641577 A TW 201641577A TW 105109149 A TW105109149 A TW 105109149A TW 105109149 A TW105109149 A TW 105109149A TW 201641577 A TW201641577 A TW 201641577A
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- acrylate
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- 239000011342 resin composition Substances 0.000 title claims abstract description 114
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000006082 mold release agent Substances 0.000 claims abstract description 33
- 239000003999 initiator Substances 0.000 claims abstract description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 137
- -1 alkylene glycol Chemical compound 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 32
- 229910019142 PO4 Inorganic materials 0.000 claims description 26
- 239000010452 phosphate Substances 0.000 claims description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 claims description 15
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 125000002723 alicyclic group Chemical group 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000047 product Substances 0.000 description 74
- 239000011148 porous material Substances 0.000 description 57
- 239000000758 substrate Substances 0.000 description 57
- 239000011347 resin Substances 0.000 description 33
- 229920005989 resin Polymers 0.000 description 33
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 31
- 229910052782 aluminium Inorganic materials 0.000 description 30
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 30
- 239000010410 layer Substances 0.000 description 27
- 239000000463 material Substances 0.000 description 25
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 24
- 230000000694 effects Effects 0.000 description 23
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 19
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000005871 repellent Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 238000002048 anodisation reaction Methods 0.000 description 9
- 239000008151 electrolyte solution Substances 0.000 description 8
- 235000006408 oxalic acid Nutrition 0.000 description 8
- 238000012546 transfer Methods 0.000 description 8
- 229920002799 BoPET Polymers 0.000 description 7
- 230000003667 anti-reflective effect Effects 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- 238000007743 anodising Methods 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 3
- 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 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 3
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 238000005401 electroluminescence Methods 0.000 description 3
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 150000002222 fluorine compounds Chemical class 0.000 description 3
- 239000004973 liquid crystal related substance Substances 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
- WRKCIHRWQZQBOL-UHFFFAOYSA-N octyl dihydrogen phosphate Chemical compound CCCCCCCCOP(O)(O)=O WRKCIHRWQZQBOL-UHFFFAOYSA-N 0.000 description 3
- 125000005702 oxyalkylene group Chemical group 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 229950000688 phenothiazine Drugs 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- VXRAAUKUZQYZRW-UHFFFAOYSA-N 3'-N'-Acetylfusarochromanone Chemical compound O1C(C)(C)CC(=O)C2=C(N)C(C(=O)CC(CO)NC(=O)C)=CC=C21 VXRAAUKUZQYZRW-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- 240000002853 Nelumbo nucifera Species 0.000 description 2
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 2
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000004113 cell culture Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- GJBXIPOYHVMPQJ-UHFFFAOYSA-N hexadecane-1,16-diol Chemical compound OCCCCCCCCCCCCCCCCO GJBXIPOYHVMPQJ-UHFFFAOYSA-N 0.000 description 2
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- 239000004611 light stabiliser Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000747 poly(lactic acid) Polymers 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
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- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-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
- PJYUCLOYEILMHQ-UHFFFAOYSA-N 1,2-bis(1-phenylethyl)-10h-phenothiazine Chemical compound C=1C=C2SC3=CC=CC=C3NC2=C(C(C)C=2C=CC=CC=2)C=1C(C)C1=CC=CC=C1 PJYUCLOYEILMHQ-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
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 1
- SIJSIIFAIYLAQW-UHFFFAOYSA-N 1-tert-butyl-9h-fluorene Chemical compound C12=CC=CC=C2CC2=C1C=CC=C2C(C)(C)C SIJSIIFAIYLAQW-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- CZZVAVMGKRNEAT-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;3-hydroxy-2,2-dimethylpropanoic acid Chemical compound OCC(C)(C)CO.OCC(C)(C)C(O)=O CZZVAVMGKRNEAT-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- SITYOOWCYAYOKL-UHFFFAOYSA-N 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(3-dodecoxy-2-hydroxypropoxy)phenol Chemical compound OC1=CC(OCC(O)COCCCCCCCCCCCC)=CC=C1C1=NC(C=2C(=CC(C)=CC=2)C)=NC(C=2C(=CC(C)=CC=2)C)=N1 SITYOOWCYAYOKL-UHFFFAOYSA-N 0.000 description 1
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 1
- DBAMLKZZDQYENY-UHFFFAOYSA-N 2-[diphenylphosphoryl(phenyl)methyl]-1,3,5-trimethylbenzene Chemical compound CC1=C(C(C2=CC=CC=C2)P(C2=CC=CC=C2)(C2=CC=CC=C2)=O)C(=CC(=C1)C)C DBAMLKZZDQYENY-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
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical compound OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-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
- SDQROPCSKIYYAV-UHFFFAOYSA-N 2-methyloctane-1,8-diol Chemical compound OCC(C)CCCCCCO SDQROPCSKIYYAV-UHFFFAOYSA-N 0.000 description 1
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- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- 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 1
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- 238000004020 luminiscence type Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 239000011259 mixed solution Substances 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
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl 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])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- UKASIOIEWZDBIT-UHFFFAOYSA-N phenyl-(2,3,4-trimethylphenyl)methanone Chemical compound CC1=C(C)C(C)=CC=C1C(=O)C1=CC=CC=C1 UKASIOIEWZDBIT-UHFFFAOYSA-N 0.000 description 1
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 1
- OJNNAJJFLWBPRS-UHFFFAOYSA-N phenyl-[(2,4,6-trimethylphenyl)methyl]-[(2,4,6-trimethylphenyl)methylidene]phosphanium Chemical compound CC1=C(C=P(C2=CC=CC=C2)=CC2=C(C=C(C=C2C)C)C)C(=CC(=C1)C)C OJNNAJJFLWBPRS-UHFFFAOYSA-N 0.000 description 1
- 150000004713 phosphodiesters Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 125000001557 phthalyl group Chemical group C(=O)(O)C1=C(C(=O)*)C=CC=C1 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000007858 starting material 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
- 239000010959 steel Substances 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
- Surface Treatment Of Optical Elements (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本發明是有關於一種適合於形成微細凹凸（奈米凹凸）結構體的活性能量線硬化性樹脂組成物、含有該活性能量線硬化性樹脂組成物的壓印用原料、及具有使用該活性能量線硬化性樹脂組成物所形成的微細凹凸結構的物品。The present invention relates to an active energy ray-curable resin composition suitable for forming a fine uneven (nano-convex) structure, an imprint material containing the active energy ray-curable resin composition, and the use of the active energy An article having a fine uneven structure formed by a linear curable resin composition.
已知奈米尺寸的微細的凹凸有規則地配置於表面上的微細凹凸結構體藉由連續的折射率的變化而顯現抗反射性能。此種微細凹凸結構通常被稱為蛾眼（moth eye）結構。另外，該微細凹凸結構顯現與具備微細的凹凸結構的荷葉所顯示出的超撥水性能（蓮花效應（Lotus effect））相同的效果亦為人所知。It is known that the fine uneven structure in which the fine irregularities of the nanometer size are regularly arranged on the surface exhibits antireflection performance by a change in the continuous refractive index. Such a fine uneven structure is generally called a moth eye structure. Further, the fine concavo-convex structure is also known to have the same effect as the super-water-repellent property (Lotus effect) exhibited by the lotus leaf having the fine concavo-convex structure.
作為表面具有微細凹凸結構的物品的製造方法，例如提出有下述方法： （i）使用表面具有微細凹凸結構的反轉結構的壓模，對熱塑性樹脂進行射出成形或壓製成形，而將微細凹凸結構轉印至熱塑性樹脂成形體的表面上的方法； （ii）將活性能量線硬化性樹脂組成物填充至表面具有微細凹凸結構的反轉結構的壓模與透明基材之間，藉由活性能量線的照射來使其硬化後，剝離壓模，而將微細凹凸結構轉印至硬化物上的方法；以及 （iii）將活性能量線硬化性樹脂組成物填充至所述壓模與透明基材之間後，剝離壓模，而將微細凹凸結構轉印至活性能量線硬化性樹脂組成物上，其後，藉由活性能量線的照射來使活性能量線硬化性樹脂組成物硬化的方法。As a method for producing an article having a fine uneven structure on the surface, for example, a method is proposed in which: (i) a thermoplastic resin is subjected to injection molding or press molding using a stamper having a reversed structure having a fine uneven structure on the surface, and fine irregularities are formed. a method of transferring the structure onto the surface of the thermoplastic resin molded body; (ii) filling the active energy ray-curable resin composition between the stamper having an inverted structure having a fine uneven structure on the surface and the transparent substrate, by active a method of transferring the fine concavo-convex structure to the cured product after the irradiation of the energy ray is hardened, and (iii) filling the active energy ray-curable resin composition to the stamper and the transparent base After the material is peeled off between the materials, the fine uneven structure is transferred onto the active energy ray-curable resin composition, and then the active energy ray-curable resin composition is cured by irradiation with the active energy ray. .
該些方法之中，若考慮微細凹凸結構的轉印性、表面組成的自由度，則適合的是（ii）的方法。該方法是特別適合於使用可連續生產的傳送帶狀或輥狀的壓模的情況、且生產性優異的方法。Among these methods, the method of (ii) is suitable in consideration of the transferability of the fine uneven structure and the degree of freedom of the surface composition. This method is particularly suitable for a case where a continuously produced belt-shaped or roll-shaped stamper is used, and the method is excellent in productivity.
當微細凹凸的鄰接的凸部或凹部為可見光的波長以下的間隔時，微細凹凸結構顯現良好的抗反射性能。但是，與表面平滑、且藉由硬塗等而進行了耐磨耗性處理的成形體相比，具有此種結構的微細凹凸結構體的耐擦傷性欠佳，於使用過程中的耐久性方面存在問題。另外，若用於製作微細凹凸結構體的樹脂組成物的硬化物不十分牢固，則於自鑄模中進行脫模時容易產生突起彼此貼近的現象、或因熱而容易產生突起彼此貼近的現象。When the adjacent convex portions or concave portions of the fine unevenness are at intervals equal to or less than the wavelength of visible light, the fine uneven structure exhibits excellent antireflection performance. However, the fine uneven structure having such a structure has poor scratch resistance as compared with a molded article which has a smooth surface and is subjected to abrasion resistance treatment by hard coating or the like, and has durability in use. There is a problem. In addition, when the cured product of the resin composition for producing the fine concavo-convex structure is not sufficiently strong, the protrusions tend to be close to each other when the mold is released from the mold, or the protrusions are likely to be close to each other due to heat.
因此，提出有如下的微細凹凸結構體或用於形成微細凹凸結構的樹脂組成物，所述微細凹凸結構體於為了形成耐久性或強度高的微細凹凸結構，而藉由活性能量線的照射來使樹脂組成物硬化時，轉印壓模的反轉微細凹凸結構而形成微細凹凸結構。Therefore, there has been proposed a fine concavo-convex structure or a resin composition for forming a fine concavo-convex structure which is irradiated with active energy rays in order to form a fine uneven structure having high durability or strength. When the resin composition is cured, the fine uneven structure of the transfer stamper is reversed to form a fine uneven structure.
例如於專利文獻1中記載有將經最密填充的二氧化矽微粒子作為鑄模來製作具有可見光的波長以下的凸部（凹部）間隔的微細凹凸結構，或作為形成該微細凹凸結構的樹脂組成物，記載有含有三羥甲基丙烷三(甲基)丙烯酸酯等每分子量的雙鍵多的多官能單體的紫外線硬化性樹脂組成物。For example, Patent Document 1 discloses a fine concavo-convex structure in which a most densely packed ceria fine particle is used as a mold to form a convex portion (concave portion) having a wavelength of visible light or less, or a resin composition forming the fine concavo-convex structure. An ultraviolet curable resin composition containing a polyfunctional monomer having a large number of double bonds per molecular weight, such as trimethylolpropane tri(meth)acrylate, is described.
另外，於專利文獻2中揭示有一種含有具有微細凹凸的硬塗層的薄膜，並記載有該硬塗層較佳為於依據JISK5400的鉛筆硬度試驗中顯示出「H」以上的硬度，而且，作為形成該硬塗層的樹脂，記載有含有二季戊四醇六丙烯酸酯、二季戊四醇五丙烯酸酯、季戊四醇四丙烯酸酯等每分子量的雙鍵數多的多官能單體的紫外線硬化性樹脂組成物。Further, Patent Document 2 discloses a film containing a hard coat layer having fine unevenness, and it is described that the hard coat layer preferably exhibits a hardness of "H" or more in a pencil hardness test according to JIS K5400, and An ultraviolet curable resin composition containing a polyfunctional monomer having a large number of double bonds per molecular weight, such as dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, or pentaerythritol tetraacrylate, is described as a resin for forming the hard coat layer.
另外，作為對於形成微細凹凸結構較佳的樹脂組成物，已知有以下者： （1）將丙烯酸胺基甲酸酯等丙烯酸酯寡聚物與脫模劑作為必需成分的光硬化性樹脂組成物（專利文獻3）； （2）包含乙氧基化雙酚A二(甲基)丙烯酸酯等(甲基)丙烯酸酯、N-乙烯基吡咯啶酮等反應性稀釋劑、光聚合起始劑及氟系界面活性劑的光硬化性樹脂組成物（專利文獻4）；以及 （3）包含三羥甲基丙烷三(甲基)丙烯酸酯等多官能(甲基)丙烯酸酯、光聚合起始劑及聚醚改質矽油等調平劑的紫外線硬化性樹脂組成物（專利文獻1）。 [現有技術文獻] [專利文獻]In addition, as a resin composition which is preferable for forming a fine uneven structure, the following are known: (1) A photocurable resin containing an acrylate oligomer such as acrylamide and a releasing agent as an essential component (Patent Document 3); (2) Containing reactive diluent such as (meth) acrylate such as ethoxylated bisphenol A di(meth)acrylate or N-vinylpyrrolidone, photopolymerization initiation Photocurable resin composition of a solvent and a fluorine-based surfactant (Patent Document 4); and (3) a polyfunctional (meth)acrylate such as trimethylolpropane tri(meth)acrylate, photopolymerization An ultraviolet curable resin composition of a leveling agent such as a starter and a polyether modified eucalyptus oil (Patent Document 1). [Prior Art Document] [Patent Literature]
[專利文獻1]日本專利特開2000-71290號公報 [專利文獻2]日本專利特開2002-107501號公報 [專利文獻3]日本專利第4156415號公報 [專利文獻4]日本專利特開2007-84625號公報[Patent Document 1] Japanese Patent Laid-Open Publication No. 2000-71290 [Patent Document 2] Japanese Patent Laid-Open Publication No. JP-A-2002-107501 (Patent Document 3) Japanese Patent No. 41564415 [Patent Document 4] Japanese Patent Laid-Open No. 2007- Bulletin No. 84625
[發明所欲解決之課題] 但是，專利文獻1、專利文獻2中所記載的微細凹凸結構體均為交聯密度高且彈性係數高的硬化物，但未必滿足耐擦傷性。另外，即便是於鉛筆硬度試驗中顯示出「H」以上的硬度的硬化樹脂，尤其於微細凹凸結構體的情況下，亦存在微細突起折斷或彎曲而導致抗反射性能受損的情況，其使用用途受到限定。另外，該些微細凹凸結構體並非微細凹凸結構表面發揮充分的撥水性者。[Problems to be Solved by the Invention] The fine concavo-convex structure described in Patent Document 1 and Patent Document 2 is a cured product having a high crosslinking density and a high elastic modulus, but does not necessarily satisfy the scratch resistance. In addition, even in the case of the fine uneven structure, the hardened resin which exhibits a hardness of "H" or more in the pencil hardness test may be broken or bent, and the antireflection performance may be impaired. Use is limited. Further, the fine uneven structure body does not exhibit sufficient water repellency on the surface of the fine uneven structure.
另一方面，為了對樹脂成形體賦予撥水性而使用矽酮化合物或氟化合物的方法已為人所知。但是，通常藉由矽酮化合物或氟化合物來發揮撥水性者與用於活性能量線硬化性樹脂組成物的通常的多官能(甲基)丙烯酸酯或(甲基)丙烯酸胺基甲酸酯等的相容性低，對於要求透明性的硬塗的應用受到限定。另外，本申請案發明者等人的研究的結果，已明確當使用可對微細凹凸結構表面賦予撥水性的樹脂組成物時，自壓模的剝離力大，難以連續生產成形體。On the other hand, a method of using an anthrone compound or a fluorine compound in order to impart water repellency to a resin molded body is known. However, usually, an oxime compound or a fluorine compound is used as a general polyfunctional (meth) acrylate or (meth) acrylate urethane for use in an active energy ray-curable resin composition. The compatibility is low and the application of hard coating requiring transparency is limited. As a result of the investigation by the inventors of the present application, it has been clarified that when a resin composition capable of imparting water repellency to the surface of the fine uneven structure is used, the peeling force from the stamper is large, and it is difficult to continuously produce the molded body.
本發明的主要目的在於提供一種具有由微細凹凸結構所產生的抗反射功能，並具有高撥水性與耐擦傷性的物品，以及可形成具有由微細凹凸結構所產生的抗反射功能、並具有高撥水性與耐擦傷性、且容易自壓模剝離的硬化物的活性能量線硬化性樹脂組成物。 [解決課題之手段]SUMMARY OF THE INVENTION A primary object of the present invention is to provide an article having an antireflection function produced by a fine uneven structure and having high water repellency and scratch resistance, and capable of forming an antireflection function by a fine uneven structure and having a high An active energy ray-curable resin composition of a cured product which is water-repellent and scratch-resistant and which is easily peeled off from a stamper. [Means for solving the problem]
根據本發明的一形態，提供一種物品，其於表面具有多個凸部， 所述多個凸部的鄰接的凸部彼此的平均間隔為400 nm以下， 所述多個凸部包含活性能量線硬化性樹脂組成物的硬化物， 所述物品的具有所述多個凸部的部分的水接觸角度為80度以上， 所述活性能量線硬化樹脂性組成物含有聚合性成分（P）、光聚合起始劑（E）及內部脫模劑（F），且含有磷酸單烷基酯及磷酸二烷基酯的至少一者作為所述內部脫模劑（F）。 根據本發明的另一形態，提供一種活性能量線硬化性樹脂組成物，其用於藉由壓印法來形成表面具有鄰接的凸部彼此的平均間隔為400 nm以下的多個凸部的微細凹凸結構， 所述活性能量線硬化性樹脂組成物至少含有聚合性成分（P）、光聚合起始劑（E）及內部脫模劑（F）， 相對於所述聚合性成分（P）的總量100質量%，含有50質量%以上、100質量%以下的作為碳數6以上的烷二醇與(甲基)丙烯酸的酯化物的烷二醇二(甲基)丙烯酸酯作為聚合性成分（A）， 相對於所述聚合性成分（P）的總量100質量%，具有脂環結構的聚合性成分的含量未滿17質量%，且 內部脫模劑（F）含有磷酸單烷基酯及磷酸二烷基酯的至少一者。 根據本發明的另一形態，提供一種物品，其包含所述活性能量線硬化性樹脂組成物的硬化物，於表面具有如下的微細凹凸結構，所述微細凹凸結構於表面具有鄰接的凸部彼此的平均間隔為400 nm以下的多個凸部，且 所述微細凹凸結構的表面上的水的接觸角度為80度以上。 [發明的效果]According to an aspect of the present invention, there is provided an article having a plurality of convex portions on a surface thereof, wherein adjacent convex portions of the plurality of convex portions have an average interval of 400 nm or less, and the plurality of convex portions include active energy rays a cured product of the curable resin composition, wherein a water contact angle of the portion having the plurality of convex portions of the article is 80 degrees or more, and the active energy ray-curable resin composition contains a polymerizable component (P) and light. The polymerization initiator (E) and the internal mold release agent (F) contain at least one of a monoalkyl phosphate and a dialkyl phosphate as the internal mold release agent (F). According to another aspect of the present invention, there is provided an active energy ray-curable resin composition for forming a fine portion of a plurality of convex portions having an average interval of 400 nm or less between adjacent convex portions on a surface by an imprint method The active energy ray-curable resin composition contains at least a polymerizable component (P), a photopolymerization initiator (E), and an internal mold release agent (F), and the polymerizable component (P) 100% by mass of the total amount, and 50% by mass or more and 100% by mass or less of the alkylene glycol di(meth)acrylate which is an esterified product of a carbon number of 6 or more and an alkyl (meth)acrylic acid ester as a polymerizable component (A), the content of the polymerizable component having an alicyclic structure is less than 17% by mass based on 100% by mass of the total amount of the polymerizable component (P), and the internal mold release agent (F) contains a monoalkyl phosphate At least one of an ester and a dialkyl phosphate. According to another aspect of the present invention, there is provided an article comprising a cured product of the active energy ray-curable resin composition having a fine concavo-convex structure having a convex portion on the surface adjacent to each other on a surface The average interval is a plurality of convex portions of 400 nm or less, and the contact angle of water on the surface of the fine uneven structure is 80 degrees or more. [Effects of the Invention]
根據本發明的實施形態，可提供一種具有由微細凹凸結構所產生的抗反射功能，並具有高撥水性與耐擦傷性的物品，以及可形成具有由微細凹凸結構所產生的抗反射功能、並具有高撥水性與耐擦傷性、且容易自壓模剝離的硬化物的活性能量線硬化性樹脂組成物。According to the embodiment of the present invention, it is possible to provide an article having an antireflection function by a fine uneven structure and having high water repellency and scratch resistance, and an antireflection function which is formed by a fine uneven structure, and An active energy ray-curable resin composition having a cured product having high water repellency and scratch resistance and easily peeled off from a stamper.
本發明的實施形態的活性能量線硬化性樹脂組成物（X）含有聚合性成分（P）、光聚合起始劑（E）及內部脫模劑（F），藉由對其照射活性能量線而進行聚合反應，並進行硬化。The active energy ray-curable resin composition (X) according to the embodiment of the present invention contains a polymerizable component (P), a photopolymerization initiator (E), and an internal mold release agent (F), and is irradiated with an active energy ray. The polymerization reaction is carried out and hardening is carried out.
該活性能量線硬化性樹脂組成物含有作為必需成分的磷酸單酯及磷酸二酯的至少一者作為內部脫模劑（F）。The active energy ray-curable resin composition contains at least one of a phosphoric acid monoester and a phosphoric acid diester as an essential component as an internal mold release agent (F).
聚合性成分（P）較佳為含有矽酮(甲基)丙烯酸酯及(甲基)丙烯酸烷基酯的至少一者作為聚合性成分（B）。The polymerizable component (P) preferably contains at least one of an anthrone (meth) acrylate and an alkyl (meth) acrylate as the polymerizable component (B).
另外，聚合性成分（P）較佳為相對於聚合性成分（P）的總量100質量%，含有50質量%以上、100質量%以下的藉由費多斯（Fedors）法所計算的溶解度參數值（solubility parameter，SP值）為19.6以下的聚合性成分作為聚合性成分（A）。另外，聚合性成分（P）較佳為含有作為碳數6以上的烷二醇與(甲基)丙烯酸的酯化物的烷二醇二(甲基)丙烯酸酯作為聚合性成分（A），更佳為該烷二醇二(甲基)丙烯酸酯的藉由費多斯法所計算的SP值為19.6以下。另外，聚合性成分（P）較佳為含有所述聚合性成分（A）與作為矽酮(甲基)丙烯酸酯及(甲基)丙烯酸烷基酯的至少一者的聚合性成分（B）。In addition, the polymerizable component (P) is preferably 100% by mass based on the total amount of the polymerizable component (P), and contains 50% by mass or more and 100% by mass or less of the solubility calculated by the Fedors method. A polymerizable component having a parameter value (solubility parameter, SP value) of 19.6 or less is used as the polymerizable component (A). In addition, the polymerizable component (P) is preferably an alkanediol di(meth)acrylate containing an esterified product of an alkylene glycol having 6 or more carbon atoms and (meth)acrylic acid as a polymerizable component (A). Preferably, the SP value of the alkanediol di(meth)acrylate calculated by the Ferdos method is 19.6 or less. Further, the polymerizable component (P) is preferably a polymerizable component (B) containing the polymerizable component (A) and at least one of an anthrone (meth)acrylate and an alkyl (meth)acrylate. .
聚合性成分（P）較佳為進而含有作為分子內具有3個以上的(甲基)丙烯醯基的多官能(甲基)丙烯酸酯的聚合性成分（C），視需要可含有其他聚合性成分（D）。另外，該活性能量線硬化性樹脂組成物視需要亦可含有其他成分（G）。The polymerizable component (P) preferably further contains a polymerizable component (C) which is a polyfunctional (meth)acrylate having three or more (meth)acrylonium groups in the molecule, and may contain other polymerizability as necessary. Ingredient (D). Further, the active energy ray-curable resin composition may contain other components (G) as needed.
當活性能量線硬化性樹脂組成物（X）的硬化物的表面具有微細凹凸結構時，重要的是調整聚合性成分（P）的組成來使硬化物變成適當的硬度。若硬化物過硬，則存在微細凹凸結構表面的耐擦傷性變低的傾向。另一方面，若硬化物過軟，則存在難以維持微細凹凸結構，多個凸部彼此合一的情況。When the surface of the cured product of the active energy ray-curable resin composition (X) has a fine uneven structure, it is important to adjust the composition of the polymerizable component (P) to make the cured product into an appropriate hardness. When the cured product is too hard, the scratch resistance of the surface of the fine uneven structure tends to be low. On the other hand, when the cured product is too soft, it may be difficult to maintain the fine uneven structure, and the plurality of convex portions may be combined with each other.
較佳為含有磷酸單烷基酯及磷酸二烷基酯的至少一者作為內部脫模劑（F）。It is preferable to contain at least one of a monoalkyl phosphate and a dialkyl phosphate as an internal mold release agent (F).
相對於聚合性成分（P）的總量100質量份，內部脫模劑（F）的含有率可設定成0.01質量份～2.0質量份的範圍。就獲得充分的脫模效果的觀點而言，較佳為0.05質量份以上，更佳為0.1質量份以上。若內部脫模劑（F）的含有率過大，則存在內部脫模劑（F）自活性能量線硬化性樹脂組成物分離或析出的情況、或者內部脫模劑（F）自活性能量線硬化性樹脂組成物的硬化物中滲出的情況。內部脫模劑（F）的含有率較佳為2.0質量份以下，更佳為1.0質量份以下。The content of the internal mold release agent (F) can be set in the range of 0.01 part by mass to 2.0 parts by mass based on 100 parts by mass of the total amount of the polymerizable component (P). From the viewpoint of obtaining a sufficient release effect, it is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more. When the content of the internal mold release agent (F) is too large, the internal mold release agent (F) is separated or precipitated from the active energy ray-curable resin composition, or the internal mold release agent (F) is hardened by the active energy ray. The case where the cured product of the resin composition oozes out. The content of the internal mold release agent (F) is preferably 2.0 parts by mass or less, more preferably 1.0 part by mass or less.
相對於聚合性成分（P）的總量100質量份，光聚合起始劑（E）的含有率可設定成0.01質量份～10質量份的範圍。The content ratio of the photopolymerization initiator (E) can be set to be in the range of 0.01 part by mass to 10 parts by mass based on 100 parts by mass of the total amount of the polymerizable component (P).
較佳為相對於聚合性成分（P）的總量100質量%， 聚合性成分（A）的含有率為50質量%～99.5質量%， 聚合性成分（B）的含有率為0.5質量%～50質量%。The content of the polymerizable component (A) is preferably 50% by mass to 99.5% by mass, and the content of the polymerizable component (B) is 0.5% by mass to 100% by mass based on the total amount of the polymerizable component (P). 50% by mass.
當聚合性成分（P）進而含有聚合性成分（C）時， 較佳為相對於聚合性成分（P）的總量100質量%， 聚合性成分（A）的含有率為50質量%～89.5質量%， 聚合性成分（B）的含有率為0.5質量%～40質量%， 聚合性成分（C）的含有率為10質量%～49.5質量%。When the polymerizable component (P) further contains the polymerizable component (C), it is preferably 100% by mass based on the total amount of the polymerizable component (P), and the content of the polymerizable component (A) is 50% by mass to 89.5. The content% of the polymerizable component (B) is 0.5% by mass to 40% by mass, and the content of the polymerizable component (C) is 10% by mass to 49.5% by mass.
聚合性成分（B）的磷酸單酯較佳為非氧基伸烷基化矽酮(甲基)丙烯酸酯。另外，聚合性成分（B）的(甲基)丙烯酸烷基酯較佳為烷基的碳數為8～22的(甲基)丙烯酸烷基酯。The phosphoric acid monoester of the polymerizable component (B) is preferably a non-oxyalkylene alkyl ketone (meth) acrylate. Further, the alkyl (meth)acrylate of the polymerizable component (B) is preferably an alkyl (meth)acrylate having an alkyl group having 8 to 22 carbon atoms.
相對於聚合性成分（P）的總量100質量%， 具有聚氧基伸烷基骨架的聚合性成分的含有率較佳為未滿10質量%，更佳為5質量%以下。另外，相對於聚合性成分（P）的總量100質量%，具有脂環結構的聚合性成分的含量較佳為未滿17質量%，更佳為10質量%以下。The content of the polymerizable component having a polyoxyalkylene group skeleton is preferably less than 10% by mass, and more preferably 5% by mass or less, based on 100% by mass of the total amount of the polymerizable component (P). In addition, the content of the polymerizable component having an alicyclic structure is preferably less than 17% by mass, and more preferably 10% by mass or less, based on 100% by mass of the total amount of the polymerizable component (P).
根據本發明的另一實施形態，可提供一種含有所述活性能量線硬化性樹脂組成物的壓印用原料。According to another embodiment of the present invention, a material for imprinting comprising the active energy ray-curable resin composition can be provided.
根據本發明的另一實施形態，可提供一種含有所述活性能量線硬化性樹脂組成物的硬化物的物品。作為該硬化物，可包含形成於基材上的硬化樹脂層。另外，可於該硬化物的表面具有包含多個凸部的微細凹凸結構。於該微細凹凸結構中，鄰接的凸部彼此的平均間隔較佳為400 nm以下。另外，微細凹凸結構的表面上的水的接觸角度較佳為80度以上，更佳為135度以上。According to another embodiment of the present invention, an article containing a cured product of the active energy ray-curable resin composition can be provided. As the cured product, a cured resin layer formed on a substrate may be included. Further, a fine uneven structure including a plurality of convex portions may be provided on the surface of the cured product. In the fine uneven structure, the average interval between adjacent convex portions is preferably 400 nm or less. Further, the contact angle of water on the surface of the fine uneven structure is preferably 80 degrees or more, more preferably 135 degrees or more.
本發明的實施形態的物品可應用於顯示器構件、抗反射物品、撥水薄膜。The article of the embodiment of the present invention can be applied to a display member, an antireflection article, and a water-repellent film.
以下，進一步說明本發明的適宜的實施形態。Hereinafter, preferred embodiments of the present invention will be further described.
[內部脫模劑（F）] 內部脫模劑（F）含有磷酸單酯及磷酸二酯的至少一者。[Internal Release Agent (F)] The internal release agent (F) contains at least one of a phosphoric acid monoester and a phosphoric acid diester.
已知於將陽極氧化多孔氧化鋁用作壓模，使活性能量線硬化性樹脂組成物硬化來將微細凹凸結構轉印至硬化物上的方法中，作為添加至活性能量線硬化性樹脂組成物中的內部脫模劑，使用磷酸酯化合物。進而，已知磷酸酯化合物之中，作為（聚）氧基伸烷基烷基磷酸化合物且作為磷酸三酯化合物者的脫模性優異。It is known that the anodized porous alumina is used as a stamper to cure the active energy ray-curable resin composition to transfer the fine uneven structure to the cured product, and is added as an active energy ray-curable resin composition. In the internal mold release agent, a phosphate compound is used. Further, among the phosphate compounds, a (poly)oxyalkylalkylphosphoric acid compound is known, and the release property is excellent as a phosphate triester compound.
但是，作為新的課題，本發明者等人發現若作為烷二醇二(甲基)丙烯酸酯的聚合性成分（A）為主成分、且氧基伸烷基骨架成分的含量少的活性能量線硬化性樹脂組成物將作為（聚）氧基伸烷基烷基磷酸化合物且作為磷酸三酯化合物者用作內部脫模劑，則硬化後的自壓模的剝離力大，另外，如聚合性成分（B）般的撥水性賦予成分的效果亦得不到充分發揮。However, as a new subject, the inventors of the present invention found that the polymerizable component (A) as the alkanediol di(meth)acrylate is a main component and the content of the alkyl group component is small. When the curable resin composition is used as a (poly)oxyalkylalkylphosphoric acid compound and used as an internal mold release agent as a phosphate triester compound, the peeling force of the self-pressing mold after curing is large, and a polymerizable component is also contained. (B) The effect of the water-repellent imparting component is not fully exerted.
因此，本發明者等人進行努力研究的結果，發現使用含有磷酸單酯及/或磷酸二酯的內部脫模劑（F）有效，作為磷酸物單酯，特別有效的是磷酸單烷基酯，作為磷酸二酯，特別有效的是磷酸二烷基酯。藉由使用該內部脫模劑（F），可充分減小將活性能量線硬化性樹脂組成物（X）的硬化物自壓模進行脫模時的剝離力，所獲得的表面具有微細凹凸結構的物品可發揮優異的撥水性能。所獲得的具有微細凹凸結構的物品較佳為微細凹凸結構的表面的水接觸角度為80度以上，更佳為100度以上，進而更佳為130度以上，特佳為135度以上。Therefore, as a result of intensive studies by the present inventors, it has been found that an internal mold release agent (F) containing a phosphoric acid monoester and/or a phosphoric acid diester is effective, and as a phosphate monoester, a monoalkyl phosphate is particularly effective. Particularly useful as a phosphodiester is a dialkyl phosphate. By using the internal mold release agent (F), the peeling force when the cured product of the active energy ray-curable resin composition (X) is released from the stamper can be sufficiently reduced, and the obtained surface has a fine uneven structure. The item can perform excellent water repellency. The article having the fine uneven structure is preferably a water contact angle of the surface of the fine uneven structure of 80 degrees or more, more preferably 100 degrees or more, still more preferably 130 degrees or more, and particularly preferably 135 degrees or more.
若與磷酸三酯進行比較，則可認為磷酸單酯及/或磷酸二酯因具有羥基，故對於包含陽極氧化多孔氧化鋁的壓模表面的吸附力優異。具體而言，可認為陽極氧化多孔氧化鋁的表面並非僅為純粹的氧化鋁，而存在氫氧化鋁或氧化鋁的水合物，且可認為磷酸單酯及/或磷酸二酯的羥基與氫氧化鋁或氧化鋁具有強的相互作用，但詳細的機制並不明確。When compared with a phosphate triester, it is considered that a phosphate monoester and/or a phosphoric acid diester has the hydroxyl group, and it is excellent in the adsorption|suction of the surface of the stamper containing an oxidized porous alumina. Specifically, it can be considered that the surface of the anodized porous alumina is not only pure alumina, but a hydrate of aluminum hydroxide or aluminum oxide is present, and the hydroxyl group and the hydroxide of the phosphoric acid monoester and/or the phosphoric acid diester can be considered. Aluminum or alumina has strong interactions, but the detailed mechanism is not clear.
另外，磷酸單酯及/或磷酸二酯之中，磷酸單烷基酯及/或磷酸二烷基酯因不具有氧基伸烷基骨架，故疏水性高，可進一步使壓模的表面變成疏水性。壓模表面變成疏水性且表面自由能下降的結果，使用該壓模所形成的作為活性能量線硬化性樹脂組成物（X）的硬化物而獲得的微細凹凸結構的表面亦容易變成疏水性。具體而言，由於壓模表面的表面自由能充分低，若活性能量線硬化性樹脂組成物（X）與壓模接觸，則活性能量線硬化性樹脂組成物（X）中所含有的撥水性賦予成分的疏水性官能基於壓模側進行配向，作為活性能量線硬化性樹脂組成物（X）的硬化物而獲得的微細凹凸結構的表面變成疏水性。Further, among the phosphoric acid monoester and/or the phosphoric acid diester, the monoalkyl phosphate and/or the dialkyl phosphate do not have an oxyalkylene skeleton, so the hydrophobicity is high, and the surface of the stamper can be further made hydrophobic. Sex. As a result of the surface of the stamper becoming hydrophobic and the surface free energy being lowered, the surface of the fine uneven structure obtained as the cured product of the active energy ray-curable resin composition (X) formed by the stamper is also likely to become hydrophobic. Specifically, the surface free energy of the surface of the stamper is sufficiently low, and when the active energy ray-curable resin composition (X) is in contact with the stamper, the water repellency contained in the active energy ray-curable resin composition (X) is contained. The hydrophobic functional group of the component is aligned on the side of the stamper, and the surface of the fine concavo-convex structure obtained as a cured product of the active energy ray-curable resin composition (X) becomes hydrophobic.
作為磷酸單烷基酯及磷酸二烷基酯，可使用烷基的碳數例如處於1～20的範圍內，較佳為處於6～20的範圍內，更佳為處於8～18的範圍內者。The monoalkyl phosphate and the dialkyl phosphate may be, for example, in the range of from 1 to 20, preferably in the range of from 6 to 20, more preferably in the range of from 8 to 18. By.
作為內部脫模劑（F）的市售品，例如可列舉：日光化學（Nikko Chemicals）公司製造的商品名：DDP-2、DDP-4、DDP-6、DDP-8、DDP-10，城北化學工業公司製造的商品名：JP-512、JP-513、JAMP-8、JAMP-12，大八化學工業公司製造的製品名：AP-8、AP-10、MP-10，SC有機化學公司製造的製品名：福斯萊克斯（Phoslex）系列：A-8、A-10、A-12、A-13、A-18、A-18D、A-180L等。As a commercial item of the internal mold release agent (F), the brand name: DDP-2, DDP-4, DDP-6, DDP-8, DDP-10 by the Nikko Chemicals Co., Ltd. Trade name made by Chemical Industry Co., Ltd.: JP-512, JP-513, JAMP-8, JAMP-12, product name manufactured by Daiba Chemical Industry Co., Ltd.: AP-8, AP-10, MP-10, SC Organic Chemical Company Product name manufactured: Phoslex series: A-8, A-10, A-12, A-13, A-18, A-18D, A-180L, etc.
該些之中，較佳為作為磷酸單烷基酯及/或磷酸二烷基酯的城北化學工業公司製造的商品名：JP-512、JP-513、JAMP-8、JAMP-12，大八化學工業公司製造的製品名：AP-8、AP-10、MP-10，SC有機化學公司製造的製品名：福斯萊克斯（Phoslex）系列：A-8、A-10、A-12、A-13、A-18、A-18D、A-180L等。Among these, it is preferably manufactured by Seibu Chemical Industry Co., Ltd., which is a monoalkyl phosphate and/or a dialkyl phosphate, JP-512, JP-513, JAMP-8, JAMP-12, and Big Eight. Product name manufactured by Chemical Industry Co., Ltd.: AP-8, AP-10, MP-10, SC Organic Chemical Company's product name: Phoslex series: A-8, A-10, A-12, A-13, A-18, A-18D, A-180L, etc.
[聚合性成分（A）] 對於本發明的實施形態的活性能量線硬化性樹脂組成物的硬化物而言，聚合性成分（A）具有提昇耐擦傷性、提昇耐候性、提昇基材密接性的效果。例如，關於基材密接性，對於聚碳酸酯樹脂或丙烯酸樹脂有效。另外，亦可獲得提昇活性能量線硬化性樹脂組成物的相容性或低黏度化的效果。[Polymerizable component (A)] The cured component (A) has improved scratch resistance, improved weather resistance, and improved substrate adhesion in the cured product of the active energy ray-curable resin composition of the embodiment of the present invention. Effect. For example, regarding the adhesion of the substrate, it is effective for a polycarbonate resin or an acrylic resin. Further, it is also possible to obtain an effect of improving the compatibility or low viscosity of the active energy ray-curable resin composition.
作為聚合性成分（A），較佳為藉由費多斯法所計算的SP值為19.6以下的聚合性成分。若SP值超過19.6，則存在聚合性成分（A）與所述內部脫模劑（F）、或聚合性成分（A）以外的聚合性成分的相容性下降，且所獲得的硬化物產生白濁之虞。另外，藉由使用SP值為19.6以下的成分，可使硬化物的表面變成疏水性。作為聚合性成分（A），可使用烷二醇二(甲基)丙烯酸酯。作為烷二醇二(甲基)丙烯酸酯的原料的烷二醇的碳數較佳為6以上，更佳為7以上，進而更佳為8以上，特佳為9以上。若烷烴部的碳數過小，則活性能量線硬化性樹脂組成物的硬化物變得過硬，微細凹凸結構變脆而容易受損。另一方面，若烷烴部的碳數過大，則存在烷二醇二(甲基)丙烯酸酯具有結晶性，操作性顯著下降的情況。因此，作為聚合性成分（A）的原料的烷二醇的碳數較佳為12以下，更佳為10以下。另外，烷烴部可為直鏈結構，亦可為分支結構，亦可為兩者的混合物。藉由具有分支結構，可降低結晶性，即便為低溫，亦變成液狀，可提昇操作性。另外，環烷烴結構具有使硬化物的玻璃轉移溫度上昇，並變硬的效果。The polymerizable component (A) is preferably a polymerizable component having an SP value of 19.6 or less calculated by the Fedos method. When the SP value is more than 19.6, the compatibility between the polymerizable component (A) and the polymerizable component other than the internal mold release agent (F) or the polymerizable component (A) is lowered, and the obtained cured product is produced. White turbidity. Further, by using a component having an SP value of 19.6 or less, the surface of the cured product can be rendered hydrophobic. As the polymerizable component (A), an alkanediol di(meth)acrylate can be used. The carbon number of the alkanediol as a raw material of the alkanediol di(meth)acrylate is preferably 6 or more, more preferably 7 or more, still more preferably 8 or more, and particularly preferably 9 or more. When the carbon number of the alkane portion is too small, the cured product of the active energy ray-curable resin composition becomes too hard, and the fine uneven structure becomes brittle and is easily damaged. On the other hand, when the carbon number of the alkane portion is too large, the alkanediol di(meth)acrylate may have crystallinity, and the workability may be remarkably lowered. Therefore, the carbon number of the alkanediol as a raw material of the polymerizable component (A) is preferably 12 or less, more preferably 10 or less. Further, the alkane portion may have a linear structure, a branched structure, or a mixture of the two. By having a branched structure, crystallinity can be lowered, and even at a low temperature, it becomes liquid, and workability can be improved. Further, the cycloalkane structure has an effect of increasing the glass transition temperature of the cured product and hardening it.
作為聚合性成分（A）的具體例，例如可列舉：1,6-己二醇二(甲基)丙烯酸酯、1,7-庚二醇二(甲基)丙烯酸酯、1,8-辛二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、1,12-十二烷二醇二(甲基)丙烯酸酯、1,16-十六烷二醇二(甲基)丙烯酸酯丙烯酸酯、鯊肝醇二(甲基)丙烯酸酯、3-甲基-1,5-戊二醇二(甲基)丙烯酸酯、2-甲基-1,8-辛二醇二(甲基)丙烯酸酯、2-乙基-2-丁基-丙二醇二(甲基)丙烯酸酯、二聚體二醇二(甲基)丙烯酸酯等。該些可單獨使用一種，亦可併用兩種以上。Specific examples of the polymerizable component (A) include 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, and 1,8-octyl group. Diol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-nonanediol di(meth)acrylate, 1,12-dodecanediol II (Meth) acrylate, 1,16-hexadecanediol di(meth)acrylate acrylate, shark liver di(meth)acrylate, 3-methyl-1,5-pentanediol (Meth) acrylate, 2-methyl-1,8-octanediol di(meth) acrylate, 2-ethyl-2-butyl-propylene glycol di(meth) acrylate, dimer II Alcohol di(meth)acrylate and the like. These may be used alone or in combination of two or more.
聚合性成分（P）的總量100質量%之中，聚合性成分（A）的含有比例可設定成50質量%～100質量%的範圍。就獲得更充分的添加效果的觀點而言，更佳為60質量%以上。就一面獲得由聚合性成分（A）所產生的充分的效果，一面獲得由其他聚合性成分所產生的效果的觀點而言，聚合性成分（A）的含有比例較佳為90質量%以下，更佳為85質量%以下。若聚合性成分（A）的含有比例為50質量%以上，則於硬化物中，可獲得優異的耐擦傷性、耐候性、基材密接性等效果，於樹脂組成物中，可期待低黏度化或提昇與聚合性成分（B）等其他聚合性成分的相容性的效果。The content ratio of the polymerizable component (A) may be in the range of 50% by mass to 100% by mass based on 100% by mass of the total amount of the polymerizable component (P). From the viewpoint of obtaining a more sufficient effect of addition, it is more preferably 60% by mass or more. The content of the polymerizable component (A) is preferably 90% by mass or less from the viewpoint of obtaining the effect of the polymerizable component (A) and obtaining the effect by the other polymerizable component. More preferably, it is 85% by mass or less. When the content ratio of the polymerizable component (A) is 50% by mass or more, excellent effects such as scratch resistance, weather resistance, and substrate adhesion can be obtained in the cured product, and low viscosity can be expected in the resin composition. The effect of compatibility with other polymerizable components such as the polymerizable component (B) is improved or improved.
[聚合性成分（B）] 對於本發明的實施形態的活性能量線硬化性樹脂組成物的硬化物而言，聚合性成分（B）具有賦予撥水性或防污性或者提昇耐擦傷性的效果。另外，關於提昇脫模性，有時起到輔助的作用。[Polymerizable component (B)] The cured component (B) has a water-repellent or anti-staining property or an effect of improving scratch resistance in the cured product of the active energy ray-curable resin composition of the embodiment of the present invention. . In addition, it may play an auxiliary role in improving the release property.
聚合性成分（B）為矽酮(甲基)丙烯酸酯及/或(甲基)丙烯酸烷基酯。以下，將矽酮(甲基)丙烯酸酯與(甲基)丙烯酸烷基酯加以區分來分別說明。The polymerizable component (B) is an anthrone (meth) acrylate and/or an alkyl (meth) acrylate. Hereinafter, the fluorenone (meth) acrylate and the alkyl (meth) acrylate are distinguished and described separately.
（矽酮(甲基)丙烯酸酯） 矽酮(甲基)丙烯酸酯為具有矽酮骨架的(甲基)丙烯酸酯。以下，關於適合於本發明的矽酮(甲基)丙烯酸酯，列舉幾例來具體地進行說明。(Anthrone (Meth) acrylate) Anthrone (meth) acrylate is a (meth) acrylate having an fluorenone skeleton. Hereinafter, the anthrone (meth) acrylate which is suitable for the present invention will be specifically described by way of a few examples.
作為矽酮(甲基)丙烯酸酯，例如可列舉：由下述式1所表示的於兩末端及/或一末端具有(甲基)丙烯酸丙酯結構的矽酮(甲基)丙烯酸酯。Examples of the fluorenone (meth) acrylate include an anthrone (meth) acrylate having a propyl (meth) acrylate structure at both terminals and/or one end represented by the following formula 1.
[化1] [Chemical 1]
由式（1）所表示的矽酮(甲基)丙烯酸酯若分子量過大，則存在與聚合性成分（A）等其他聚合性成分的相容性下降的傾向。另一方面，若分子量過小，則難以獲得提昇撥水性或耐擦傷性的效果。因此，由式（1）所表示的矽酮(甲基)丙烯酸酯的重量平均分子量較佳為500～2000左右。When the molecular weight of the fluorenone (meth) acrylate represented by the formula (1) is too large, the compatibility with other polymerizable components such as the polymerizable component (A) tends to decrease. On the other hand, if the molecular weight is too small, it is difficult to obtain an effect of improving water repellency or scratch resistance. Therefore, the weight average molecular weight of the anthrone (meth) acrylate represented by the formula (1) is preferably about 500 to 2,000.
作為此種聚合性成分（B）的市售品，例如可列舉：JNC公司製造的「塞拉普雷（Silaplane）（註冊商標）」系列的製品名：FM-0711、FM-0721、FM-0725、FM-7711、FM-7721、FM-7725，信越化學工業公司製造的製品名：X-22-2445、X-22-174ASX、X-22-174BX、X-22-174DX、KF-2012、X-22-2426、X-22-2475、X-22-164、X-22-164AS、X-22-164A、X-22-164B、X-22-164C、X-22-164E，東麗·道康寧公司製造的製品名：BY16-152C等。As a commercial item of such a polymerizable component (B), the product name of the "Silaplane (registered trademark)" series by JNC Corporation: FM-0711, FM-0721, FM- 0725, FM-7711, FM-7721, FM-7725, product names manufactured by Shin-Etsu Chemical Co., Ltd.: X-22-2445, X-22-174ASX, X-22-174BX, X-22-174DX, KF-2012 , X-22-2426, X-22-2475, X-22-164, X-22-164AS, X-22-164A, X-22-164B, X-22-164C, X-22-164E, East Product name manufactured by Li Dow Corning Company: BY16-152C, etc.
此外，作為矽酮(甲基)丙烯酸酯，例如可列舉：由下述式（2）所表示的矽酮環氧(甲基)丙烯酸酯。In addition, examples of the fluorenone (meth) acrylate include an fluorenone epoxy (meth) acrylate represented by the following formula (2).
[化2] [Chemical 2]
作為由式（2）所表示的矽酮(甲基)丙烯酸酯的市售品，例如可列舉：日本贏創（Evonik·Japan）公司製造的「迪高（Tego）（註冊商標）系列」的製品名：Rad2011、Rad2100、Rad2500等。The commercially available product of the fluorenone (meth) acrylate represented by the formula (2), for example, "Tego (registered trademark) series" manufactured by Evonik Japan Co., Ltd. Product name: Rad2011, Rad2100, Rad2500, etc.
作為其他矽酮(甲基)丙烯酸酯，可列舉對聚二甲基矽氧烷的兩末端進行環氧乙烷（Ethylene Oxide，EO）及/或環氧丙烷（Propylene Oxide，PO）改質而成的(甲基)丙烯酸酯。作為其市售品，例如可列舉：信越化學工業公司製造的製品名：X-22-1602，日本畢克化學（BYK-Chemie·Japan）公司製造的製品名：BYK-UV3500、BYK-UV3530，日本贏創公司製造的製品名：「迪高（Tego）」（註冊商標）系列：Rad2200N、Rad2250、Rad2300，大賽璐-湛新（Daicel-Allnex）公司製造的製品名：艾巴克力（EBECRYL）350等。所述「EO改質」是指環氧乙烷改質，「PO改質」是指環氧丙烷改質。Examples of the other anthrone (meth) acrylate include ethylene oxide (Ethylene Oxide, EO) and/or propylene oxide (Propylene Oxide, PO) at both ends of the polydimethyl siloxane. (M) acrylate. As a commercial item, the product name of the product manufactured by Shin-Etsu Chemical Co., Ltd.: X-22-1602, and the product name of BYK-Chemie Japan, BYK-UV3500, BYK-UV3530, etc. Product name manufactured by Evonik Japan: "Tego" (registered trademark) series: Rad2200N, Rad2250, Rad2300, Daicel-Allnex company name: EBCERRYL 350 and so on. The "EO modification" refers to the modification of ethylene oxide, and the "PO modification" refers to the modification of propylene oxide.
此外，作為矽酮(甲基)丙烯酸酯，可列舉：作為(甲基)丙烯酸胺基甲酸酯及/或聚酯(甲基)丙烯酸酯且具有矽酮骨架者，例如具有(甲基)丙烯醯基的聚酯改質聚二甲基矽氧烷、具有聚二甲基矽氧烷結構的(甲基)丙烯酸胺基甲酸酯。作為其市售品，例如可列舉：日本畢克化學公司製造的製品名：BYK-UV3570，美源特殊化工（Miwon Speciality Chemical）公司製造的製品名：「米拉瑪（Miramer）（註冊商標）」系列：SIU100、SIU1000、SIU2400、SIP900等。In addition, examples of the fluorenone (meth) acrylate include (meth)acrylic acid urethane and/or polyester (meth) acrylate and have an fluorenone skeleton, for example, (meth) The acryl oxime-based polyester is modified with polydimethyl siloxane, a (meth) acrylate urethane having a polydimethyl siloxane structure. As a commercial item, for example, the product name of BYK-UV3570, manufactured by Mi Keon Chemical Co., Ltd., and the product name: "Miramer (registered trademark)" Series: SIU100, SIU1000, SIU2400, SIP900, etc.
作為所述以外的矽酮(甲基)丙烯酸酯的市售品，例如可列舉：日本畢克化學公司製造的製品名：BYK-UV3505、3530、3575、3576，大賽璐-湛新公司製造的製品名：艾巴克力（EBECRYL）1360等。As a commercial item of the fluorenone (meth) acrylate other than the above, the product name of BYK-UV3505, 3530, 3575, 3576, and the Daicel-Zhanshin company are mentioned, for example. Product name: Ebikery (EBECRYL) 1360 and so on.
以上所列舉的用作聚合性成分（B）的矽酮(甲基)丙烯酸酯之中，就撥水性、耐擦傷性、耐候性的觀點而言，較佳為選自由式（1）所表示的矽酮(甲基)丙烯酸酯、由式（2）所表示的矽酮(甲基)丙烯酸酯、及BYK-UV3570中者。尤其就賦予超撥水性的觀點而言，較佳為使用由式（1）所表示的矽酮(甲基)丙烯酸酯。Among the fluorenone (meth) acrylates used as the polymerizable component (B) listed above, from the viewpoint of water repellency, scratch resistance, and weather resistance, it is preferably selected from the formula (1). The fluorenone (meth) acrylate, the fluorenone (meth) acrylate represented by the formula (2), and BYK-UV3570. In particular, from the viewpoint of imparting super-water repellency, it is preferred to use an anthrone (meth) acrylate represented by the formula (1).
具有氧基伸烷基結構的矽酮(甲基)丙烯酸酯雖然相容性良好，但就耐候性的觀點而言，存在結果欠佳的情況。因此，就耐候性的觀點而言，作為聚合性成分（B），較佳為不具有氧基伸烷基骨架的非氧基伸烷基化矽酮(甲基)丙烯酸酯。The anthrone (meth) acrylate having an oxyalkylene structure has good compatibility, but has a poor result in terms of weather resistance. Therefore, from the viewpoint of weather resistance, the polymerizable component (B) is preferably a non-oxyalkylene ketone (meth) acrylate having no oxyalkylene skeleton.
（(甲基)丙烯酸烷基酯） 就提昇硬化物的撥水性與耐擦傷性的觀點而言，用作聚合性成分（B）的(甲基)丙烯酸烷基酯較佳為烷基比較長者。具體而言，烷基的碳數較佳為8～22，更佳為12～18。烷基可為直鏈，亦可為分支。若烷基過長，則結晶性變高且於液狀下的處理變得困難，若過短，則存在揮發性成為問題的情況。作為(甲基)丙烯酸烷基酯的具體例，可列舉：(甲基)丙烯酸（異）辛酯、(甲基)丙烯酸（異）癸酯、(甲基)丙烯酸（異）月桂酯、(甲基)丙烯酸（異）十六酯、(甲基)丙烯酸（異）硬脂基酯、(甲基)丙烯酸（異）二十二酯等。該些之中，就撥水性的賦予與操作性的觀點而言，特佳為(甲基)丙烯酸異硬脂基酯。(alkyl (meth) acrylate) The alkyl (meth) acrylate used as the polymerizable component (B) is preferably an alkyl group in terms of the water repellency and scratch resistance of the cured product. . Specifically, the alkyl group preferably has 8 to 22 carbon atoms, more preferably 12 to 18 carbon atoms. The alkyl group may be straight or branched. When the alkyl group is too long, the crystallinity becomes high and the treatment in the liquid state becomes difficult, and if it is too short, the volatility may become a problem. Specific examples of the (meth)acrylic acid alkyl ester include (iso)octyl (meth)acrylate, (iso)decyl (meth)acrylate, (iso) lauryl (meth)acrylate, ( (Iso) hexadecyl (meth) acrylate, (iso) stearyl (meth) acrylate, (iso) docosa (meth) acrylate, and the like. Among these, from the viewpoint of imparting water repellency and handling properties, it is particularly preferred to be isostearyl (meth)acrylate.
聚合性成分（P）的總量100質量%之中，聚合性成分（B）的含有比例可設定成0.5質量%～50質量%的範圍。就獲得充分的添加效果的觀點而言，更佳為1質量%以上。若聚合性成分（B）的添加量過多，則存在硬化物的物性下降且耐擦傷性下降的情況。因此，聚合性成分（B）的含有比例較佳為40質量%以下，更佳為20質量%以下，特佳為10質量%以下。The content ratio of the polymerizable component (B) may be in the range of 0.5% by mass to 50% by mass based on 100% by mass of the total amount of the polymerizable component (P). From the viewpoint of obtaining a sufficient effect of addition, it is more preferably 1% by mass or more. When the amount of the polymerizable component (B) to be added is too large, the physical properties of the cured product may be lowered and the scratch resistance may be lowered. Therefore, the content ratio of the polymerizable component (B) is preferably 40% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less.
當聚合性成分（B）的含有比例為0.5質量%以上時，例如可設定成聚合性成分（A）50質量%～99.5質量%、聚合性成分（B）0.5質量%～50質量%、聚合性成分（C）0質量%～49.5質量%，另外，可設定成聚合性成分（A）50質量%～89.5質量%、聚合性成分（B）0.5質量%～40質量%、聚合性成分（C）10質量%～49.5質量%。When the content ratio of the polymerizable component (B) is 0.5% by mass or more, for example, the polymerizable component (A) may be 50% by mass to 99.5% by mass, and the polymerizable component (B) may be 0.5% by mass to 50% by mass. The component (C) is 0% by mass to 49.5% by mass, and the polymerizable component (A) is 50% by mass to 89.5 % by mass, and the polymerizable component (B) is 0.5% by mass to 40% by mass, and the polymerizable component ( C) 10% by mass to 49.5% by mass.
當聚合性成分（B）的含有比例為1質量%以上時，例如可設定成聚合性成分（A）50質量%～99質量%、聚合性成分（B）1質量%～50質量%、聚合性成分（C）0質量%～49質量%，另外，可設定成聚合性成分（A）50質量%～89質量%、聚合性成分（B）1質量%～40質量%、聚合性成分（C）10質量%～49質量%。When the content ratio of the polymerizable component (B) is 1% by mass or more, for example, the polymerizable component (A) may be 50% by mass to 99% by mass, and the polymerizable component (B) may be 1% by mass to 50% by mass. The component (C) is 0% by mass to 49% by mass, and the polymerizable component (A) is 50% by mass to 89% by mass, the polymerizable component (B) is 1% by mass to 40% by mass, and the polymerizable component ( C) 10% by mass to 49% by mass.
[聚合性成分（C）] 聚合性成分（C）為具有3個以上的(甲基)丙烯醯基的多官能(甲基)丙烯酸酯。藉由聚合性成分（C），可調節活性能量線硬化性樹脂組成物的硬化物的硬度，並可提昇耐擦傷性。聚合性成分（C）的每分子量的(甲基)丙烯醯基的數量越多，越可對硬化物賦予硬度。另外，分子量更小者或分子內具有甲基者與聚合性成分（B）等其他聚合性成分的相容性優異。相反地，具有聚醚結構者存在與聚合性成分（B）等其他聚合性成分的相容性或耐候性欠佳的情況。[Polymerizable component (C)] The polymerizable component (C) is a polyfunctional (meth)acrylate having three or more (meth)acrylonyl groups. By the polymerizable component (C), the hardness of the cured product of the active energy ray-curable resin composition can be adjusted, and the scratch resistance can be improved. The more the number of (meth) acrylonitrile groups per molecular weight of the polymerizable component (C), the more the hardness can be imparted to the cured product. Further, those having a smaller molecular weight or having a methyl group in the molecule are excellent in compatibility with other polymerizable components such as the polymerizable component (B). Conversely, those having a polyether structure may have poor compatibility or weather resistance with other polymerizable components such as the polymerizable component (B).
作為聚合性成分（C）的具體例，例如可列舉：三羥甲基丙烷三(甲基)丙烯酸酯，二-三羥甲基丙烷三(甲基)丙烯酸酯，二-三羥甲基丙烷四(甲基)丙烯酸酯，（聚）甘油（聚）丙烯酸酯，季戊四醇三（四）丙烯酸酯，季戊四醇三（四）甲基丙烯酸酯，二季戊四醇（五）六丙烯酸酯，二季戊四醇（五）六甲基丙烯酸酯，聚季戊四醇聚(甲基)丙烯酸酯，及該些的EO改質、PO改質或己內酯改質(甲基)丙烯酸酯，以及三官能以上的(甲基)丙烯酸胺基甲酸酯，三官能以上的環氧(甲基)丙烯酸酯，三官能以上的聚酯(甲基)丙烯酸酯等。該些之中，就與聚合性成分（B）的相容性或耐擦傷性的觀點而言，較佳為三羥甲基丙烷三(甲基)丙烯酸酯、二-三羥甲基丙烷三(甲基)丙烯酸酯、二-三羥甲基丙烷四(甲基)丙烯酸酯、季戊四醇三（四）丙烯酸酯、季戊四醇三（四）甲基丙烯酸酯。另外，EO改質物及PO改質物就耐候性的觀點而言令人擔憂，因此就耐候性的觀點而言，較佳為己內酯改質物。Specific examples of the polymerizable component (C) include trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tri(meth)acrylate, and di-trimethylolpropane. Tetra(meth)acrylate, (poly)glycerol (poly)acrylate, pentaerythritol tri(tetra)acrylate, pentaerythritol tris(tetra)methacrylate, dipentaerythritol (penta)hexaacrylate, dipentaerythritol (v) Hexamethyl acrylate, polypentaerythritol poly(meth) acrylate, and EO modification, PO modification or caprolactone modification (meth) acrylate, and trifunctional or higher (meth) acrylate A urethane, a trifunctional or higher epoxy (meth) acrylate, a trifunctional or higher polyester (meth) acrylate, or the like. Among these, from the viewpoint of compatibility with the polymerizable component (B) or scratch resistance, trimethylolpropane tri(meth)acrylate and di-trimethylolpropane are preferable. (Meth) acrylate, di-trimethylolpropane tetra(meth) acrylate, pentaerythritol tri (tetra) acrylate, pentaerythritol tri (tetra) methacrylate. Further, since the EO modified product and the PO modified product are worrying from the viewpoint of weather resistance, from the viewpoint of weather resistance, a caprolactone modified product is preferable.
聚合性成分（P）的總量100質量%之中，聚合性成分（C）的含有比例可設定成0質量%～50質量%的範圍。就獲得充分的添加效果的觀點而言，較佳為5質量%以上，更佳為10質量%以上。若聚合性成分（C）的添加量過多，則因與聚合性成分（B）等其他聚合性成分的相容性的問題，而存在無法維持活性能量線硬化性樹脂組成物及其硬化物的透明性的情況。另外，就充分地確保其他聚合性成分的含量的觀點而言，聚合性成分（C）的含有比例可設定成49.5質量%以下，較佳為30質量%以下，更佳為25質量%以下。The content ratio of the polymerizable component (C) may be in the range of 0% by mass to 50% by mass, based on 100% by mass of the total amount of the polymerizable component (P). From the viewpoint of obtaining a sufficient effect of addition, it is preferably 5% by mass or more, and more preferably 10% by mass or more. When the amount of the polymerizable component (C) is too large, the active energy ray-curable resin composition and the cured product thereof cannot be maintained due to compatibility with other polymerizable components such as the polymerizable component (B). The case of transparency. In addition, the content ratio of the polymerizable component (C) can be set to 49.5% by mass or less, preferably 30% by mass or less, and more preferably 25% by mass or less, from the viewpoint of sufficiently ensuring the content of the other polymerizable component.
[聚合性成分（D）] 其他聚合性成分（D）是含有具有與聚合性成分（P）中的其他聚合性成分的共聚性的聚合性官能基，且不屬於聚合性成分（A）、聚合性成分（B）、聚合性成分（C）者。聚合性成分（D）所具有的聚合性的官能基較佳為自由基聚合性者，例如可列舉：甲基丙烯醯基、丙烯醯基、丙烯醯胺基、乙烯基醚基、乙烯基等。作為可由聚合性成分（D）所賦予的功能，例如可列舉：基材密接性、稀釋性、撥水性、親水性、抗靜電性、滑動性、調平性、耐擦傷性、耐候性、發光性、螢光性、顯色性、導電性、折射率調整、抗氧化等。[Polymerizable component (D)] The polymerizable component (D) is a polymerizable functional group having copolymerizability with another polymerizable component in the polymerizable component (P), and does not belong to the polymerizable component (A). The polymerizable component (B) and the polymerizable component (C). The polymerizable functional group of the polymerizable component (D) is preferably a radical polymerizable one, and examples thereof include a methyl methacrylate group, an acryl fluorenyl group, an acrylamide group, a vinyl ether group, and a vinyl group. . Examples of the function which can be imparted by the polymerizable component (D) include substrate adhesion, dilution, water repellency, hydrophilicity, antistatic property, slidability, leveling property, scratch resistance, weather resistance, and luminescence. Properties, fluorescence, color rendering, conductivity, refractive index adjustment, oxidation resistance, etc.
作為單官能的聚合性成分（D），例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸月桂酯等(甲基)丙烯酸烷基酯；(甲基)丙烯酸苄酯；(甲基)丙烯酸異冰片酯、(甲基)丙烯酸四氫糠酯、(甲基)丙烯酸金剛烷酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊烯酯等具有脂環結構的(甲基)丙烯酸酯；(甲基)丙烯酸二甲基胺基乙酯、(甲基)丙烯酸二甲基胺基丙酯等具有胺基的(甲基)丙烯酸酯；(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸羥基丙酯等具有羥基的(甲基)丙烯酸酯；(甲基)丙烯醯基嗎啉、N,N-二甲基(甲基)丙烯醯胺等(甲基)丙烯醯胺衍生物；2-乙烯基吡啶、4-乙烯基吡啶、N-乙烯基吡咯啶酮、N-乙烯基甲醯胺、乙酸乙烯酯等，1,2,2,6,6-五甲基-4-哌啶基=(甲基)丙烯酸酯、2,2,6,6-四甲基-4-哌啶基=(甲基)丙烯酸酯、丙烯酸2-第三丁基-6-(3-第三丁基-2-羥基-5-甲基苄基)-4-甲基苯酯、丙烯酸2-[1-(2-羥基-3,5-二-第三戊基苯基)乙基]-4,6-二-第三戊基苯酯、3-(2H-1,2,3-苯并***-2-基)-4-羥基苯乙基=甲基丙烯酸酯、(甲基)丙烯酸3,3,4,4,5,5,6,6,7,7,8,8,8-十三氟辛酯等含有氟的(甲基)丙烯酸酯。Examples of the monofunctional polymerizable component (D) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate. (meth)acrylic acid alkyl ester such as tert-butyl methacrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate; benzyl (meth) acrylate; (methyl) Isobornyl acrylate, tetrahydrofurfuryl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, etc. having an alicyclic structure (meth) acrylate; (meth) acrylate having an amine group such as dimethylaminoethyl (meth) acrylate or dimethyl aminopropyl methacrylate; hydroxy group (meth) acrylate (meth) acrylate having a hydroxyl group such as ethyl ester or hydroxypropyl (meth) acrylate; (meth) acryl hydrazinomorph, N, N-dimethyl (meth) acrylamide, etc. (methyl a acrylamide derivative; 2-vinylpyridine, 4-vinylpyridine, N-vinylpyrrolidone, N-vinylformamide, vinyl acetate, etc., 1, 2, 2, 6, 6- Pentamethyl-4-piperidinyl = (methyl) propyl Ethyl ester, 2,2,6,6-tetramethyl-4-piperidinyl = (meth) acrylate, 2-tert-butyl-6-(3-tert-butyl-2-hydroxyl acrylate -5-Methylbenzyl)-4-methylphenyl ester, 2-[1-(2-hydroxy-3,5-di-tripentylphenyl)ethyl]-4,6-di-acrylic acid- Third amyl phenyl ester, 3-(2H-1,2,3-benzotriazol-2-yl)-4-hydroxyphenethyl=methacrylate, (meth)acrylic acid 3,3,4 a fluorine-containing (meth) acrylate such as 4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl ester.
二官能的聚合性成分（D）包括所有不包含於聚合性成分（A）與聚合性成分（B）中的二官能的聚合性成分。作為此種二官能的聚合性成分（D），例如可列舉：1,3-丁二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,5-戊二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、烷氧基化烷二醇二(甲基)丙烯酸酯、烷氧基化雙酚A二(甲基)丙烯酸酯、羥基三甲基乙酸新戊二醇二(甲基)丙烯酸酯、己內酯改質羥基三甲基乙酸新戊二醇二(甲基)丙烯酸酯、烷氧基化新戊二醇二(甲基)丙烯酸酯、聚碳酸酯二醇二(甲基)丙烯酸酯、（氫化）聚丁二烯末端(甲基)丙烯酸酯、二官能的(甲基)丙烯酸胺基甲酸酯、二官能的環氧(甲基)丙烯酸酯、二官能的聚酯(甲基)丙烯酸酯、含有氟的二官能的(甲基)丙烯酸酯等。The difunctional polymerizable component (D) includes all difunctional polymerizable components which are not contained in the polymerizable component (A) and the polymerizable component (B). Examples of such a difunctional polymerizable component (D) include 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, and 1,5. - pentanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethyl Diol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, alkoxylated alkanediol II (Meth) acrylate, alkoxylated bisphenol A di(meth) acrylate, hydroxytrimethyl acetic acid neopentyl glycol di(meth) acrylate, caprolactone modified hydroxytrimethyl acetic acid Pentyl glycol di(meth) acrylate, alkoxylated neopentyl glycol di(meth) acrylate, polycarbonate diol di(meth) acrylate, (hydrogenated) polybutadiene end (A) Acrylate, difunctional (meth) acrylate urethane, difunctional epoxy (meth) acrylate, difunctional polyester (meth) acrylate, fluorine-containing difunctional ( Methyl) acrylate
聚合性成分（D）的含有比例只要是不阻礙聚合性成分（A）、聚合性成分（B）、聚合性成分（C）的功能的範圍，則並無特別限制，例如可設定成0質量%～50質量%的範圍，較佳為0質量%～30質量%，更佳為0質量%～10質量%。The content ratio of the polymerizable component (D) is not particularly limited as long as it does not inhibit the functions of the polymerizable component (A), the polymerizable component (B), and the polymerizable component (C), and can be set to 0 mass, for example. The range of % to 50% by mass is preferably 0% by mass to 30% by mass, more preferably 0% by mass to 10% by mass.
聚合性成分（P）較佳為相對於聚合性成分的總量100質量%，具有聚氧基伸烷基骨架的聚合性成分的含量未滿10質量%。若含有10質量份以上的具有聚氧基伸烷基骨架的聚合性成分，則活性能量線硬化性組成物的硬化物變成親水性，存在具有微細凹凸結構的物品無法發揮充分的撥水性之虞，另外，存在耐擦傷性或耐候性下降之虞。相對於聚合性成分的總量100質量%，具有聚氧基伸烷基骨架的聚合性成分的含量較佳為8質量%以下，更佳為6質量%以下。The polymerizable component (P) is preferably 100% by mass based on the total amount of the polymerizable component, and the content of the polymerizable component having a polyoxyalkylene group skeleton is less than 10% by mass. When the polymerizable component having a polyoxyalkylene group skeleton is contained in an amount of 10 parts by mass or more, the cured product of the active energy ray-curable composition becomes hydrophilic, and the article having the fine uneven structure cannot exhibit sufficient water repellency. In addition, there is a problem that the scratch resistance or the weather resistance is lowered. The content of the polymerizable component having a polyoxyalkylene group skeleton is preferably 8% by mass or less, and more preferably 6% by mass or less based on 100% by mass of the total amount of the polymerizable component.
另外，聚合性成分（P）較佳為相對於聚合性成分的總量100質量%，具有脂環結構的成分的聚合成分的含量未滿17質量%。若含有17質量%以上的具有脂環結構的聚合性成分，則硬化物的Tg上昇，當形成微細凹凸結構時，存在形成凹凸的凸部變脆，耐擦傷性下降之虞。相對於聚合性成分的總量100質量%，具有脂環結構的聚合性成分的含量較佳為10質量%以下，更佳為5質量%以下，進而更佳為0質量%。Further, the polymerizable component (P) is preferably 100% by mass based on the total amount of the polymerizable component, and the content of the polymer component of the component having an alicyclic structure is less than 17% by mass. When the polymerizable component having an alicyclic structure is contained in an amount of 17% by mass or more, the Tg of the cured product increases, and when the fine uneven structure is formed, the convex portion in which the unevenness is formed becomes brittle and the scratch resistance is lowered. The content of the polymerizable component having an alicyclic structure is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 0% by mass based on 100% by mass of the total amount of the polymerizable component.
[光聚合起始劑（E）] 光聚合起始劑（E）是藉由照射活性能量線而開裂，並產生使聚合反應開始的自由基的化合物。作為活性能量線，就裝置成本或生產性的觀點而言，較佳為紫外線。[Photopolymerization initiator (E)] The photopolymerization initiator (E) is a compound which is cleaved by irradiation with an active energy ray and generates a radical which starts a polymerization reaction. As the active energy ray, ultraviolet rays are preferred from the viewpoint of device cost or productivity.
作為藉由紫外線而產生自由基的光聚合起始劑（E），例如可列舉：二苯甲酮、4,4-雙(二乙基胺基)二苯甲酮、2,4,6-三甲基二苯甲酮、甲基鄰苯甲醯基苯甲酸酯、4-苯基二苯甲酮、第三丁基蒽醌、2-乙基蒽醌、硫雜蒽酮類（2,4-二乙基硫雜蒽酮、異丙基硫雜蒽酮、2,4-二氯硫雜蒽酮等）、苯乙酮類（二乙氧基苯乙酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、苄基二甲基縮酮、1-羥基環己基-苯基酮、2-甲基-2-嗎啉基(4-硫甲基苯基)丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-丁酮等）、安息香醚類（安息香甲基醚、安息香乙基醚、安息香異丙基醚、安息香異丁基醚等）、醯基氧化膦類（2,4,6-三甲基苯甲醯基二苯基氧化膦、雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基戊基氧化膦、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦等）、苯甲醯甲酸甲酯、1,7-雙吖啶基庚烷、9-苯基吖啶等。Examples of the photopolymerization initiator (E) which generates a radical by ultraviolet rays include benzophenone, 4,4-bis(diethylamino)benzophenone, and 2,4,6-. Trimethylbenzophenone, methyl phthalyl benzoate, 4-phenyl benzophenone, tert-butyl fluorene, 2-ethyl hydrazine, thioxanthone (2 , 4-diethyl thianonanone, isopropyl thioxanthone, 2,4-dichlorothiazepinone, etc.), acetophenone (diethoxyacetophenone, 2-hydroxy-2) -methyl-1-phenylpropan-1-one, benzyldimethylketal, 1-hydroxycyclohexyl-phenyl ketone, 2-methyl-2-morpholinyl (4-thiomethylphenyl) Propane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, etc., benzoin ether (benzoin methyl ether, benzoin ethyl ether) , benzoin isopropyl ether, benzoin isobutyl ether, etc.), fluorenylphosphine oxides (2,4,6-trimethylbenzhydryldiphenylphosphine oxide, bis(2,6-dimethoxy) Benzopyridyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide, etc., methyl benzamidinecarboxylate 1,7-diacridine heptane, 9-phenyl acridine, and the like.
光聚合起始劑（E）可單獨使用一種，亦可併用兩種以上。當併用時，較佳為併用吸收波長不同的兩種以上。另外，視需要亦可併用過硫酸鹽（過硫酸鉀、過硫酸銨等）、過氧化物（過氧化苯甲醯等）、偶氮系起始劑等熱聚合起始劑。The photopolymerization initiator (E) may be used alone or in combination of two or more. When used in combination, it is preferred to use two or more kinds of absorption wavelengths in combination. Further, a thermal polymerization initiator such as persulfate (potassium persulfate or ammonium persulfate), a peroxide (such as benzamidine peroxide) or an azo initiator may be used in combination.
相對於活性能量線硬化性樹脂組成物（X）所含有的聚合性成分（P）的合計100質量份，光聚合起始劑（E）的含有率較佳為0.01質量份～10質量份，更佳為0.1質量份～5質量份，進而更佳為0.2質量份～3質量份。若光聚合起始劑（E）的含量過少，則存在活性能量線硬化性樹脂組成物（X）的硬化未完成，而損害表面具有微細凹凸結構的物品的機械物性的情況。若光聚合起始劑（E）的含量過多，則亦存在未反應的光聚合起始劑（E）殘留於硬化物內，作為塑化劑發揮作用，使硬化物的彈性係數下降，而損害耐擦傷性的情況。另外，亦存在成為著色的原因的情況。The content of the photopolymerization initiator (E) is preferably 0.01 parts by mass to 10 parts by mass based on 100 parts by mass of the total of the polymerizable component (P) contained in the active energy ray-curable resin composition (X). It is more preferably 0.1 part by mass to 5 parts by mass, still more preferably 0.2 part by mass to 3 parts by mass. When the content of the photopolymerization initiator (E) is too small, the curing of the active energy ray-curable resin composition (X) is not completed, and the mechanical properties of the article having a fine uneven structure on the surface are impaired. When the content of the photopolymerization initiator (E) is too large, the unreacted photopolymerization initiator (E) remains in the cured product, and acts as a plasticizer to lower the elastic modulus of the cured product. Scratch resistant condition. In addition, there are cases where coloring is caused.
[其他成分（G）] 其他成分（G）是視需要而添加的成分，且為所述聚合性成分（P）、光聚合起始劑（E）、內部脫模劑（F）以外的成分。其他成分（G）包括：阻燃助劑、塑化劑、界面活性劑、抗靜電劑、抗氧化劑、光穩定劑、聚合抑制劑、紫外線吸收劑、填充劑、密接性賦予劑、著色劑、強化劑、無機填料、耐衝擊性改質劑等。此外，亦可包含不具有自由基聚合性的官能基的寡聚物或聚合物、微量的有機溶媒等。另外，亦可併用內部脫模劑（F）以外的脫模性賦予成分。[Other components (G)] The other component (G) is a component added as needed, and is a component other than the polymerizable component (P), the photopolymerization initiator (E), and the internal mold release agent (F). . Other components (G) include: flame retardant auxiliary, plasticizer, surfactant, antistatic agent, antioxidant, light stabilizer, polymerization inhibitor, ultraviolet absorber, filler, adhesion imparting agent, colorant, A strengthening agent, an inorganic filler, an impact modifier, and the like. Further, an oligomer or polymer having no radical polymerizable functional group, a trace amount of an organic solvent, or the like may be contained. Further, a mold release imparting component other than the internal mold release agent (F) may be used in combination.
作為聚合抑制劑，例如作為對苯二酚系聚合抑制劑，可列舉對苯二酚（Hydroquinone，HQ）、對苯二酚單甲基醚（Hydroquinone Monomethyl Ether，MEHQ），作為酚系聚合抑制劑，可列舉2,2'-亞甲基-雙(4-甲基-6-第三丁基苯酚)、兒茶酚、苦味酸、第三丁基兒茶酚、2,6-二第三丁基-對甲酚（Butylated Hydroxytoluene，BHT）、4,4'-硫代雙[伸乙基(氧基)(羰基)(伸乙基)]雙[2,6-雙(1,1-二甲基乙基)苯酚]等。作為啡噻嗪系聚合抑制劑，可列舉啡噻嗪、雙(α-甲基苄基)啡噻嗪、3,7-二辛基啡噻嗪、雙(α,α-二甲基苄基)啡噻嗪等。此處所列舉的聚合抑制劑之中，BHT等酚系聚合抑制劑亦可用作抗氧化劑。As a polymerization inhibitor, for example, hydroquinone (HQ) or hydroquinone monomethyl Ether (MEHQ) can be cited as a phenolic polymerization inhibitor. Examples include 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), catechol, picric acid, tert-butylcatechol, 2,6-two, and third Butylated Hydroxytoluene (BHT), 4,4'-thiobis[extended ethyl(oxy)(carbonyl)(extended ethyl)]bis[2,6-bis(1,1- Dimethylethyl)phenol] and the like. Examples of the phenothiazine polymerization inhibitor include phenothiazine, bis(α-methylbenzyl) phenothiazine, 3,7-dioctylphthylthiazine, and bis(α,α-dimethylbenzyl group. ) phenothiazine and the like. Among the polymerization inhibitors exemplified herein, a phenol-based polymerization inhibitor such as BHT can also be used as an antioxidant.
作為抗氧化劑，例如可列舉：受阻酚系、苯并咪唑系、磷系、硫系、受阻胺系等的抗氧化劑。作為市售品，可列舉巴斯夫（BASF）公司製造的「易璐諾斯（IRGANOX）」（註冊商標）系列等。Examples of the antioxidant include antioxidants such as hindered phenol type, benzimidazole type, phosphorus type, sulfur type, and hindered amine type. As a commercial item, the "IRGANOX" (registered trademark) series manufactured by BASF Corporation, etc. are mentioned.
作為光穩定劑，例如可列舉：受阻胺系的抗氧化劑。作為受阻胺系的自由基補充劑的一次抗氧化劑例如可列舉下述者。巴斯夫公司製造，商品名：齊馬素布（Chimassorb）2020FDL、齊馬素布（Chimassorb）944FDL、帝奴彬（Tinuvin）622SF、尤維納（Uvinul）5050H、帝奴彬（Tinuvin）144、帝奴彬（Tinuvin）765、帝奴彬（Tinuvin）770DF、帝奴彬（Tinuvin）4050FF。Examples of the light stabilizer include hindered amine-based antioxidants. The primary antioxidant which is a hindered amine-based radical supplement is exemplified by the following. Made by BASF, trade name: Chimassorb 2020FDL, Chimassorb 944FDL, Tinuvin 622SF, Uvinul 5050H, Tinuvin 144, Emperor Tinuvin 765, Tinuvin 770DF, Tinuvin 4050FF.
作為紫外線吸收劑，例如可列舉：二苯甲酮系、苯并***系、受阻胺系、苯甲酸酯系、三嗪系等。作為市售品，可列舉：巴斯夫公司製造的商品名：帝奴彬（Tinuvin）400、帝奴彬（Tinuvin）479，共同藥品（股份）製造的商品名：維奧素布（Viosorb）110等。Examples of the ultraviolet absorber include a benzophenone type, a benzotriazole type, a hindered amine type, a benzoate type, and a triazine type. As a commercial item, the trade name of the BASF company: Tinuvin 400, Tinuvin 479, and the name of the common drug (share): Viosorb 110, etc. .
[樹脂組成物的黏度] 當藉由壓模來形成微細凹凸結構並使其硬化時，就朝壓模的表面的微細凹凸結構中的流入容易性的觀點而言，本發明的實施形態的樹脂組成物（X）較佳為具有適度的黏度。25℃下的藉由旋轉式B型黏度計所測定的樹脂組成物的黏度較佳為10000 mPa·s以下，更佳為5000 mPa·s以下，進而更佳為2000 mPa·s以下。再者，樹脂組成物即便25℃下的黏度為10000 mPa·s以上，若藉由增溫而變成所述範圍的黏度，藉此可接觸壓模，則亦可適宜地使用。於此情況下，樹脂組成物的70℃下的藉由旋轉式B型黏度計所得的黏度較佳為5000 mPa·s以下，更佳為2000 mPa·s以下。另外，若樹脂組成物的黏度為10 mPa·s以上，則可與壓模接觸，可形成表面具有微細凹凸結構的硬化物。[Viscosity of Resin Composition] When the fine concavo-convex structure is formed by a stamper and is cured, the resin of the embodiment of the present invention is obtained from the viewpoint of ease of inflow into the fine concavo-convex structure on the surface of the stamper. The composition (X) preferably has a moderate viscosity. The viscosity of the resin composition measured by a rotary B-type viscometer at 25 ° C is preferably 10,000 mPa·s or less, more preferably 5,000 mPa·s or less, and still more preferably 2,000 mPa·s or less. In addition, the resin composition can be suitably used even if the viscosity at 25 ° C is 10,000 mPa·s or more and the viscosity is in the range by increasing the temperature, whereby the stamper can be contacted. In this case, the viscosity of the resin composition at 70 ° C by a rotary B-type viscometer is preferably 5,000 mPa·s or less, more preferably 2,000 mPa·s or less. In addition, when the viscosity of the resin composition is 10 mPa·s or more, it can be brought into contact with the stamper, and a cured product having a fine uneven structure on the surface can be formed.
於調整樹脂組成物的黏度時，可選擇所含有的單體的種類或含量來進行調整、或者使用黏度調整劑進行調整。具體而言，若大量地使用包含具有氫鍵等分子間相互作用的官能基或化學結構的單體，則樹脂組成物的黏度變高。另外，若大量地使用無分子間相互作用的低分子量的單體，則樹脂組成物的黏度變低。When the viscosity of the resin composition is adjusted, the type or content of the monomer to be contained may be selected for adjustment or adjustment using a viscosity adjuster. Specifically, when a monomer having a functional group or a chemical structure having an intermolecular interaction such as a hydrogen bond is used in a large amount, the viscosity of the resin composition becomes high. Further, when a low molecular weight monomer having no intermolecular interaction is used in a large amount, the viscosity of the resin composition becomes low.
本發明的實施形態的樹脂組成物（X）不論黏度是否比較低，所獲得的硬化物均可具有適度的硬度。其結果，可良好地進行壓模的剝離，且所形成的微細凹凸結構得到維持，可獲得耐擦傷性高、且發揮優異的撥水性的硬化物。The resin composition (X) according to the embodiment of the present invention may have an appropriate hardness regardless of whether the viscosity is relatively low or not. As a result, peeling of the stamper can be favorably performed, and the fine uneven structure formed can be maintained, and a cured product having high scratch resistance and exhibiting excellent water repellency can be obtained.
[成形品（微細凹凸結構體）/具有微細凹凸結構的物品] 可使本發明的實施形態的樹脂組成物（X）進行聚合及硬化來製成成形品。作為此種成形品，尤其表面具有微細凹凸結構的微細凹凸結構體極其有用。作為使用此種微細凹凸結構體的物品（具有微細凹凸結構的物品），例如可列舉：含有基材與表面具有微細凹凸結構的硬化樹脂層（微細凹凸結構體）者。[Molded product (fine concavo-convex structure) / article having a fine concavo-convex structure] The resin composition (X) of the embodiment of the present invention can be polymerized and cured to obtain a molded article. As such a molded article, a fine uneven structure having a fine uneven structure on the surface is particularly useful. For example, the article (the article having a fine concavo-convex structure) having such a fine concavo-convex structure is a cured resin layer (fine concavo-convex structure) containing a base material and a fine concavo-convex structure on its surface.
將使用此種微細凹凸結構體的物品的一例的示意剖面圖示於圖1的（a）、圖1的（b）中。A schematic cross-sectional view of an example of an article using such a fine uneven structure is shown in (a) of FIG. 1 and (b) of FIG. 1 .
圖1的（a）中所示的具有微細凹凸結構的物品10是於基材11（形成於基材11上的塗佈層15）上積層有使本發明的實施形態的活性能量線硬化性樹脂組成物（X）硬化而成的硬化樹脂層（表層）12者。硬化樹脂層12的表面具有微細凹凸結構。於該微細凹凸結構中，圓錐狀的凸部13（凹部14）以大致等間隔w1來形成。凸部13的形狀較佳為與高度方向垂直的剖面（與基材平面平行的面）的剖面面積自凸部的頂點側朝基材側連續地增大的形狀。藉由此種形狀，可連續地增大折射率，抑制由波長所引起的反射率的變動（波長依存性），並抑制可見光的散射，可形成低反射率的微細凹凸結構。另外，使用本發明的實施形態的樹脂組成物（X）所形成的具有微細凹凸結構的物品的具有多個凸部的部分中的水的接觸角度為80度以上。The article 10 having the fine uneven structure shown in Fig. 1(a) is laminated on the substrate 11 (the coating layer 15 formed on the substrate 11) to have active energy ray curability in the embodiment of the present invention. The cured resin layer (surface layer) 12 obtained by curing the resin composition (X). The surface of the hardened resin layer 12 has a fine uneven structure. In the fine uneven structure, the conical convex portions 13 (recess portions 14) are formed at substantially equal intervals w1. The shape of the convex portion 13 is preferably a shape in which the cross-sectional area of the cross section perpendicular to the height direction (the surface parallel to the substrate plane) continuously increases from the vertex side of the convex portion toward the substrate side. With such a shape, the refractive index can be continuously increased, the fluctuation of the reflectance due to the wavelength (wavelength dependence) can be suppressed, and the scattering of visible light can be suppressed, and a fine uneven structure having a low reflectance can be formed. In addition, the contact angle of water in the portion having the plurality of convex portions of the article having the fine uneven structure formed by the resin composition (X) of the embodiment of the present invention is 80 degrees or more.
於微細凹凸結構中，凸部（凹部）的間隔w1較佳為設為可見光的波長（具體而言，400 nm～780 nm）以下的距離。若凸部的間隔w1為400 nm以下，則可抑制可見光的散射，可作為抗反射膜而適宜地用於光學用途。w1更佳為50 nm～400 nm，進而更佳為50 nm～250 nm，特佳為80 nm～200 nm。In the fine uneven structure, the interval w1 between the convex portions (concave portions) is preferably a distance equal to or less than the wavelength of visible light (specifically, 400 nm to 780 nm). When the interval w1 of the convex portions is 400 nm or less, scattering of visible light can be suppressed, and it can be suitably used as an antireflection film for optical applications. The w1 is preferably from 50 nm to 400 nm, more preferably from 50 nm to 250 nm, and particularly preferably from 80 nm to 200 nm.
另外，凸部的高度（凹部的深度），即凹部的底點14a與凸部的頂部13a的垂直距離d1（以下，只要事先無特別說明，則稱為「凸部的高度」或「d1」）較佳為設為可抑制反射率因波長而變動的深度。具體而言，較佳為60 nm以上，更佳為90 nm以上，進而更佳為150 nm以上，特佳為180 nm以上。若d1為150 nm左右，則可使人最容易識別的550 nm的波長區域的光的反射率變得最低，若d1變成150 nm以上，則d1越高，可見光區域中的最高反射率與最低反射率的差變得越小。因此，若d1為150 nm以上，則反射光的波長依存性變小，目視下的色澤的差異不會被識別。Further, the height of the convex portion (the depth of the concave portion), that is, the vertical distance d1 between the bottom point 14a of the concave portion and the top portion 13a of the convex portion (hereinafter, unless otherwise specified, it is referred to as "the height of the convex portion" or "d1" It is preferable to make it possible to suppress the depth at which the reflectance changes due to the wavelength. Specifically, it is preferably 60 nm or more, more preferably 90 nm or more, further preferably 150 nm or more, and particularly preferably 180 nm or more. If d1 is about 150 nm, the reflectance of light in the wavelength region of 550 nm that is most easily recognized by humans becomes the lowest. If d1 becomes 150 nm or more, the higher the d1, the highest reflectance and the lowest in the visible light region. The difference in reflectance becomes smaller. Therefore, when d1 is 150 nm or more, the wavelength dependence of the reflected light becomes small, and the difference in color under visual observation is not recognized.
此處，凸部的間隔w1及高度d1可採用藉由如下的測定所獲得的測定值的算術平均值，所述測定是於利用場發射式掃描電子顯微鏡（商品名：JSM-7400F，日本電子（股份）製造）所得的加速電壓為3.00 kV的圖像中的測定。Here, the arithmetic mean value of the measured value obtained by the measurement using the field emission type scanning electron microscope (trade name: JSM-7400F, Japan Electronics) can be used for the interval w1 and the height d1 of the convex portion. (Production) (manufactured by the company) The obtained acceleration voltage is measured in an image of 3.00 kV.
另外，凸部13亦可為如圖1的（b）中所示的吊鐘狀。此外，作為垂直面的剖面面積自凸部的頂點側朝基材側連續地增大的形狀，例如可採用圓錐台狀。Further, the convex portion 13 may have a bell shape as shown in (b) of FIG. 1 . Further, a shape in which the cross-sectional area of the vertical surface continuously increases from the vertex side of the convex portion toward the base material side can be, for example, a truncated cone shape.
作為微細凹凸結構，較佳為大致圓錐形狀、角錐形狀等的突起（凸部）有規則地排列的結構。凸部的形狀較佳為與高度方向垂直的剖面（與基材平面平行的面）的剖面面積自基材側朝頂部連續地減少的形狀，即，沿著凸部的高度方向的剖面形狀較佳為三角形、梯形、吊鐘形等形狀。The fine concavo-convex structure is preferably a structure in which protrusions (convex portions) such as a substantially conical shape or a pyramid shape are regularly arranged. The shape of the convex portion is preferably a shape in which the cross-sectional area of the cross section perpendicular to the height direction (the surface parallel to the plane of the substrate) continuously decreases from the substrate side toward the top portion, that is, the cross-sectional shape along the height direction of the convex portion is higher. Good shape is triangular, trapezoidal, bell-shaped, etc.
微細凹凸結構並不限定於圖1的（a）、圖1的（b）中所示的實施形態。微細凹凸結構只要形成於硬化樹脂層（微細凹凸結構體）的表面上即可，例如可提供於基材的一面或兩面、或者整個面或一部分（需要透明性、超撥水性的部位）上設置硬化樹脂層，並於該硬化樹脂層的外側表面形成有微細凹凸結構者。The fine concavo-convex structure is not limited to the embodiment shown in (a) of FIG. 1 and (b) of FIG. The fine concavo-convex structure may be formed on the surface of the cured resin layer (fine concavo-convex structure), and may be provided, for example, on one or both sides of the substrate, or on the entire surface or a part (portion requiring transparency or super-water repellency). The resin layer is cured, and a fine uneven structure is formed on the outer surface of the cured resin layer.
作為此種微細凹凸結構，較佳為凸部間的間隔為可見光的波長以下的蛾眼結構，硬化物的表面的蛾眼結構藉由使折射率自空氣的折射率朝硬化物（凸部的根部分）的折射率連續地增大，而成為有效的抗反射手段。如上所述，凸部間的平均間隔w1較佳為可見光的波長以下，即400 nm以下，更佳為50 nm～400 nm，進而更佳為50 nm～250 nm，特佳為80 nm～200 nm。As such a fine concavo-convex structure, it is preferable that the interval between the convex portions is a moth-eye structure having a wavelength equal to or less than the wavelength of visible light, and the moth-eye structure on the surface of the cured product is made to have a refractive index from the refractive index of the air toward the cured material (the convex portion) The refractive index of the root portion is continuously increased to become an effective anti-reflection means. As described above, the average interval w1 between the convex portions is preferably below the wavelength of visible light, that is, below 400 nm, more preferably from 50 nm to 400 nm, further preferably from 50 nm to 250 nm, and particularly preferably from 80 nm to 200. Nm.
凸部間的平均間隔w1採用如下的值：於電子顯微鏡圖像中，測定50處鄰接的凸部間的間隔（自凸部的中心至鄰接的凸部的中心為止的距離），並對該些測定值進行算術平均所求出的值。The average interval w1 between the convex portions is a value obtained by measuring the interval between the adjacent convex portions (the distance from the center of the convex portion to the center of the adjacent convex portion) in the electron microscope image, and These measured values are obtained by arithmetic mean.
當w1處於所述範圍內時，尤其當w1為100 nm左右時，凸部的高度d1較佳為80 nm以上，更佳為120 nm以上，特佳為150 nm以上。若d1為80 nm以上，則謀求反射率的充分的降低，且由波長所引起的反射率的變動，即反射率的波長依存性少。就微細凹凸結構的耐擦傷性變得良好的觀點而言，d1較佳為500 nm以下，更佳為400 nm以下，特佳為300 nm以下。When w1 is in the above range, especially when w1 is about 100 nm, the height d1 of the convex portion is preferably 80 nm or more, more preferably 120 nm or more, and particularly preferably 150 nm or more. When d1 is 80 nm or more, the reflectance is sufficiently lowered, and the fluctuation of the reflectance due to the wavelength, that is, the wavelength dependency of the reflectance is small. From the viewpoint of the excellent scratch resistance of the fine uneven structure, d1 is preferably 500 nm or less, more preferably 400 nm or less, and particularly preferably 300 nm or less.
凸部的高度d1採用如下的值：於電子顯微鏡的30000倍圖像中，測定50處凸部的最頂部與存在於凸部間的凹部的最底部之間的沿著與基材平面垂直的方向的高度，並對該些測定值進行算術平均所求出的值。The height d1 of the convex portion is a value obtained by measuring the perpendicularly to the substrate plane between the topmost portion of the convex portion at 50 points and the bottommost portion of the concave portion existing between the convex portions in an image of 30,000 times of an electron microscope. The height of the direction and the value obtained by arithmetically averaging the measured values.
就充分地抑制反射率的觀點而言，凸部的縱橫比（凸部的高度d1/凸部間的平均間隔w1）較佳為0.3以上，更佳為0.5以上，特佳為0.7以上。就耐擦傷性變得良好的觀點而言，該縱橫比較佳為6以下，更佳為4以下，特佳為2以下。The aspect ratio of the convex portion (the height d1 of the convex portion or the average interval w1 between the convex portions) is preferably 0.3 or more, more preferably 0.5 or more, and particularly preferably 0.7 or more, from the viewpoint of sufficiently suppressing the reflectance. In view of the fact that the scratch resistance is good, the aspect ratio is preferably 6 or less, more preferably 4 or less, and particularly preferably 2 or less.
硬化樹脂層與基材較佳為其折射率的差為0.2以內，更佳為0.1以內，特佳為0.05以內。若折射率差為0.2以內，則可抑制硬化樹脂層與基材的界面中的反射。The hardened resin layer and the substrate preferably have a difference in refractive index of 0.2 or less, more preferably 0.1 or less, and particularly preferably 0.05 or less. When the refractive index difference is within 0.2, reflection in the interface between the cured resin layer and the substrate can be suppressed.
微細凹凸結構層的厚度例如可設定成0.5 μm～100 μm的範圍，較佳為可設定成1 μm～50 μm的範圍。The thickness of the fine uneven structure layer can be set, for example, in the range of 0.5 μm to 100 μm, and preferably in the range of 1 μm to 50 μm.
作為基材，只要是可支撐具有微細凹凸結構的硬化樹脂層者，則可為任何基材，當將微細凹凸結構體應用於顯示器構件時，較佳為透明的基材，即透光的基材。作為構成透明的基材的材料，例如可列舉：甲基丙烯酸甲酯（共）聚合體、聚碳酸酯、苯乙烯（共）聚合體、甲基丙烯酸甲酯-苯乙烯共聚物等合成高分子，二乙酸纖維素、三乙酸纖維素、乙酸丁酸纖維素等半合成高分子；聚對苯二甲酸乙二酯、聚乳酸等聚酯，聚醯胺，聚醯亞胺，聚醚碸，聚碸，聚乙烯，聚丙烯，聚甲基戊烯，聚氯乙烯，聚乙烯縮醛，聚醚酮，聚胺基甲酸酯，該些高分子的複合物（聚甲基丙烯酸甲酯與聚乳酸的複合物、聚甲基丙烯酸甲酯與聚氯乙烯的複合物等），玻璃等透明無機材料。As the substrate, any substrate can be used as long as it can support a hardened resin layer having a fine uneven structure. When the fine uneven structure is applied to a display member, a transparent substrate, that is, a light-transmitting substrate is preferable. material. Examples of the material constituting the transparent substrate include synthetic polymers such as methyl methacrylate (co)polymer, polycarbonate, styrene (co)polymer, and methyl methacrylate-styrene copolymer. , semi-synthetic polymer such as cellulose diacetate, cellulose triacetate, cellulose acetate butyrate; polyester such as polyethylene terephthalate or polylactic acid, polydecylamine, polyimine, polyether oxime, Polyfluorene, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinyl acetal, polyether ketone, polyurethane, complex of these polymers (polymethyl methacrylate and A composite of polylactic acid, a composite of polymethyl methacrylate and polyvinyl chloride, or a transparent inorganic material such as glass.
基材的形狀可為片狀、薄膜狀等的任一種。基材的製造方法亦無特別限定，例如可使用藉由射出成形、擠出成形、澆鑄成形等任一種製法所製造者。另外，出於改良密接性、抗靜電性、耐擦傷性、耐候性等特性的目的，亦可對透明基材的表面實施塗佈或電暈處理。The shape of the substrate may be any of a sheet shape, a film shape, and the like. The method for producing the substrate is not particularly limited, and for example, any one of production methods such as injection molding, extrusion molding, and casting molding can be used. Further, for the purpose of improving properties such as adhesion, antistatic property, scratch resistance, and weather resistance, the surface of the transparent substrate may be coated or corona treated.
此種微細凹凸結構體可用作抗反射膜，並可具有高耐擦傷性。另外，藉由選擇樹脂組成物（X）的組成種類或控制組成比，其硬化物除可獲得高耐擦傷性以外，亦可獲得優異的指紋去除性等污染物的去除效果。Such a fine uneven structure can be used as an antireflection film and can have high scratch resistance. Further, by selecting the composition type or the control composition ratio of the resin composition (X), in addition to obtaining high scratch resistance, the cured product can also obtain an excellent effect of removing contaminants such as fingerprint removal property.
[微細凹凸結構體的製造方法] 作為微細凹凸結構體的製造方法，例如可列舉：（1）將樹脂組成物配置在形成有微細凹凸結構的反轉結構的壓模與基材之間，藉由活性能量線的照射來使樹脂組成物硬化，而轉印壓模的凹凸形狀，其後剝離壓模的方法；（2）將壓模的凹凸形狀轉印至樹脂組成物上後剝離壓模，其後照射活性能量線來使樹脂組成物硬化的方法等。該些方法之中，就微細凹凸結構的轉印性、表面組成的自由度的觀點而言，特佳為（1）的方法。該方法是特別適合於使用可連續生產的傳送帶狀輥狀的壓模的情況、且生產性優異的方法。[Manufacturing Method of Fine Concavo-Convex Structure] As a method for producing the fine concavo-convex structure, for example, (1) the resin composition is disposed between a stamper having a reversed structure in which a fine uneven structure is formed, and a substrate. The method of curing the resin composition by irradiation of an active energy ray, transferring the uneven shape of the stamper, and then peeling off the stamper; (2) transferring the uneven shape of the stamper to the resin composition, and peeling off the stamper Then, a method of irradiating the active energy ray to cure the resin composition, and the like. Among these methods, the method of (1) is particularly preferable from the viewpoint of the transferability of the fine uneven structure and the degree of freedom of the surface composition. This method is particularly suitable for a case where a continuously-produced belt-shaped roll-shaped stamper is used, and the method is excellent in productivity.
（壓模） 壓模是於表面具有形成於微細凹凸結構體的表面上的微細凹凸結構的反轉結構者。作為壓模的材料，可列舉：金屬（包含表面形成有氧化皮膜者）、石英、玻璃、樹脂、陶瓷等。作為壓模的形狀，可列舉：輥狀、圓管狀、平板狀、片狀等。(Mold) The stamper is a reverse structure having a fine uneven structure formed on the surface of the fine uneven structure on the surface. Examples of the material of the stamper include metal (including those in which an oxide film is formed on the surface), quartz, glass, resin, ceramics, and the like. Examples of the shape of the stamper include a roll shape, a circular tube shape, a flat plate shape, and a sheet shape.
於壓模上形成微細凹凸結構的反轉結構的方法並無特別限定，作為其具體例，可列舉：電子束微影法、雷射光干涉法。例如，亦可將適當的光阻劑膜塗佈於適當的支撐基板上，利用紫外線雷射、電子束、X射線等光進行曝光，並進行顯影，藉此獲得形成有反轉微細凹凸結構的模具，並將該模具直接用作壓模。另外，亦可隔著藉由曝光·顯影而圖案化的光阻劑膜，利用乾式蝕刻選擇性地對支撐基板進行蝕刻，然後去除光阻劑膜，藉此於支撐基板本身上直接形成反轉微細凹凸結構。The method of forming the inverted structure of the fine uneven structure on the stamper is not particularly limited, and specific examples thereof include an electron beam lithography method and a laser light interference method. For example, an appropriate photoresist film may be applied onto a suitable support substrate, exposed to light such as ultraviolet laser, electron beam, or X-ray, and developed, thereby obtaining an inverted fine uneven structure. The mold is used directly as a stamper. Further, the support substrate may be selectively etched by dry etching through a photoresist film patterned by exposure and development, and then the photoresist film may be removed, thereby directly forming a reversal on the support substrate itself. Fine uneven structure.
另外，作為其他方法，亦可將陽極氧化多孔氧化鋁用作壓模。例如，亦可將如下的直徑為20 nm～200 nm的細孔結構用作壓模，所述直徑為20 nm～200 nm的細孔結構藉由將草酸、硫酸、磷酸等作為電解液，以規定的電壓對鋁基材進行陽極氧化而形成。根據該方法，以恆定電壓長時間對高純度鋁基材進行陽極氧化後，暫時去除氧化皮膜，並再次進行陽極氧化，藉此可自組織化地形成規則性非常高的細孔。進而，於第二次進行陽極氧化的步驟中，藉由將陽極氧化處理與孔徑擴大處理加以組合，亦可形成剖面為三角形或吊鐘形而非矩形的微細凹凸結構。另外，亦可藉由適宜調節陽極氧化處理與孔徑擴大處理的時間或條件，來使細孔最內部的角度變尖。Further, as another method, anodized porous alumina can also be used as a stamper. For example, the following pore structure having a diameter of 20 nm to 200 nm can be used as a stamper, and the pore structure having a diameter of 20 nm to 200 nm is obtained by using oxalic acid, sulfuric acid, phosphoric acid or the like as an electrolyte. The predetermined voltage is formed by anodizing the aluminum substrate. According to this method, after the high-purity aluminum substrate is anodized at a constant voltage for a long period of time, the oxide film is temporarily removed, and anodization is performed again, whereby pores having extremely high regularity can be formed self-organized. Further, in the step of performing the anodization for the second time, by combining the anodizing treatment and the pore diameter expanding treatment, it is also possible to form a fine uneven structure having a triangular or bell-shaped cross section instead of a rectangular shape. Further, the innermost angle of the pores can be sharpened by appropriately adjusting the time or condition of the anodizing treatment and the pore diameter expanding treatment.
進而，作為其他方法，亦可利用電鑄法等自具有微細凹凸結構的原始模具製作複製模具，並將其用作壓模。Further, as another method, a replica mold can be produced from an original mold having a fine uneven structure by an electroforming method or the like, and used as a stamper.
壓模本身的形狀並無特別限定，例如可為平板狀、傳送帶狀、輥狀的任一種。尤其，若設為傳送帶狀或輥狀，則可連續地轉印微細凹凸結構，而可進一步提高生產性。The shape of the stamper itself is not particularly limited, and may be, for example, a flat plate shape, a conveyor belt shape, or a roll shape. In particular, when it is set to a belt shape or a roll shape, the fine uneven structure can be continuously transferred, and productivity can be further improved.
（樹脂組成物（X）的供給與硬化步驟） 將樹脂組成物（X）供給並配置在此種壓模與基材之間。作為將樹脂組成物配置在壓模與基材間的方法，例如可於將樹脂組成物配置在壓模與基材間的狀態下按壓壓模與基材，藉此朝成型模腔中注入樹脂組成物。(Supply and Hardening Step of Resin Composition (X)) The resin composition (X) is supplied and disposed between the stamper and the substrate. As a method of disposing the resin composition between the stamper and the substrate, for example, the resin composition and the substrate can be pressed while the resin composition is placed between the stamper and the substrate, thereby injecting the resin into the molding cavity. Composition.
將樹脂組成物配置在壓模與基材間後，對樹脂組成物照射活性能量線來進行聚合硬化。作為聚合硬化的方法，較佳為利用紫外線照射的硬化處理。作為照射紫外線的燈，例如可使用：高壓水銀燈，金屬鹵化物燈、作為無電極燈的聚變燈（fusion lamp）、紫外線發光二極體（Ultraviolet-Light Emitting Diode，UV-LED）。After the resin composition is placed between the stamper and the substrate, the resin composition is irradiated with an active energy ray to carry out polymerization hardening. As a method of the polymerization hardening, a hardening treatment by ultraviolet irradiation is preferred. As the lamp that emits ultraviolet rays, for example, a high pressure mercury lamp, a metal halide lamp, a fusion lamp as an electrodeless lamp, and an ultraviolet-light emitting diode (UV-LED) can be used.
紫外線的照射量只要對應於聚合起始劑的吸收波長或含量來決定即可。通常，其累計光量較佳為400 mJ/cm2 ～4000 mJ/cm2 ，更佳為400 mJ/cm2 ～2000 mJ/cm2 。若累計光量為400 mJ/cm2 以上，則可使樹脂組成物充分硬化而抑制由硬化不足所引起的耐擦傷性下降。另外，就防止硬化物的著色或基材的劣化的觀點而言，較佳為將累計光量設定成4000 mJ/cm2 以下。照射強度亦無特別限制，但較佳為抑制成不會引起基材的劣化等的程度的輸出。The amount of ultraviolet rays to be irradiated may be determined in accordance with the absorption wavelength or content of the polymerization initiator. In general, the cumulative amount of light is preferably from 400 mJ/cm 2 to 4000 mJ/cm 2 , more preferably from 400 mJ/cm 2 to 2000 mJ/cm 2 . When the integrated light amount is 400 mJ/cm 2 or more, the resin composition can be sufficiently cured to suppress the deterioration of the scratch resistance caused by insufficient curing. Moreover, from the viewpoint of preventing the coloration of the cured product or the deterioration of the substrate, it is preferable to set the cumulative light amount to 4000 mJ/cm 2 or less. The irradiation intensity is not particularly limited, but it is preferably suppressed to an output that does not cause deterioration of the substrate or the like.
於樹脂組成物的聚合硬化後，剝離壓模，而可獲得作為具有微細凹凸結構的硬化物的微細凹凸結構體。After the polymerization curing of the resin composition, the stamper is peeled off, and a fine uneven structure as a cured product having a fine uneven structure can be obtained.
[微細凹凸結構體的用途] 以所述方式獲得的微細凹凸結構體中，壓模的微細凹凸結構以鑰匙與鑰匙孔的關係轉印至微細凹凸結構體的表面上，而具備高耐擦傷性。另外，可具有撥水性，並兼具污染物的附著防止效果。此種微細凹凸結構體可藉由連續的折射率的變化而顯現優異的抗反射性能，適合作為抗反射薄膜或立體形狀的成形品的抗反射膜。[Application of Fine Concavo-Convex Structure] In the fine concavo-convex structure obtained as described above, the fine concavo-convex structure of the stamper is transferred to the surface of the fine concavo-convex structure by the relationship between the key and the keyhole, and has high scratch resistance. . In addition, it has water repellency and has an effect of preventing adhesion of contaminants. Such a fine concavo-convex structure can exhibit excellent antireflection performance by a change in continuous refractive index, and is suitable as an antireflection film for an antireflection film or a molded article of a three-dimensional shape.
此種微細凹凸結構體適合作為如電腦、電視機、行動電話等液晶顯示裝置，電漿顯示面板，電致發光顯示器，陰極管顯示裝置般的圖像顯示裝置的顯示器構件。另外，可將微細凹凸結構體貼附於透鏡、櫥窗、眼鏡鏡片等透明構件的表面上來使用。此外，亦可應用於光波導、浮雕型全息圖（relief hologram）、透鏡、偏光分離元件等光學用途，或細胞培養片的用途。另外，可發揮撥水性而應用於鏡子或窗等建材、後視鏡用薄膜或窗戶用薄膜等車載用途、船底材料等。Such a fine uneven structure is suitable as a display member of an image display device such as a liquid crystal display device such as a computer, a television, or a mobile phone, a plasma display panel, an electroluminescence display, or a cathode tube display device. Further, the fine uneven structure body can be attached to the surface of a transparent member such as a lens, a window, or an eyeglass lens. In addition, it can also be applied to optical applications such as optical waveguides, relief holograms, lenses, and polarized light separation elements, or to cell culture sheets. In addition, it can be applied to vehicle materials such as mirrors or windows, mirrors for mirrors, and films for windows, etc., for water-repellent use, ship bottom materials, and the like.
[壓模的製作方法] 作為用於製作微細凹凸結構體的壓模，如上所述，利用陽極氧化多孔氧化鋁所製作者有用。以下，作為壓模的製作方法，使用圖2的（a）～圖2的（f）的步驟圖來說明藉由陽極氧化而於鋁基板的表面上形成規定形狀的多個微細細孔的方法。[Manufacturing Method of Die] As a stamper for producing a fine uneven structure, as described above, it is useful for producing an anodized porous alumina. Hereinafter, as a method of producing a stamper, a method of forming a plurality of fine pores having a predetermined shape on the surface of an aluminum substrate by anodization using a step diagram of (a) to (f) of FIG. 2 will be described. .
步驟（a） 步驟（a）是於恆定電壓下，在電解液中對鋁基材30進行陽極氧化而於鋁基材的表面上形成氧化皮膜的步驟。 鋁基材較佳為使用純度99%以上的鋁，更佳為純度99.5%以上，進而更佳為純度99.8%以上。若鋁的純度高，則當進行了陽極氧化時，難以形成因雜質的偏析而使可見光散射的大小的凹凸結構，另外，藉由陽極氧化所形成的細孔有規則地形成。鋁基材的形狀可為輥狀、圓管狀、平板狀、片狀等所期望的形狀，當以連續的薄膜或片的形態獲得微細凹凸結構體時，較佳為設為輥狀。Step (a) Step (a) is a step of forming an oxide film on the surface of the aluminum substrate by anodizing the aluminum substrate 30 in an electrolytic solution at a constant voltage. The aluminum substrate is preferably aluminum having a purity of 99% or more, more preferably 99.5% or more, and still more preferably 99.8% or more. When the purity of aluminum is high, when anodization is performed, it is difficult to form a concavo-convex structure having a size that scatters by visible light due to segregation of impurities, and pores formed by anodization are regularly formed. The shape of the aluminum base material may be a desired shape such as a roll shape, a circular tube shape, a flat plate shape, or a sheet shape. When the fine uneven structure body is obtained in the form of a continuous film or sheet, it is preferably a roll shape.
鋁基材因附著有加工成規定的形狀時所使用的油，故較佳為事先進行脫脂處理，並藉由電解研磨處理（蝕刻處理）來使表面變得平滑。Since the aluminum base material adheres to the oil used in processing into a predetermined shape, it is preferable to perform degreasing treatment in advance and to smooth the surface by electrolytic polishing treatment (etching treatment).
若對此種表面處理鋁基材進行陽極氧化，則形成具有細孔31的氧化皮膜32。When such a surface-treated aluminum substrate is anodized, an oxide film 32 having pores 31 is formed.
作為電解液，可使用硫酸、草酸、磷酸等。當使用草酸作為電解液時，草酸的濃度較佳為0.7 M以下。若草酸的濃度為0.7 M以下，則將電流值抑制得低，可形成組織細密的氧化皮膜。化成電壓較佳為30 V～60 V。若化成電壓為30 V～60 V，則可形成以週期為100 nm左右的規則性形成有細孔的陽極氧化多孔氧化鋁層。不論化成電壓高於該範圍還是低於該範圍，均存在所形成的細孔的規則性下降的傾向。電解液的溫度較佳為60℃以下，更佳為45℃以下。若電解液的溫度為60℃以下，則抑制所謂的「燃燒」的產生，並抑制細孔破損、或表面融化而形成不規則的細孔。As the electrolytic solution, sulfuric acid, oxalic acid, phosphoric acid or the like can be used. When oxalic acid is used as the electrolytic solution, the concentration of oxalic acid is preferably 0.7 M or less. When the concentration of oxalic acid is 0.7 M or less, the current value is suppressed to be low, and an oxide film having a fine structure can be formed. The formation voltage is preferably from 30 V to 60 V. When the formation voltage is 30 V to 60 V, an anodized porous alumina layer having pores regularly formed at a cycle of about 100 nm can be formed. Regardless of whether the formation voltage is higher than the range or lower than the range, there is a tendency that the regularity of the formed pores is lowered. The temperature of the electrolytic solution is preferably 60 ° C or lower, more preferably 45 ° C or lower. When the temperature of the electrolytic solution is 60° C. or less, the occurrence of so-called “burning” is suppressed, and the pores are prevented from being damaged or the surface is melted to form irregular pores.
另外，當使用硫酸作為電解液時，硫酸的濃度較佳為0.7 M以下。若硫酸的濃度為0.7 M以下，則將電流值抑制得低，可形成組織細密的氧化皮膜。化成電壓較佳為25 V～30 V。若化成電壓為25 V～30 V，則可形成以週期為63 nm左右的規則性形成有細孔的陽極氧化多孔氧化鋁層。不論化成電壓高於該範圍還是低於該範圍，均存在所形成的細孔的規則性下降的傾向。電解液的溫度較佳為30℃以下，更佳為20℃以下。若電解液的溫度為30℃以下，則抑制所謂的「燃燒」的產生，並抑制細孔破損、或表面融化而形成不規則的細孔。Further, when sulfuric acid is used as the electrolytic solution, the concentration of sulfuric acid is preferably 0.7 M or less. When the concentration of sulfuric acid is 0.7 M or less, the current value is suppressed to be low, and an oxide film having a fine structure can be formed. The formation voltage is preferably 25 V to 30 V. When the formation voltage is 25 V to 30 V, an anodized porous alumina layer having pores regularly formed with a period of about 63 nm can be formed. Regardless of whether the formation voltage is higher than the range or lower than the range, there is a tendency that the regularity of the formed pores is lowered. The temperature of the electrolytic solution is preferably 30 ° C or lower, more preferably 20 ° C or lower. When the temperature of the electrolytic solution is 30° C. or less, the occurrence of so-called “burning” is suppressed, and the pores are prevented from being damaged or the surface is melted to form irregular pores.
步驟（b） 步驟（b）是去除氧化皮膜，並以與在步驟（a）中形成於氧化皮膜上的細孔31部分相對應的方式，於鋁基材的表面上形成陽極氧化的細孔產生點的步驟。即，若去除步驟（a）中所形成的氧化皮膜32，則在對應於細孔31部分的位置的鋁基材表面上形成凹部33。Step (b) Step (b) is to remove the oxide film and form anodized pores on the surface of the aluminum substrate in a manner corresponding to the portion of the pores 31 formed on the oxide film in the step (a). The step of generating points. That is, when the oxide film 32 formed in the step (a) is removed, the concave portion 33 is formed on the surface of the aluminum substrate corresponding to the portion of the pore 31.
藉由將該凹部33設為陽極氧化的細孔產生點，可產生有規則地排列的細孔。於去除氧化皮膜時，使用不溶解鋁、而選擇性地溶解氧化皮膜的溶液。作為此種溶液，例如有鉻酸/磷酸混合液等。By forming the dots in the recessed portion 33 as anodized pores, regular pores can be produced. When the oxide film is removed, a solution which does not dissolve aluminum and selectively dissolves the oxide film is used. Examples of such a solution include a chromic acid/phosphoric acid mixed solution.
步驟（c） 步驟（c）是再次對鋁基材進行陽極氧化，而於細孔產生點上形成氧化皮膜，藉此形成細孔的步驟。即，再次對在步驟（b）中去除了氧化皮膜的鋁基材30進行陽極氧化，而形成具有圓柱狀的細孔35的氧化皮膜34。陽極氧化能夠以與步驟（a）相同的條件來進行。越延長陽極氧化的時間，可獲得越深的細孔。Step (c) Step (c) is a step of anodizing the aluminum substrate again to form an oxide film on the pore generating point, thereby forming pores. That is, the aluminum base material 30 from which the oxide film has been removed in the step (b) is anodized again to form the oxide film 34 having the cylindrical pores 35. The anodization can be carried out under the same conditions as in the step (a). The longer the anodization time is, the deeper the pores can be obtained.
步驟（d） 步驟（d）是擴大細孔的直徑的步驟。即，使再次進行了陽極氧化的鋁基材浸漬於溶解氧化皮膜的溶液中來擴大細孔35的直徑（以下稱為「細孔直徑擴大處理」）。 作為溶解氧化皮膜的溶液，例如可使用5質量%左右的磷酸水溶液等。越延長細孔直徑擴大處理的時間，越可擴大細孔直徑，因此對應於目標形狀來設定處理時間。Step (d) Step (d) is a step of enlarging the diameter of the pores. In other words, the aluminum substrate which has been anodized again is immersed in a solution in which the oxide film is dissolved to enlarge the diameter of the pores 35 (hereinafter referred to as "pore diameter enlargement treatment"). As the solution for dissolving the oxide film, for example, a phosphoric acid aqueous solution of about 5% by mass or the like can be used. The longer the pore diameter enlargement treatment is performed, the larger the pore diameter can be enlarged, and thus the treatment time is set corresponding to the target shape.
步驟（e） 步驟（e）是再次對細孔直徑擴大處理後的鋁基材進行陽極氧化的步驟。若再次對鋁基材進行陽極氧化，則伴隨氧化皮膜34變厚，細孔35的深度伸長。再者，陽極氧化能夠以與步驟（a）（及步驟（c））相同的條件來進行。越延長陽極氧化的時間，越可將細孔形成得深。Step (e) Step (e) is a step of anodizing the aluminum substrate after the pore diameter expansion treatment. When the aluminum base material is anodized again, the thickness of the pores 35 is elongated as the oxide film 34 is thickened. Further, the anodization can be carried out under the same conditions as in the step (a) (and the step (c)). The longer the anodization time is, the deeper the pores can be formed.
步驟（f） 步驟（f）是重複進行步驟（d）與步驟（e），而反覆進行細孔35的直徑擴大與伸長的步驟。藉由該步驟，形成具有直徑自開口部朝深度方向連續地減少的形狀的細孔35的氧化皮膜34，其結果，可獲得具有多個微細細孔的陽極氧化鋁形成於鋁基材的表面上的壓模20。步驟（f）的最後較佳為以步驟（d）來結束。Step (f) Step (f) is a step of repeating steps (d) and (e), and repeating the diameter expansion and elongation of the pores 35. By this step, the oxide film 34 having the pores 35 having a shape continuously decreasing in diameter from the opening portion in the depth direction is formed, and as a result, anodized alumina having a plurality of fine pores can be obtained on the surface of the aluminum substrate. The upper mold 20. The end of step (f) preferably ends with step (d).
步驟（f）的重複次數較佳為合計為3次以上，更佳為5次以上。若重複次數為3次以上，則可形成直徑連續地變化的細孔，藉由此種壓模，可形成具有能夠降低反射率的蛾眼結構的表面的硬化物。The number of repetitions of the step (f) is preferably 3 or more, more preferably 5 or more. When the number of repetitions is three or more, pores having a continuously varying diameter can be formed, and by such a stamper, a cured product having a surface of a moth-eye structure capable of reducing reflectance can be formed.
細孔35的形狀為形成於物品的表面上的微細凹凸結構的反轉結構，具體而言，可列舉大致圓錐形狀、角錐形狀、圓柱形狀等，較佳為如圓錐形狀、角錐形狀等般，與深度方向正交的方向的細孔剖面面積自最表面朝深度方向連續地減少的形狀。The shape of the pores 35 is an inverted structure of the fine concavo-convex structure formed on the surface of the article, and specifically, a substantially conical shape, a pyramid shape, a cylindrical shape, or the like is preferable, and a conical shape, a pyramid shape, or the like is preferable. The shape of the pore cross-sectional area in the direction orthogonal to the depth direction continuously decreases from the outermost surface toward the depth direction.
細孔35間的平均間隔較佳為可見光的波長以下，即400 nm以下，另外，較佳為20 nm以上。細孔間的平均間隔是測定50處電子顯微鏡圖像中的鄰接的細孔間的間隔（自細孔的中心至鄰接的細孔的中心為止的距離），並採用該些值的平均值。The average interval between the pores 35 is preferably not more than the wavelength of visible light, that is, 400 nm or less, and more preferably 20 nm or more. The average interval between the pores was measured by the interval between adjacent pores in the electron microscope image at 50 (the distance from the center of the pore to the center of the adjacent pore), and the average value of these values was used.
細孔35的深度較佳為80 nm～500 nm，更佳為120 nm～400 nm，進而更佳為150 nm～300 nm，尤其當平均間隔為100 nm左右時，理想的是處於此種範圍內。細孔的深度是測定50處電子顯微鏡30000倍圖像中的細孔的最底部與頂部間的距離，並採用該些值的平均值。The depth of the pores 35 is preferably from 80 nm to 500 nm, more preferably from 120 nm to 400 nm, and even more preferably from 150 nm to 300 nm, especially when the average interval is about 100 nm, and it is desirable to be in such a range. Inside. The depth of the pores is the distance between the bottommost portion and the top of the pores in the 30,000-times image of the 50 electron microscope, and the average value of the values is used.
細孔35的縱橫比（深度/平均間隔）較佳為0.8～5.0，更佳為1.2～4.0，進而更佳為1.5～3.0。The aspect ratio (depth/average interval) of the pores 35 is preferably from 0.8 to 5.0, more preferably from 1.2 to 4.0, still more preferably from 1.5 to 3.0.
亦可利用脫模劑對壓模的形成有微細凹凸結構之側的表面進行處理。作為脫模劑，可列舉矽酮樹脂、氟樹脂、氟化合物、磷酸酯等，特佳為磷酸酯。作為市售品，可列舉：阿克塞爾（Axel）公司製造的商品名：Mold Uiz INT-1856，日光化學公司製造的商品名：TDP-10、TDP-8、TDP-6、TDP-2、DDP-10、DDP-8、DDP-6、DDP-4、DDP-2、TLP-4、TCP-5、DLP-10，城北化學工業公司製造的商品名：JP-506H、JP-512、JP-513、JAMP-8、JAMP-12，大八化學工業公司製造的製品名：AP-8、AP-10、MP-10，SC有機化學公司製造的商品名：福斯萊克斯（Phoslex）系列：A-8、A-10、A-12、A-13、A-18、A-18D、A-180L等。The surface of the stamper on the side where the fine uneven structure is formed may be treated with a release agent. Examples of the release agent include an anthrone resin, a fluororesin, a fluorine compound, a phosphate, and the like, and particularly preferably a phosphate. As a commercial item, the brand name: Mold Uiz INT-1856, and the brand name of TDP-10, TDP-8, TDP-6, TDP-2 by Axel Corporation are mentioned. , DDP-10, DDP-8, DDP-6, DDP-4, DDP-2, TLP-4, TCP-5, DLP-10, trade names manufactured by Seongbuk Chemical Industry Co., Ltd.: JP-506H, JP-512, JP-513, JAMP-8, JAMP-12, manufactured by Daiba Chemical Industry Co., Ltd. Product name: AP-8, AP-10, MP-10, manufactured by SC Organic Chemical Co., Ltd. Trade name: Phoslex Series: A-8, A-10, A-12, A-13, A-18, A-18D, A-180L, etc.
表面具有使用於上所製作的壓模所形成的微細凹凸結構的物品例如如圖1的（a）所示，具有形成於基材11的表面上的硬化樹脂層12。硬化樹脂層12具有自使樹脂組成物與所述壓模接觸並進行硬化而成的樹脂硬化物所形成的具有多個凸部13的微細凹凸結構。The article having the fine uneven structure formed on the surface of the stamper produced on the surface has a cured resin layer 12 formed on the surface of the substrate 11, for example, as shown in FIG. 1(a). The hardened resin layer 12 has a fine uneven structure having a plurality of convex portions 13 formed of a cured resin obtained by bringing a resin composition into contact with the stamper and curing the resin.
[壓印用原料等] 本發明的壓印用原料只要是包含本發明的樹脂組成物者，則並無特別限制，可直接使用樹脂組成物，亦可對應於目標成形品而含有各種添加劑。[Materials for Imprinting, etc.] The raw material for imprint of the present invention is not particularly limited as long as it contains the resin composition of the present invention, and a resin composition may be used as it is, or various additives may be contained in accordance with the target molded article.
壓印用原料亦可用於使用壓模，並藉由UV硬化、或進而藉由加熱硬化所進行的硬化物的成形。亦可使用如下的方法：將壓模按壓於藉由加熱等而半硬化的狀態的樹脂組成物上，進行形狀轉印後自壓模剝離，然後藉由熱或UV來完全地進行硬化。The raw material for imprinting can also be used for forming a cured product by using a stamper and hardening by UV or further by heat hardening. A method in which the stamper is pressed against a resin composition in a state of being semi-cured by heating or the like, and the shape is transferred and peeled off from the stamper, and then completely cured by heat or UV.
此外，所述樹脂組成物亦可用作於各種基材上形成硬化被膜的原料，亦可作為塗佈材來形成塗膜，並照射活性能量線來形成硬化物。Further, the resin composition may be used as a raw material for forming a cured film on various substrates, or may be formed as a coating material to form a coating film, and irradiated with an active energy ray to form a cured product.
[具有微細凹凸結構的物品的連續的製造方法] 表面具有微細凹凸結構的物品例如可使用圖3所示的製造裝置來連續地製造。[Continuous Manufacturing Method of Article Having Fine Concavo-Concave Structure] An article having a fine uneven structure on the surface can be continuously manufactured, for example, using the manufacturing apparatus shown in Fig. 3 .
於圖3所示的製造裝置中設置有表面具有微細凹凸結構的反轉結構（省略圖示）的輥狀壓模41、及收納樹脂組成物的槽43。自槽43朝伴隨輥狀壓模41的旋轉而沿著其表面移動的透光性的帶狀薄膜的基材42與輥狀壓模41之間供給樹脂組成物。在輥狀壓模41與藉由氣壓缸45來調整夾持壓（nip pressure）的夾輥46之間，夾持基材42及樹脂組成物，將樹脂組成物均勻地遍布於基材42與輥狀壓模41之間的同時，填充至輥狀壓模41的微細凹凸結構的凹部內。於輥狀壓模41的下方設置活性能量線照射裝置48，透過基材42對樹脂組成物照射活性能量線，而可使樹脂組成物硬化。藉此，形成轉印有輥狀壓模41的表面的微細凹凸結構的硬化樹脂層44。其後，利用剝離輥47，自輥狀壓模41剝離表面形成有微細凹凸結構的硬化樹脂層44與基材42一體化而成的連續的物品（微細凹凸結構體）40。In the manufacturing apparatus shown in FIG. 3, a roll-shaped stamper 41 having an inverted structure (not shown) having a fine uneven structure on the surface, and a groove 43 accommodating a resin composition are provided. The resin composition is supplied from the groove 43 to the base material 42 of the light-transmissive strip-shaped film which moves along the surface along with the rotation of the roll-shaped stamper 41, and the roll-shaped stamper 41. The base material 42 and the resin composition are sandwiched between the roll-shaped stamper 41 and the nip roller 46 which adjusts the nip pressure by the pneumatic cylinder 45, and the resin composition is uniformly distributed over the base material 42 and At the same time as the roll-shaped stamper 41, it is filled in the concave portion of the fine uneven structure of the roll-shaped stamper 41. The active energy ray irradiation device 48 is disposed below the roll-shaped stamper 41, and the resin composition is irradiated with the active energy ray through the base material 42 to cure the resin composition. Thereby, the hardened resin layer 44 of the fine uneven structure which transferred the surface of the roll-shaped stamper 41 was formed. Then, the continuous article (fine uneven structure) 40 in which the cured resin layer 44 having the fine uneven structure and the base material 42 are formed on the surface is peeled off from the roll-shaped stamper 41 by the peeling roller 47.
作為活性能量線照射裝置48，較佳為高壓水銀燈、金屬鹵化物燈等，該情況下的光照射能量較佳為100 mJ/cm2 ～10000 mJ/cm2 。作為基材42的材質，可使用：丙烯酸系樹脂、聚碳酸酯、苯乙烯系樹脂、聚酯、纖維素系樹脂（三乙醯纖維素等）、聚烯烴、脂環式聚烯烴等。The active energy ray irradiation device 48 is preferably a high pressure mercury lamp, a metal halide lamp or the like, and the light irradiation energy in this case is preferably from 100 mJ/cm 2 to 10000 mJ/cm 2 . As a material of the base material 42, an acrylic resin, a polycarbonate, a styrene resin, a polyester, a cellulose resin (such as triacetonitrile cellulose), a polyolefin, or an alicyclic polyolefin can be used.
[具有微細凹凸結構的物品的用途] 本發明的實施形態的具有微細凹凸結構的物品因微細凹凸結構的耐擦傷性高、且具有優異的撥水性，故可期待作為抗反射物品（抗反射薄膜、抗反射膜等）、光波導、浮雕型全息圖、透鏡、偏光分離元件等光學物品，及撥水薄膜的用途展開，尤其適合於作為抗反射物品與撥水薄膜的用途。[Application of the article having the fine uneven structure] The article having the fine uneven structure according to the embodiment of the present invention is expected to be an antireflection article (antireflection film) because the fine uneven structure has high scratch resistance and excellent water repellency. Optical instruments such as optical waveguides, embossed holograms, lenses, and polarized light separation elements, and the use of water-repellent films are particularly suitable for use as anti-reflective articles and water-repellent films.
作為抗反射物品，例如可列舉：設置於圖像顯示裝置（液晶顯示裝置、電漿顯示面板、電致發光顯示器、陰極管顯示裝置等）、透鏡、櫥窗、眼鏡等的表面上的抗反射膜、抗反射薄膜、抗反射片等。當用於圖像顯示裝置時，可將抗反射薄膜直接貼附於圖像顯示面上，亦可於構成圖像顯示面的構件的表面上直接形成抗反射膜，亦可於前面板上形成抗反射膜。Examples of the antireflection article include an antireflection film provided on the surface of an image display device (a liquid crystal display device, a plasma display panel, an electroluminescence display, a cathode tube display device, etc.), a lens, a window, glasses, or the like. , anti-reflective film, anti-reflective sheet, etc. When used in an image display device, the anti-reflection film may be directly attached to the image display surface, or an anti-reflection film may be directly formed on the surface of the member constituting the image display surface, or may be formed on the front panel. Anti-reflective film.
作為撥水薄膜，可用作汽車用後視鏡或窗戶類的防積液薄膜、或防積雪薄膜。另外，藉由用於太陽電池或建材用玻璃等在室外使用的透明基材，可同時利用提昇透光率的效果與賦予由撥水性所產生的防污性的效果。 [實施例]As a water-repellent film, it can be used as an anti-liquid film for automotive rearview mirrors or windows, or as a snow-proof film. In addition, the transparent substrate used for outdoor use in solar cells or glass for building materials can simultaneously utilize the effect of improving the light transmittance and the effect of imparting antifouling properties by water repellency. [Examples]
以下，藉由實施例來更詳細地說明本發明。首先，對評價方法及壓模的製造例進行說明。Hereinafter, the present invention will be described in more detail by way of examples. First, an evaluation method and a manufacturing example of a stamper will be described.
[評價方法] [1.硬化性液體的外觀] 向透明的玻璃瓶（容量為20 mL）中加入硬化性液體10 mL，於室溫23℃的條件下照著螢光燈而以目視觀察有無混濁，並藉由以下的指標來評價硬化性液體（活性能量線硬化性樹脂組成物）的外觀。 ○：完全無混濁，透明。 ×：有混濁。[Evaluation method] [1. Appearance of curable liquid] Add 10 mL of a curable liquid to a transparent glass bottle (capacity: 20 mL), and visually observe the presence or absence of a fluorescent lamp at room temperature of 23 ° C. It was turbid, and the appearance of the curable liquid (active energy ray-curable resin composition) was evaluated by the following indexes. ○: completely turbid and transparent. ×: There is turbidity.
[2.耐擦傷性] 使用磨耗試驗機（新東科學公司製造，製品名：海東特里博吉爾型（HEIDON TRIBOGEAR TYPE）-30S），對放置於物品的表面上的切割成2 cm見方的鋼絲絨（日本鋼絲絨（Nippon Steel Wool）公司製造，製品名：邦斯達（Bonstar）#0000）施加100 g（25 gf/cm2 =0.245 N/cm2 ）的負荷，以往返距離：30 mm、頂端速度：平均100 mm/sec往返10次，並評價物品的表面的外觀。於評價外觀時，將物品貼附於2.0 mm厚的黑色壓克力板（三菱麗陽公司製造，製品名：艾克里萊特（Acrylite））的一面上，於室內照著螢光燈而以目視進行觀察，並藉由以下的指標來進行評價。 A：於擦傷部分中可確認的劃痕未滿10條。 B：於擦傷部分中可確認的劃痕為10條以上、未滿50條。 C：於擦傷部分中可確認的劃痕為50條以上。或擦傷部分看上去白色模糊。[2. Scratch resistance] Using an abrasion tester (manufactured by Shinto Scientific Co., Ltd., product name: HEIDON TRIBOGEAR TYPE -30S), the surface placed on the surface of the article was cut into 2 cm square. Steel wool (manufactured by Nippon Steel Wool Co., Ltd., product name: Bonstar #0000), applying a load of 100 g (25 gf/cm 2 = 0.245 N/cm 2 ) at a round trip distance: 30 Mm, tip speed: 10 round trips on average of 100 mm/sec, and evaluated the appearance of the surface of the article. When evaluating the appearance, the article is attached to one side of a 2.0 mm thick black acrylic plate (manufactured by Mitsubishi Rayon Co., Ltd., product name: Acrylite), and is illuminated indoors with a fluorescent lamp. The observation was visually observed and evaluated by the following indicators. A: There are less than 10 scratches that can be confirmed in the scratched portion. B: The number of scratches that can be confirmed in the scratched portion is 10 or more and less than 50. C: 50 or more scratches can be confirmed in the scratched portion. Or the scratched part looks white and blurred.
[3.連續轉印性試驗] 將10 μL的活性能量線硬化性樹脂組成物滴加至壓模的形成有微細凹凸結構之側，使聚對苯二甲酸乙二酯薄膜（以下記作「PET薄膜」）覆蓋後，施加50 N的負荷。其後，利用UV照射機（高壓水銀燈，累計光量為1100 mJ/cm2 ）照射紫外線，而使樹脂組成物硬化。繼而，將硬化樹脂層連同PET薄膜自壓模進行脫模，藉此獲得於PET薄膜的表面上轉印有微細凹凸結構的物品。對1個壓模重複進行以上的轉印作業，於轉印次數為第200次時測定自壓模的剝離力。剝離力的測定是於自壓模對硬化後的樣品（PET薄膜上的硬化樹脂層）進行脫模時，將壓模當作被黏著體，將硬化樹脂層與基材（PET薄膜）當作黏著膠帶，進行依據JISZ0237的90°剝離試驗，並測定自壓模進行脫模時的剝離力。[3. Continuous transfer property test] 10 μL of the active energy ray-curable resin composition was dropped onto the side of the stamper where the fine uneven structure was formed, and a polyethylene terephthalate film (hereinafter referred to as " After the PET film was covered, a load of 50 N was applied. Thereafter, the resin composition was cured by irradiating ultraviolet rays with a UV irradiator (high-pressure mercury lamp and an integrated light amount of 1,100 mJ/cm 2 ). Then, the cured resin layer was released from the stamper together with the PET film, whereby an article having a fine uneven structure transferred onto the surface of the PET film was obtained. The above transfer operation was repeated for one stamper, and the peeling force from the stamper was measured when the number of times of transfer was 200. The peeling force is measured by demolding the cured sample (the hardened resin layer on the PET film) from the stamper, using the stamper as the adherend, and treating the cured resin layer and the substrate (PET film) as The adhesive tape was subjected to a 90° peel test in accordance with JIS Z0237, and the peeling force at the time of demolding from the stamper was measured.
[4.水接觸角] 使用自動接觸角計（協和界面科學公司製造，製品名：DM-501），將離子交換水1 μL滴加至物品的表面上，並測定接觸角。接觸角的測定是於3處實施，並採用其平均值。[4. Water contact angle] Using an automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., product name: DM-501), 1 μL of ion-exchanged water was dropped onto the surface of the article, and the contact angle was measured. The contact angle was measured at three locations and the average was used.
[5.壓模的細孔的測定] 對包含陽極氧化多孔氧化鋁的壓模的一部分的縱剖面進行1分鐘鉑（Pt）蒸鍍，然後利用場發射式掃描電子顯微鏡（日本電子公司製造，製品名：JSM-7400F）以加速電壓3.00 kV進行觀察，並測定鄰接的細孔的間隔（週期）及細孔的深度。具體而言，分別各測定10處，並將其平均值設為測定值。[5. Measurement of pores of a stamper] A longitudinal section of a part of a stamper containing anodized porous alumina was subjected to platinum (Pt) vapor deposition for 1 minute, and then a field emission scanning electron microscope (manufactured by JEOL Ltd., Product name: JSM-7400F) The acceleration voltage was observed at 3.00 kV, and the interval (period) of the adjacent pores and the depth of the pores were measured. Specifically, 10 points were each measured, and the average value was made into the measured value.
[微細凹凸結構轉印用壓模的製作] 將純度為99.99質量%、且經電解研磨的厚度為2 mm的f65mm鋁圓盤用作鋁基材。[Preparation of a stamper for fine uneven structure transfer] An f65 mm aluminum disk having a purity of 99.99% by mass and having an electrolytically polished thickness of 2 mm was used as an aluminum substrate.
步驟（a）： 於0.3 M草酸水溶液中，以直流40 V、溫度16℃的條件對該鋁圓盤進行6小時陽極氧化。 步驟（b）： 使形成有氧化皮膜的鋁圓盤於6質量%磷酸/1.8質量%鉻酸混合水溶液中浸漬3小時，而去除氧化皮膜。 步驟（c）： 於0.3 M草酸水溶液中，以直流40 V、溫度16℃的條件對去除了氧化皮膜的鋁圓盤進行30秒陽極氧化。Step (a): The aluminum disk was anodized for 6 hours in a 0.3 M aqueous solution of oxalic acid under the conditions of a direct current of 40 V and a temperature of 16 °C. Step (b): The aluminum disk formed with the oxide film was immersed in a 6 mass% phosphoric acid/1.8 mass% chromic acid mixed aqueous solution for 3 hours to remove the oxide film. Step (c): The aluminum disk from which the oxide film was removed was anodized in a 0.3 M aqueous solution of oxalic acid under the conditions of a direct current of 40 V and a temperature of 16 ° C for 30 seconds.
步驟（d）： 使形成有氧化皮膜的鋁圓盤於32℃的5質量%磷酸水溶液中浸漬8分鐘，而進行細孔直徑擴大處理。 步驟（e）： 於0.3 M草酸水溶液中，以直流40 V、溫度16℃的條件對該處理後的鋁圓盤進行30秒陽極氧化。Step (d): The aluminum disk on which the oxide film was formed was immersed in a 5 mass% phosphoric acid aqueous solution at 32 ° C for 8 minutes to carry out a pore diameter enlargement treatment. Step (e): The treated aluminum disk was anodized in a 0.3 M aqueous solution of oxalic acid under the conditions of a direct current of 40 V and a temperature of 16 ° C for 30 seconds.
步驟（f）： 將所述步驟（d）及步驟（e）合計重複5次，而獲得表面形成有具有細孔的平均間隔（週期）：100 nm、深度：200 nm的大致圓錐形狀的細孔的陽極氧化鋁的模具（壓模）。Step (f): repeating the steps (d) and (e) in total 5 times, and obtaining a surface having an average interval (period) having pores: 100 nm, depth: 200 nm, a substantially conical shape Hole in the anodized aluminum mold (die).
使所獲得的模具於脫模劑（商品名：TDP-8，日光化學公司製造）的0.1質量%水溶液中浸漬10分鐘，然後提起並風乾一夜，藉此實施脫模處理。The obtained mold was immersed in a 0.1% by mass aqueous solution of a release agent (trade name: TDP-8, manufactured by Nikko Chemical Co., Ltd.) for 10 minutes, and then lifted and air-dried overnight to carry out a mold release treatment.
[活性能量線硬化性樹脂組成物（X）] 實施例及比較例中所使用的活性能量線硬化性樹脂組成物（X）中所含有的聚合性成分（A）、聚合性成分（B）、聚合性成分（C）、其他聚合性成分（D）、光聚合起始劑（E）、其他成分（G）、內部脫模劑（F）如下述的表1所述。[Active energy ray-curable resin composition (X)] The polymerizable component (A) and the polymerizable component (B) contained in the active energy ray-curable resin composition (X) used in the examples and the comparative examples. The polymerizable component (C), the other polymerizable component (D), the photopolymerization initiator (E), the other component (G), and the internal mold release agent (F) are as described in Table 1 below.
[表1]
[實施例1] 作為活性能量線硬化性樹脂組成物（X），製備表2中所示的組成的樹脂。將數滴該活性能量線硬化性樹脂組成物滴落至微細凹凸結構轉印用壓模的表面上，利用PET薄膜（東洋紡公司製造，製品名：A4300，厚度：50 μm）一面擠壓擴大一面包覆。其後，使用無電極型的UV燈（賀利氏（Heraeus）公司製造，D閥），以於365 nm的波長中所測定的累計光量變成1000 mJ/cm2 的方式，自薄膜側照射紫外線，而使樹脂組成物硬化。將硬化樹脂層連同PET薄膜自壓模進行脫模，而獲得表面具有凸部的平均間隔w1：100 nm、高度d1：200 nm的微細凹凸結構的物品。將評價結果示於表2中。[Example 1] As the active energy ray-curable resin composition (X), a resin having the composition shown in Table 2 was prepared. A few drops of the active energy ray-curable resin composition were dropped onto the surface of the fine uneven structure transfer stamper, and the PET film (manufactured by Toyobo Co., Ltd., product name: A4300, thickness: 50 μm) was extruded and expanded. Coated. Thereafter, an electrodeless UV lamp (manufactured by Heraeus, D valve) was used to irradiate ultraviolet rays from the film side so that the integrated light amount measured at a wavelength of 365 nm became 1000 mJ/cm 2 . And the resin composition is hardened. The hardened resin layer was released from the press film together with the PET film to obtain an article having a fine uneven structure having a convex portion with an average interval w1: 100 nm and a height d1: 200 nm. The evaluation results are shown in Table 2.
[實施例2～實施例4] 除將活性能量線硬化性樹脂組成物（X）變更成表2中所示者以外，與實施例1同樣地製作表面具有微細凹凸結構的物品，並進行評價。將評價結果示於表2中。[Examples 2 to 4] An article having a fine uneven structure on the surface was produced and evaluated in the same manner as in Example 1 except that the active energy ray-curable resin composition (X) was changed to that shown in Table 2. . The evaluation results are shown in Table 2.
[比較例1～比較例3] 除將活性能量線硬化性樹脂組成物（X）變更成表2中所示者以外，與實施例1同樣地製作表面具有微細凹凸結構的物品，並進行評價。將評價結果示於表2中。[Comparative Example 1 to Comparative Example 3] An article having a fine uneven structure on the surface was produced and evaluated in the same manner as in Example 1 except that the active energy ray-curable resin composition (X) was changed to that shown in Table 2. . The evaluation results are shown in Table 2.
[表2]
[評價結果/實施例與比較例的對比] 根據表2，可知實施例1～實施例4因內部脫模劑（F）的效果而使自壓模的剝離力十分低，而脫模性優異。另外，可知實施例1～實施例4除所獲得的表面具有微細凹凸結構的物品的耐擦傷性優異以外，水接觸角大，撥水性亦高。另一方面，於比較例1及比較例2中，因不含內部脫模劑（F），故自壓模的剝離力高，所獲得的微細凹凸結構表面的接觸角亦變低。[Evaluation Result/Comparative Example and Comparative Example] According to Table 2, it is understood that Examples 1 to 4 have a very low peeling force from the stamper due to the effect of the internal mold release agent (F), and are excellent in mold release property. . Further, it is understood that the articles 1 to 4 of the examples 1 to 4 have excellent scratch resistance of the article having a fine uneven structure on the surface, and have a large water contact angle and high water repellency. On the other hand, in Comparative Example 1 and Comparative Example 2, since the internal mold release agent (F) was not contained, the peeling force from the stamper was high, and the contact angle of the surface of the fine uneven structure obtained was also low.
具體而言，若對實施例1與比較例1、比較例2進行對比，則聚合性成分（A）、聚合性成分（B）、聚合性成分（C）、光聚合起始劑（E）均為相同的組成，不同點在於有無內部脫模劑（F）及其他成分（G）。於含有0.5 w%的作為內部脫模劑（F）的JP-513的實施例1中，200次轉印時的剝離力為5[N/m]而十分低，水接觸角亦為142[°]而變成超撥水。另一方面，可知於分別含有作為磷酸三酯的TOP與TDP-2的比較例1與比較例2中，不僅剝離力變高，水接觸角亦變低。Specifically, when the first embodiment is compared with the comparative example 1 and the comparative example 2, the polymerizable component (A), the polymerizable component (B), the polymerizable component (C), and the photopolymerization initiator (E) are used. All have the same composition, with the difference being the presence or absence of internal mold release agent (F) and other ingredients (G). In Example 1 containing 0.5 w% of JP-513 as the internal mold release agent (F), the peeling force at the 200th transfer was 5 [N/m] and was very low, and the water contact angle was also 142 [ °] and become super water. On the other hand, in Comparative Example 1 and Comparative Example 2 in which TOP and TDP-2, which are phosphoric acid triesters, respectively, it was found that not only the peeling force was high but also the water contact angle was low.
比較例3是不含聚合性成分（A）、且包含大量含有氧基伸乙基的成分（成分（D））作為聚合性成分的樹脂組成物的情況，但可知與實施例相比，不僅剝離力變高，水接觸角亦變得非常低。因此，可知內部脫模劑（F）在與聚合性成分（A）或聚合性成分（B）的組合中發揮特別優異的效果。 [產業上之可利用性]Comparative Example 3 is a resin composition containing no polymerizable component (A) and containing a large amount of a component (D) containing an oxyethyl group as a polymerizable component. However, it is understood that not only the resin composition is peeled off from the examples. The force becomes higher and the water contact angle becomes very low. Therefore, it is understood that the internal mold release agent (F) exhibits particularly excellent effects in combination with the polymerizable component (A) or the polymerizable component (B). [Industrial availability]
本發明的實施形態的表面具有微細凹凸結構的物品可期待作為抗反射物品（抗反射薄膜、抗反射膜等）、超撥水物品（超撥水薄膜、防污薄膜等）、光波導、浮雕型全息圖、透鏡、偏光分離元件等光學物品，細胞培養片的用途展開，尤其適合於作為抗反射物品與超撥水物品的用途。An article having a fine uneven structure on the surface of the embodiment of the present invention can be expected as an antireflection article (antireflection film, antireflection film, etc.), super water-repellent articles (super-water-repellent film, antifouling film, etc.), optical waveguide, embossing Optical articles such as holograms, lenses, and polarized separation elements, and the use of cell culture sheets are particularly suitable for use as anti-reflective articles and super-water-repellent articles.
作為抗反射物品，例如可列舉：設置於圖像顯示裝置（液晶顯示裝置、電漿顯示面板、電致發光顯示器、陰極管顯示裝置等）、透鏡、櫥窗、眼鏡等的表面上的抗反射膜、抗反射薄膜、抗反射片等。Examples of the antireflection article include an antireflection film provided on the surface of an image display device (a liquid crystal display device, a plasma display panel, an electroluminescence display, a cathode tube display device, etc.), a lens, a window, glasses, or the like. , anti-reflective film, anti-reflective sheet, etc.
作為超撥水物品，例如可列舉：汽車等運輸機器的鏡子（後視鏡等）用的薄膜、住宅用水處用翻新薄膜、窗戶薄膜等建材用的薄膜。Examples of the super-water-repellent articles include films for mirrors (such as rearview mirrors) of transportation equipment such as automobiles, refractory films for residential water use, and films for building materials such as window films.
10‧‧‧積層體（具有微細凹凸結構的物品）
11‧‧‧基材
12‧‧‧表層（樹脂硬化層）
13、13b‧‧‧凸部
13a‧‧‧凸部的頂點
14‧‧‧凹部
14a‧‧‧凹部的底點
15‧‧‧塗佈層
20‧‧‧壓模
30‧‧‧鋁基材
31‧‧‧細孔
32‧‧‧氧化皮膜
33‧‧‧細孔產生點
34‧‧‧氧化皮膜
35‧‧‧細孔
40‧‧‧具有微細凹凸結構的物品
41‧‧‧輥狀壓模
42‧‧‧基材
43‧‧‧槽
44‧‧‧硬化樹脂層
45‧‧‧氣壓缸
46‧‧‧夾輥
47‧‧‧剝離輥
48‧‧‧活性能量線照射裝置
d1‧‧‧自凹部的底點至凸部的頂點為止的垂直距離
W1‧‧‧鄰接的凸部的間隔10‧‧‧Laminated bodies (items with fine concave and convex structures)
11‧‧‧Substrate
12‧‧‧ surface layer (resin hardened layer)
13, 13b‧‧‧ convex
13a‧‧‧The apex of the convex
14‧‧‧ recess
14a‧‧‧ bottom point of the recess
15‧‧‧ Coating layer
20‧‧‧Molding
30‧‧‧Aluminum substrate
31‧‧‧Pore
32‧‧‧Oxide film
33‧‧‧Pore generation points
34‧‧‧Oxide film
35‧‧‧Pore
40‧‧‧Items with fine concave and convex structures
41‧‧‧ Roller stamper
42‧‧‧Substrate
43‧‧‧ slots
44‧‧‧ hardened resin layer
45‧‧‧ pneumatic cylinder
46‧‧‧ nip rollers
47‧‧‧ peeling roller
48‧‧‧Active energy line irradiation device
D1‧‧‧ vertical distance from the bottom point of the recess to the apex of the convex part
W1‧‧‧ spacing of adjacent convex parts
圖1的（a）、圖1的（b）是表示本發明的實施形態的具有微細凹凸結構的物品的示意剖面圖。 圖2的（a）～圖2的（f）是表示用於形成本發明的實施形態的物品的微細凹凸結構的壓模的製造步驟的圖。 圖3是表示本發明的實施形態的具有微細凹凸結構的物品的製造裝置的一例的構成圖。(a) and (b) of FIG. 1 are schematic cross-sectional views showing an article having a fine uneven structure according to an embodiment of the present invention. (a) to (f) of FIG. 2 are views showing a manufacturing procedure of a stamper for forming a fine uneven structure of an article according to an embodiment of the present invention. FIG. 3 is a configuration diagram showing an example of an apparatus for manufacturing an article having a fine uneven structure according to an embodiment of the present invention.
10‧‧‧積層體(具有微細凹凸結構的物品) 10‧‧‧Laminated bodies (items with fine concave and convex structures)
11‧‧‧基材 11‧‧‧Substrate
12‧‧‧表層(樹脂硬化層) 12‧‧‧ surface layer (resin hardened layer)
13、13b‧‧‧凸部 13, 13b‧‧‧ convex
13a‧‧‧凸部的頂點 13a‧‧‧The apex of the convex
14‧‧‧凹部 14‧‧‧ recess
14a‧‧‧凹部的底點 14a‧‧‧ bottom point of the recess
15‧‧‧塗佈層 15‧‧‧ Coating layer
d1‧‧‧自凹部的底點至凸部的頂點為止的垂直距離 D1‧‧‧ vertical distance from the bottom point of the recess to the apex of the convex part
w1‧‧‧鄰接的凸部的間隔 W1‧‧‧ spacing of adjacent convex parts
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| Application Number | Priority Date | Filing Date | Title |
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| JP2015069043 | 2015-03-30 |
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| TW105109149A TW201641577A (en) | 2015-03-30 | 2016-03-24 | Active energy ray-curable resin composition and article |
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| JP (1) | JPWO2016158979A1 (en) |
| TW (1) | TW201641577A (en) |
| WO (1) | WO2016158979A1 (en) |
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| TWI799550B (en) * | 2018-03-27 | 2023-04-21 | 日商富士軟片股份有限公司 | Curable composition for imprint, release agent, cured product, pattern forming method and lithography method |
| WO2020050207A1 (en) * | 2018-09-07 | 2020-03-12 | 富士フイルム株式会社 | Curable composition for imprinting, pattern production method, semiconductor element production method, and cured article |
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| EP1874531A2 (en) * | 2005-04-26 | 2008-01-09 | Nanosys, Inc. | Paintable nanofiber coatings |
| CN103237837B (en) * | 2010-12-28 | 2014-09-03 | 三菱丽阳株式会社 | Method for producing light-transmitting film, active energy ray-curable composition, and light-transmitting film |
| TWI453108B (en) * | 2011-01-31 | 2014-09-21 | Mitsubishi Rayon Co | Active energy ray-hardenable composition, and method for producing light transmissive film having fine concavo-convex structure on the surface |
| JP2014077040A (en) * | 2012-10-10 | 2014-05-01 | Mitsubishi Rayon Co Ltd | Active energy ray-curable composition and fine uneven structure using the same |
| JP2015214101A (en) * | 2014-05-12 | 2015-12-03 | 三菱レイヨン株式会社 | Mold for nanoimprint and method for manufacturing the same, molded product having fine rugged structure, and aluminum base material used as mold for nanoimprint |
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| WO2016158979A1 (en) | 2016-10-06 |
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