TWI418454B - Method of manufacturing product having micro protrusion and recess face structure on surface thereof and manufacturing device thereof - Google Patents
Method of manufacturing product having micro protrusion and recess face structure on surface thereof and manufacturing device thereof Download PDFInfo
- Publication number
- TWI418454B TWI418454B TW100112046A TW100112046A TWI418454B TW I418454 B TWI418454 B TW I418454B TW 100112046 A TW100112046 A TW 100112046A TW 100112046 A TW100112046 A TW 100112046A TW I418454 B TWI418454 B TW I418454B
- Authority
- TW
- Taiwan
- Prior art keywords
- mold
- article
- release agent
- fine uneven
- uneven structure
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 48
- 239000003795 chemical substances by application Substances 0.000 claims description 94
- 238000002835 absorbance Methods 0.000 claims description 55
- 238000001228 spectrum Methods 0.000 claims description 41
- 238000012546 transfer Methods 0.000 claims description 34
- 239000000126 substance Substances 0.000 claims description 23
- 150000002222 fluorine compounds Chemical group 0.000 claims description 17
- 230000007246 mechanism Effects 0.000 claims description 10
- 238000002329 infrared spectrum Methods 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 75
- 229910052782 aluminium Inorganic materials 0.000 description 59
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 59
- 239000011148 porous material Substances 0.000 description 56
- 239000000178 monomer Substances 0.000 description 44
- 239000011347 resin Substances 0.000 description 36
- 229920005989 resin Polymers 0.000 description 36
- 238000000034 method Methods 0.000 description 34
- 239000011342 resin composition Substances 0.000 description 33
- -1 fluoroalkyl decane Chemical compound 0.000 description 30
- 150000001875 compounds Chemical class 0.000 description 27
- 239000000463 material Substances 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 21
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 19
- 239000000758 substrate Substances 0.000 description 19
- 229910052731 fluorine Inorganic materials 0.000 description 15
- 125000003709 fluoroalkyl group Chemical group 0.000 description 15
- 238000012360 testing method Methods 0.000 description 14
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 13
- 238000002048 anodisation reaction Methods 0.000 description 13
- 239000011737 fluorine Substances 0.000 description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000004566 IR spectroscopy Methods 0.000 description 11
- 125000000524 functional group Chemical group 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 238000012545 processing Methods 0.000 description 10
- 238000003860 storage Methods 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- 239000002202 Polyethylene glycol Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 125000002947 alkylene group Chemical group 0.000 description 8
- 230000003373 anti-fouling effect Effects 0.000 description 8
- 230000002950 deficient Effects 0.000 description 8
- 239000008151 electrolyte solution Substances 0.000 description 8
- 229920001223 polyethylene glycol Polymers 0.000 description 8
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 235000006408 oxalic acid Nutrition 0.000 description 7
- 239000003505 polymerization initiator Substances 0.000 description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 238000005498 polishing Methods 0.000 description 6
- 229920002098 polyfluorene Polymers 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 239000007822 coupling agent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000006870 function Effects 0.000 description 5
- 125000003827 glycol group Chemical group 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 239000006082 mold release agent Substances 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 5
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- RGXWDWUGBIJHDO-UHFFFAOYSA-N ethyl decanoate Chemical compound CCCCCCCCCC(=O)OCC RGXWDWUGBIJHDO-UHFFFAOYSA-N 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 229940059574 pentaerithrityl Drugs 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 4
- 229920013730 reactive polymer Polymers 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229920002313 fluoropolymer Polymers 0.000 description 3
- 239000004811 fluoropolymer Substances 0.000 description 3
- 125000005702 oxyalkylene group Chemical group 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000005011 time of flight secondary ion mass spectroscopy Methods 0.000 description 3
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- 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 2
- RSROEZYGRKHVMN-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;oxirane Chemical compound C1CO1.CCC(CO)(CO)CO RSROEZYGRKHVMN-UHFFFAOYSA-N 0.000 description 2
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 2
- 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 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-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
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 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
- 230000001588 bifunctional effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000012461 cellulose resin Substances 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 125000001153 fluoro group Chemical group F* 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
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- YRHYCMZPEVDGFQ-UHFFFAOYSA-N methyl decanoate Chemical compound CCCCCCCCCC(=O)OC YRHYCMZPEVDGFQ-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid group Chemical group C(C=1C(C(=O)O)=CC=CC1)(=O)O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000002328 sterol group Chemical group 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- CSUUDNFYSFENAE-UHFFFAOYSA-N (2-methoxyphenyl)-phenylmethanone Chemical compound COC1=CC=CC=C1C(=O)C1=CC=CC=C1 CSUUDNFYSFENAE-UHFFFAOYSA-N 0.000 description 1
- VBCUEUULCJFHAZ-VKHMYHEASA-N (4S)-4-amino-5-(1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctylsulfonyloxy)-5-oxopentanoic acid Chemical compound OC(=O)CC[C@H](N)C(=O)OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F VBCUEUULCJFHAZ-VKHMYHEASA-N 0.000 description 1
- KYUCWJRUVWJDOF-UHFFFAOYSA-N 1,1,1-trifluoro-4-(triethoxymethyl)dodecane Chemical compound FC(CCC(C(OCC)(OCC)OCC)CCCCCCCC)(F)F KYUCWJRUVWJDOF-UHFFFAOYSA-N 0.000 description 1
- DQGPWNBGAYGUPK-UHFFFAOYSA-N 1,1,1-trifluoro-4-(trimethoxymethyl)dodecane Chemical compound FC(CCC(C(OC)(OC)OC)CCCCCCCC)(F)F DQGPWNBGAYGUPK-UHFFFAOYSA-N 0.000 description 1
- CSFHANQRJZCMPQ-UHFFFAOYSA-N 1,1,1-trifluoro-4-methoxy-4,5-dimethyltridecane Chemical compound CC(C(OC)(CCC(F)(F)F)C)CCCCCCCC CSFHANQRJZCMPQ-UHFFFAOYSA-N 0.000 description 1
- OHPZNXYJAZBDSJ-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonic acid;2-(2-hydroxyethylamino)ethanol Chemical compound OCCNCCO.OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F OHPZNXYJAZBDSJ-UHFFFAOYSA-N 0.000 description 1
- YMSACYRPLFCCON-UHFFFAOYSA-N 1,2-diphenylethane-1,2-dione;2-hydroxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1.C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 YMSACYRPLFCCON-UHFFFAOYSA-N 0.000 description 1
- 229940043375 1,5-pentanediol Drugs 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- GCZWJRLXIPVNLU-UHFFFAOYSA-N 2,2-dimethoxy-3-methylundecane Chemical compound CC(C(OC)(OC)C)CCCCCCCC GCZWJRLXIPVNLU-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
- UXCIJKOCUAQMKD-UHFFFAOYSA-N 2,4-dichlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC(Cl)=C3SC2=C1 UXCIJKOCUAQMKD-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- 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 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
- 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
- SFDKXYOSCPCHNR-UHFFFAOYSA-N 2-diethoxyphosphorylquinoline Chemical compound C1=CC=CC2=NC(P(=O)(OCC)OCC)=CC=C21 SFDKXYOSCPCHNR-UHFFFAOYSA-N 0.000 description 1
- PRGOMJUDGZDSQZ-UHFFFAOYSA-N 2-ethylbenzohydrazide Chemical compound CCC1=CC=CC=C1C(=O)NN PRGOMJUDGZDSQZ-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- SGJUFIMCHSLMRJ-UHFFFAOYSA-N 2-hydroperoxypropane Chemical compound CC(C)OO SGJUFIMCHSLMRJ-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- KFXLXEQCRFGDRU-UHFFFAOYSA-N 2-methylbenzohydrazide Chemical compound CC1=CC=CC=C1C(=O)NN KFXLXEQCRFGDRU-UHFFFAOYSA-N 0.000 description 1
- WSULUIILRBXVFA-UHFFFAOYSA-N 2-methyloxirane;propane Chemical compound CCC.CC1CO1 WSULUIILRBXVFA-UHFFFAOYSA-N 0.000 description 1
- BYUDZGDPWSSECZ-UHFFFAOYSA-N 2-propan-2-ylthiophene 1-oxide Chemical class CC(C)C1=CC=CS1=O BYUDZGDPWSSECZ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- JCEAFZUEUSBESW-UHFFFAOYSA-N 4-(4-formylphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C=O)C=C1 JCEAFZUEUSBESW-UHFFFAOYSA-N 0.000 description 1
- WPSWDCBWMRJJED-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;oxirane Chemical compound C1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WPSWDCBWMRJJED-UHFFFAOYSA-N 0.000 description 1
- 125000004864 4-thiomethylphenyl group Chemical group 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- MTRFEWTWIPAXLG-UHFFFAOYSA-N 9-phenylacridine Chemical compound C1=CC=CC=C1C1=C(C=CC=C2)C2=NC2=CC=CC=C12 MTRFEWTWIPAXLG-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- UIPPPDFAPKLAFS-UHFFFAOYSA-N C1(=CC=CC=C1)C(=O)C(O)C1=CC=CC=C1.C(C(C)C)OC(C(C1=CC=CC=C1)=O)C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)C(=O)C(O)C1=CC=CC=C1.C(C(C)C)OC(C(C1=CC=CC=C1)=O)C1=CC=CC=C1 UIPPPDFAPKLAFS-UHFFFAOYSA-N 0.000 description 1
- LNEJJQMNHUGXDW-UHFFFAOYSA-N CC(C(OCC)(OCC)C)CCCCCCCC Chemical compound CC(C(OCC)(OCC)C)CCCCCCCC LNEJJQMNHUGXDW-UHFFFAOYSA-N 0.000 description 1
- PZKBIVOXIFYDRI-UHFFFAOYSA-N CC(C(OCC)(OCC)OCC)CCCCCCCC Chemical compound CC(C(OCC)(OCC)OCC)CCCCCCCC PZKBIVOXIFYDRI-UHFFFAOYSA-N 0.000 description 1
- KXEOJQGXZGUSRW-UHFFFAOYSA-N CC(C(OCCC)(OCCC)OCCC)CCCCCCCC Chemical compound CC(C(OCCC)(OCCC)OCCC)CCCCCCCC KXEOJQGXZGUSRW-UHFFFAOYSA-N 0.000 description 1
- DJUZRLZFAOOONK-UHFFFAOYSA-N CC(C(OCCCC)(OCCCC)OCCCC)CCCCCCCC Chemical compound CC(C(OCCCC)(OCCCC)OCCCC)CCCCCCCC DJUZRLZFAOOONK-UHFFFAOYSA-N 0.000 description 1
- COQYUAJAXLUAHF-UHFFFAOYSA-N CC(CCCCCCCCCOC)(C)C Chemical compound CC(CCCCCCCCCOC)(C)C COQYUAJAXLUAHF-UHFFFAOYSA-N 0.000 description 1
- ICLWANDVDRTPBG-UHFFFAOYSA-N CC(CCCCCCCCCOCC)(C)C Chemical compound CC(CCCCCCCCCOCC)(C)C ICLWANDVDRTPBG-UHFFFAOYSA-N 0.000 description 1
- JVNGBOZHOKVQOO-UHFFFAOYSA-N CC(CCCCCCCCCOCCC)(C)C Chemical compound CC(CCCCCCCCCOCCC)(C)C JVNGBOZHOKVQOO-UHFFFAOYSA-N 0.000 description 1
- MUYHWHXUCMTWGW-UHFFFAOYSA-N CC(CCCCCCCCCOCCCC)(C)C Chemical compound CC(CCCCCCCCCOCCCC)(C)C MUYHWHXUCMTWGW-UHFFFAOYSA-N 0.000 description 1
- CZKDHMFTTQOJCJ-UHFFFAOYSA-N CC1=CC(=C(C=C1)C(C)(C)C1=C(C=C(C=C1)C)OCCOC=CC)OCCOC=CC Chemical compound CC1=CC(=C(C=C1)C(C)(C)C1=C(C=C(C=C1)C)OCCOC=CC)OCCOC=CC CZKDHMFTTQOJCJ-UHFFFAOYSA-N 0.000 description 1
- PRCYQHLXGXGJFN-UHFFFAOYSA-N CCC=COCC(COCCCCOCC(COC=CCC)O)O Chemical compound CCC=COCC(COCCCCOCC(COC=CCC)O)O PRCYQHLXGXGJFN-UHFFFAOYSA-N 0.000 description 1
- BUMLFFFSYGNSBJ-UHFFFAOYSA-N CCC=COCC(COCCOCC(COC=CCC)O)O Chemical compound CCC=COCC(COCCOCC(COC=CCC)O)O BUMLFFFSYGNSBJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XBLJCYOUYPSETL-UHFFFAOYSA-N Isopropyl citrate Chemical compound CC(C)O.CC(=O)CC(O)(C(O)=O)CC(O)=O XBLJCYOUYPSETL-UHFFFAOYSA-N 0.000 description 1
- 239000002310 Isopropyl citrate Substances 0.000 description 1
- 244000147568 Laurus nobilis Species 0.000 description 1
- 235000017858 Laurus nobilis Nutrition 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000005640 Methyl decanoate Substances 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- GSBKRFGXEJLVMI-UHFFFAOYSA-N Nervonyl carnitine Chemical class CCC[N+](C)(C)C GSBKRFGXEJLVMI-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- 235000005212 Terminalia tomentosa Nutrition 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- XRMBQHTWUBGQDN-UHFFFAOYSA-N [2-[2,2-bis(prop-2-enoyloxymethyl)butoxymethyl]-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CC)COCC(CC)(COC(=O)C=C)COC(=O)C=C XRMBQHTWUBGQDN-UHFFFAOYSA-N 0.000 description 1
- YPCHGLDQZXOZFW-UHFFFAOYSA-N [2-[[4-methyl-3-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]carbonylamino]phenyl]carbamoyloxymethyl]-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound CC1=CC=C(NC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C)C=C1NC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C YPCHGLDQZXOZFW-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- IPTLKMXBROVJJF-UHFFFAOYSA-N azanium;methyl sulfate Chemical compound N.COS(O)(=O)=O IPTLKMXBROVJJF-UHFFFAOYSA-N 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- CYDRXTMLKJDRQH-UHFFFAOYSA-N benzododecinium Chemical class CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 CYDRXTMLKJDRQH-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical group CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- ZRNCNTSXSYXHOW-UHFFFAOYSA-N butyl decanoate Chemical compound CCCCCCCCCC(=O)OCCCC ZRNCNTSXSYXHOW-UHFFFAOYSA-N 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000002933 cyclohexyloxy group Chemical group C1(CCCCC1)O* 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical class CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- SIYLLGKDQZGJHK-UHFFFAOYSA-N dimethyl-(phenylmethyl)-[2-[2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethoxy]ethyl]ammonium Chemical compound C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 SIYLLGKDQZGJHK-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 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 1
- 238000001035 drying Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- WHRIKZCFRVTHJH-UHFFFAOYSA-N ethylhydrazine Chemical compound CCNN WHRIKZCFRVTHJH-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- WSFJFIDCQBAQQZ-UHFFFAOYSA-N hydroxy(sulfido)phosphanium Chemical compound S[PH2]=O WSFJFIDCQBAQQZ-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical class C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 235000019300 isopropyl citrate Nutrition 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- IHBKAGRPNRKYAO-UHFFFAOYSA-M methyl sulfate;trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium Chemical compound COS([O-])(=O)=O.CC(=C)C(=O)OCC[N+](C)(C)C IHBKAGRPNRKYAO-UHFFFAOYSA-M 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 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
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- 125000003544 oxime group Chemical group 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- RRRXPPIDPYTNJG-UHFFFAOYSA-N perfluorooctanesulfonamide Chemical compound NS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RRRXPPIDPYTNJG-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- HPAFOABSQZMTHE-UHFFFAOYSA-N phenyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)C1=CC=CC=C1 HPAFOABSQZMTHE-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
- 125000001557 phthalyl group Chemical group C(=O)(O)C1=C(C(=O)*)C=CC=C1 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- UFUASNAHBMBJIX-UHFFFAOYSA-N propan-1-one Chemical compound CC[C]=O UFUASNAHBMBJIX-UHFFFAOYSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007717 redox polymerization reaction 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
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 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
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- BWSZXUOMATYHHI-UHFFFAOYSA-N tert-butyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(C)(C)C BWSZXUOMATYHHI-UHFFFAOYSA-N 0.000 description 1
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 1
- MUQNAPSBHXFMHT-UHFFFAOYSA-N tert-butylhydrazine Chemical compound CC(C)(C)NN MUQNAPSBHXFMHT-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 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
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 125000002889 tridecyl 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])[H] 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- VZTGWJFIMGVKSN-UHFFFAOYSA-O trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium Chemical compound CC(=C)C(=O)NCCC[N+](C)(C)C VZTGWJFIMGVKSN-UHFFFAOYSA-O 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical class CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
- B29C33/58—Applying the releasing agents
-
- 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
- B29C37/00—Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
- B29C37/0067—Using separating agents during or after moulding; Applying separating agents on preforms or articles, e.g. to prevent sticking to each other
-
- 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
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/22—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length
- B29C43/222—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length characterised by the shape of the surface
-
- 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
- B29C59/04—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing using rollers or endless belts
- B29C59/046—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing using rollers or endless belts for layered or coated substantially flat surfaces
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3563—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing solids; Preparation of samples therefor
Description
本申請案主張於2010年4月9號向日本智慧財產局提出申請之日本專利申請案第2010-090456號的優先權，該專利申請案所揭露之內容係完整結合於本說明書中。The present application claims the priority of Japanese Patent Application No. 2010-090456, filed on Apr. 9, 2010, to the Japanese Provisional.
本發明是有關於一種將表面經脫模劑處理之模具之表面的微細凹凸結構轉印至物品本體之表面，製造表面具有微細凹凸結構的物品的方法及裝置。The present invention relates to a method and apparatus for producing a fine uneven structure having a surface treated with a release agent onto a surface of an article body to produce an article having a fine uneven structure on its surface.
近年來，已知在表面具有可見光之波長以下之週期的微細凹凸結構的物品表現出抗反射效果及蓮花效應(lotus effect)等，因此其有用性受到關注。特別是被稱為蛾眼結構(Moth-eye-structure)之微細凹凸結構，由於折射率自空氣之折射率連續地增大至物品之材料之折射率，從而成為有效之抗反射機構。In recent years, it has been known that an article having a fine uneven structure having a period of a wavelength equal to or less than the wavelength of visible light exhibits an antireflection effect, a lotus effect, and the like, and thus its usefulness has been attracting attention. In particular, a fine concavo-convex structure called a Moth-eye structure is an effective anti-reflection mechanism because the refractive index continuously increases from the refractive index of air to the refractive index of the material of the article.
表面具有微細凹凸結構的物品的製造方法例如已知有具有如下步驟(i)~步驟(iii)之方法(例如日本專利特開2007-326367號公報)。For example, a method having the following steps (i) to (iii) is known as a method for producing an article having a fine uneven structure on the surface (for example, Japanese Patent Laid-Open Publication No. 2007-326367).
(i)於表面具有微細凹凸結構之反轉結構且所述表面經脫模劑處理之模具、與成為物品之本體的基材薄膜之間，夾持紫外線硬化性樹脂組成物的步驟。(i) a step of sandwiching an ultraviolet curable resin composition between a mold having a reversed structure of a fine uneven structure and a surface treated with a release agent and a base film which is a body of the article.
(ii)對紫外線硬化性樹脂組成物照射紫外線，使所述紫外線硬化性樹脂組成物硬化而形成具有微細凹凸結構之硬化樹脂層的步驟。(ii) A step of irradiating the ultraviolet curable resin composition with ultraviolet rays and curing the ultraviolet curable resin composition to form a cured resin layer having a fine uneven structure.
(iii)使基材薄膜之表面的硬化樹脂層自模具脫模，獲得表面具有微細凹凸結構的物品的步驟。(iii) A step of releasing the hardened resin layer on the surface of the base film from the mold to obtain an article having a fine uneven structure on the surface.
藉由脫模劑進行了處理的模具多數情況下會由於反覆進行微細凹凸結構之轉印而造成性能降低，從而導致變得無法使模具自硬化樹脂層脫模。若成為所述狀態，則於模具之表面附著硬化樹脂而造成清洗變困難，或者基材薄膜於製造中破斷。因此，造成製造長時間中斷，生產性顯著降低。為了解決所述問題，需求一種可在線(online)簡易地監控模具表面之脫模劑之狀態的方法。In many cases, the mold treated by the release agent causes a decrease in performance due to the transfer of the fine uneven structure, and the mold cannot be released from the cured resin layer. When it is in this state, it is difficult to wash the hardened resin on the surface of the mold, or the base film is broken during production. Therefore, the manufacturing is interrupted for a long time, and the productivity is remarkably lowered. In order to solve the problem, there is a need for a method for easily monitoring the state of a release agent on a mold surface online.
本發明可提供一種可在線簡易地監控模具表面之脫模劑之狀態、且可抑制生產性之降低的表面具有微細凹凸結構的物品的製造方法及製造裝置。The present invention can provide a method and a device for producing an article having a fine uneven structure on the surface which can monitor the state of the release agent on the surface of the mold and can suppress the decrease in productivity.
本發明的表面具有微細凹凸結構的物品的製造方法是將表面經脫模劑處理之模具之表面的微細凹凸結構轉印至物品本體之表面，製造表面具有微細凹凸結構的物品的方法，其特徵在於：將微細凹凸結構轉印至物品本體之表面，測定將所述物品本體自模具上剝離後的模具之表面的紅外分光光譜，基於所述紅外分光光譜而判定模具之表面的脫模劑之狀態的良否。The method for producing an article having a fine uneven structure on the surface of the present invention is a method of producing a fine uneven structure having a surface treated with a release agent onto a surface of an article body to produce an article having a fine uneven structure on its surface, and its characteristics In the method of transferring the fine uneven structure to the surface of the article body, measuring the infrared spectrum of the surface of the mold after peeling the article body from the mold, and determining the release agent on the surface of the mold based on the infrared spectrum. The quality of the state.
於本發明之表面具有微細凹凸結構的物品的製造方法中，於模具之表面的脫模劑之狀態被判定為不良時，可停止將模具之表面的微細凹凸結構轉印至物品本體之表面上，且亦可將脫模劑供給至模具之表面的微細凹凸結構上。In the method for producing an article having a fine uneven structure on the surface of the present invention, when the state of the release agent on the surface of the mold is judged to be defective, the fine uneven structure on the surface of the mold can be stopped from being transferred onto the surface of the article body. Further, the release agent may be supplied to the fine uneven structure on the surface of the mold.
於本發明之表面具有微細凹凸結構的物品的製造方法中，較佳的是連續地或斷續地測定模具之表面的紅外分光光譜。In the method for producing an article having a fine uneven structure on the surface of the present invention, it is preferred to continuously or intermittently measure the infrared spectrum of the surface of the mold.
於本發明之表面具有微細凹凸結構的物品的製造方法中，較佳的是於紅外分光光譜中的源自脫模劑之化學結構的波數附近之峰值的吸光度面積(A)與源自存在於模具之表面之化學結構的波數附近之峰值的吸光度面積(B)之面積比((A)/(B))為預先設定之臨限值以上時，將模具之表面的脫模劑之狀態判定為良好。In the method for producing an article having a fine uneven structure on the surface of the present invention, it is preferred that the absorbance area (A) derived from the peak near the wave number of the chemical structure of the release agent in the infrared spectroscopic spectrum is derived from the presence of When the area ratio ((A)/(B)) of the absorbance area (B) of the peak near the wave number of the chemical structure on the surface of the mold is equal to or greater than a predetermined threshold, the release agent of the surface of the mold is used. The state is judged to be good.
本發明之表面具有微細凹凸結構的物品的製造裝置是將表面經脫模劑處理之模具之表面的微細凹凸結構轉印至物品本體之表面，製造表面具有微細凹凸結構的物品的裝置，其包含：模具，其於表面具有微細凹凸結構，且所述表面經脫模劑處理；反射型紅外分光裝置，其測定將微細凹凸結構轉印至物品本體之表面，將所述物品本體自模具剝離後的模具之表面的紅外分光光譜；判定機構，其基於所述紅外分光光譜，判定模具之表面的脫模劑之狀態的良否。The apparatus for producing an article having a fine uneven structure on the surface of the present invention is a device for transferring a fine uneven structure on the surface of a mold subjected to a release agent treatment to the surface of the article body, and producing an article having a fine uneven structure on the surface, which comprises a mold having a fine concavo-convex structure on a surface thereof, wherein the surface is treated with a release agent; and a reflective infrared spectroscopic device for measuring a fine concavo-convex structure to be transferred onto a surface of the article body to peel the article body from the mold Infrared spectroscopic spectrum of the surface of the mold; a determining mechanism that determines the quality of the release agent on the surface of the mold based on the infrared spectroscopic spectrum.
即，本發明是關於以下者。That is, the present invention relates to the following.
(1)一種表面具有微細凹凸結構的物品的製造方法，其是將表面經脫模劑處理之模具之表面的微細凹凸結構轉印至物品本體之表面，製造表面具有微細凹凸結構的物品的方法，其包含：將微細凹凸結構轉印至物品本體之表面；測定將所述物品本體自模具上剝離後的模具之表面的紅外 分光光譜；以及根據模具之表面的脫模劑之狀態的良否而判定是否適合繼續製造。(1) A method for producing an article having a fine uneven structure on a surface thereof, which is a method for producing a fine uneven structure having a surface treated with a release agent onto a surface of an article body to produce an article having a fine uneven structure on its surface The method comprises: transferring the fine uneven structure to the surface of the article body; and measuring the infrared of the surface of the mold after peeling the article body from the mold The spectroscopic spectrum; and whether or not it is suitable for continued manufacture according to the quality of the release agent on the surface of the mold.
(2)如(1)所述之表面具有微細凹凸結構的物品的製造方法，其進一步包含：於判定模具之表面的脫模劑之狀態為不良時，停止將模具表面之微細凹凸結構轉印至物品本體之表面上；及/或，再次以脫模劑對模具之表面進行處理。(2) The method for producing an article having a fine uneven structure on the surface according to (1), further comprising: stopping the transfer of the fine uneven structure on the surface of the mold when the state of the release agent on the surface of the mold is determined to be defective Onto the surface of the article body; and/or, again, the surface of the mold is treated with a release agent.
(3)如(1)或(2)項所述之表面具有微細凹凸結構的物品的製造方法，其中，所述模具之表面的紅外分光光譜之測定包括連續地或斷續地測定所述模具之表面的紅外分光光譜。(3) The method for producing an article having a fine uneven structure on the surface according to (1) or (2), wherein the measurement of the infrared spectroscopic spectrum of the surface of the mold comprises continuously or intermittently measuring the mold The infrared spectroscopic spectrum of the surface.
(4)如(1)~(3)中任一項所述之表面具有微細凹凸結構的物品的製造方法，其包含：於紅外分光光譜中的源自脫模劑之化學結構的波數附近之峰值的吸光度面積(A)、或者源自脫模劑之化學結構的波數附近之峰值的吸光度面積(A)與源自存在於模具之表面之化學結構的波數附近之峰值的吸光度面積(B)之面積比((A)/(B))為預先設定之臨限值以上時，將模具之表面的脫模劑之狀態判定為良好。(4) The method for producing an article having a fine uneven structure on the surface according to any one of (1) to (3), comprising: a wave number near a chemical structure derived from a release agent in an infrared spectroscopic spectrum The absorbance area (A) of the peak value, or the absorbance area (A) of the peak near the wave number of the chemical structure of the release agent and the absorbance area derived from the peak near the wave number of the chemical structure existing on the surface of the mold When the area ratio ((A)/(B)) of (B) is equal to or greater than the predetermined threshold value, the state of the release agent on the surface of the mold is judged to be good.
(5)如(4)所述之表面具有微細凹凸結構的物品的製造方法，其中，所述模具由氧化鋁所構成，所述脫模劑為氟化合物，所述吸光度面積(A)之臨限值為0.13，且所述吸光度之面積比((A)/(B))之臨限值為0.047。(5) The method for producing an article having a fine uneven structure on the surface as described in (4), wherein the mold is composed of alumina, the release agent is a fluorine compound, and the absorbance area (A) is The limit value is 0.13, and the area ratio of the absorbance ((A)/(B)) is 0.047.
(6)如(5)所述之表面具有微細凹凸結構的物品的 製造方法，其中，所述吸光度面積(A)為0.13以上1以下，且所述吸光度之面積比((A)/(B))為0.047以上10以下。(6) The article having a fine uneven structure on the surface as described in (5) In the production method, the absorbance area (A) is 0.13 or more and 1 or less, and the area ratio ((A)/(B)) of the absorbance is 0.047 or more and 10 or less.
(7)一種表面具有微細凹凸結構的物品的製造裝置，其是將表面經脫模劑處理之模具之表面的微細凹凸結構轉印至物品本體之表面，製造表面具有微細凹凸結構的物品的裝置，其包含：模具，其於表面具有微細凹凸結構，且所述表面經脫模劑處理；反射型紅外分光裝置，其測定將微細凹凸結構轉印至物品本體之表面，將所述物品本體自模具剝離後的模具之表面的紅外分光光譜；判定機構，其基於所述紅外分光光譜，判定模具之表面的脫模劑之狀態的良否。(7) A device for producing an article having a fine uneven structure on the surface, which is a device for transferring a fine uneven structure on the surface of a mold treated with a release agent to the surface of the article body to produce an article having a fine uneven structure on its surface And comprising: a mold having a fine concavo-convex structure on a surface thereof, wherein the surface is treated by a release agent; and a reflective infrared spectroscopic device for measuring transfer of the fine concavo-convex structure to a surface of the article body, the article body being self-contained An infrared spectroscopic spectrum of the surface of the mold after the mold is peeled off; and a determining means for determining the quality of the release agent on the surface of the mold based on the infrared spectroscopic spectrum.
藉由本發明之表面具有微細凹凸結構的物品的製造方法，可在線簡易地監控模具表面之脫模劑之狀態、且可抑制生產性之降低。According to the method for producing an article having a fine uneven structure on the surface of the present invention, the state of the release agent on the surface of the mold can be easily monitored on the line, and the decrease in productivity can be suppressed.
藉由本發明之表面具有微細凹凸結構的物品的製造裝置，可在線簡易地監控模具表面之脫模劑之狀態、且可抑制生產性之降低。According to the apparatus for producing an article having a fine uneven structure on the surface of the present invention, the state of the release agent on the surface of the mold can be easily monitored on the line, and the decrease in productivity can be suppressed.
為讓本發明之上述和其他目的、特徵和優點能更明顯易懂，下文特舉較佳實施例，並配合所附圖式，作詳細說明如下。The above and other objects, features and advantages of the present invention will become more <RTIgt;
於本說明書中，(甲基)丙烯酸酯表示丙烯酸酯或甲基 丙烯酸酯。而且，透明表示至少透過波長為400nm~1170nm之光。而且，活性能量線表示可見光線、紫外線、電子束、電漿、及熱射線(紅外線等)等。In the present specification, (meth) acrylate means acrylate or methyl Acrylate. Moreover, transparent means that at least light having a wavelength of 400 nm to 1170 nm is transmitted. Further, the active energy ray indicates visible light, ultraviolet light, electron beam, plasma, and heat rays (infrared rays, etc.).
<表面具有微細凹凸結構的物品的製造裝置><Manufacturing device for articles having a fine uneven structure on the surface>
本發明之表面具有微細凹凸結構的物品的製造裝置包含：模具，其於表面具有微細凹凸結構，且所述表面經脫模劑處理；反射型紅外分光裝置，其測定將微細凹凸結構轉印至物品本體之表面，將所述物品本體自模具剝離之後的模具之表面的紅外分光光譜；判定機構，其基於所述紅外分光光譜，判定模具之表面的脫模劑之狀態的良否。An apparatus for manufacturing an article having a fine uneven structure on the surface of the present invention comprises: a mold having a fine uneven structure on a surface thereof, and the surface is treated with a release agent; and a reflective infrared spectroscopic device for measuring transfer of the fine uneven structure to The surface of the article body, an infrared spectroscopic spectrum of the surface of the mold after the article body is peeled off from the mold; and a determining mechanism that determines the quality of the release agent on the surface of the mold based on the infrared spectroscopic spectrum.
圖1是表示本發明之表面具有微細凹凸結構的物品的製造裝置之一例的概略構成圖。所述製造裝置具有：輥狀模具20，於表面具有微細凹凸結構(圖示略)，且所述表面經脫模劑處理；貯槽22，將活性能量線硬化性樹脂組成物供給至與輥狀模具20之旋轉同步而沿輥狀模具20之表面移動之帶狀薄膜42(物品本體)與輥狀模具20之間；軋輥26，於其與輥狀模具20之間夾持薄膜42及活性能量線硬化性樹脂組成物；氣壓缸24，調整軋輥26之夾持壓；活性能量線照射裝置28，設置於輥狀模具20之下方，通過薄膜42而對活性能量線硬化性樹脂組成物照射活性能量線；剝離輥30，將表面形成有硬化樹脂層44之薄膜42自輥狀模具20剝離；反射型紅外分光裝置50，測定將硬化樹脂層44與薄膜42一同剝離之後的輥狀模具20之表面的紅外分光光譜；判定機構60，基於紅外分光光譜而判定 模具之表面的脫模劑之狀態的良否；控制裝置62，控制製造裝置之運轉。另外，於本發明中，所謂「剝離之後」是指自將表面具有微細凹凸結構的物品本體從模具上剝離時，直至所述模具再次與物品本體接觸。具體而言，是指自將硬化樹脂層44與薄膜42一同自輥狀模具20剝離時，直至將活性能量線硬化性樹脂組成物供給至薄膜42與輥狀模具20之間。Fig. 1 is a schematic configuration diagram showing an example of a manufacturing apparatus for an article having a fine uneven structure on the surface of the present invention. The manufacturing apparatus has a roll-shaped mold 20 having a fine uneven structure on the surface (not shown), and the surface is treated with a release agent; and the storage tank 22 supplies the active energy ray-curable resin composition to a roll shape. The rotation of the mold 20 is synchronized between the strip film 42 (object body) moving along the surface of the roll mold 20 and the roll mold 20; the roll 26 sandwiches the film 42 and the active energy between it and the roll mold 20. The line curable resin composition; the pneumatic cylinder 24 adjusts the nip pressure of the roll 26; the active energy ray irradiation device 28 is disposed below the roll mold 20, and irradiates the active energy ray-curable resin composition with the film 42 The peeling roller 30 peels the film 42 on which the hardened resin layer 44 is formed from the roll-shaped mold 20; the reflective infrared ray splitting device 50 measures the roll-shaped mold 20 after the cured resin layer 44 is peeled off together with the film 42. Infrared spectroscopic spectrum of the surface; the determining mechanism 60 is determined based on the infrared spectroscopic spectrum Whether the state of the release agent on the surface of the mold is good or not; the control device 62 controls the operation of the manufacturing device. In the present invention, the term "after peeling" means that the article body having the fine uneven structure on the surface is peeled off from the mold until the mold comes into contact with the article body again. Specifically, when the cured resin layer 44 is peeled off from the roll mold 20 together with the film 42 , the active energy ray-curable resin composition is supplied between the film 42 and the roll mold 20 .
(反射型紅外分光裝置)(Reflective infrared spectroscopic device)
反射型紅外分光裝置50具有：光源52，對輥狀模具20之表面照射紅外線；檢測器54，對輥狀模具20之表面所反射的紅外線進行受光及分光，對所分光之紅外線進行檢測而獲得紅外分光光譜；操作控制機器56，控制光源52及檢測器54，將檢測器54中所得之紅外分光光譜傳遞至判定機構60。反射型紅外分光裝置50設置於可測定如下時間段之間的輥狀模具20之表面的紅外線分光光譜的位置：自將硬化樹脂層44與薄膜42一同從輥狀模具20上剝離時，直至將活性能量線硬化性樹脂組成物供給至薄膜42與輥狀模具20之間。The reflective infrared spectroscopic device 50 includes a light source 52 that irradiates the surface of the roll-shaped mold 20 with infrared rays, and a detector 54 that receives and splits the infrared rays reflected on the surface of the roll-shaped mold 20, and detects the infrared rays of the split light. Infrared spectroscopic spectroscopy; an operation control device 56, a control light source 52 and a detector 54, and the infrared spectroscopic spectrum obtained in the detector 54 is transmitted to the determination mechanism 60. The reflective infrared spectroscopic device 50 is disposed at a position where the infrared spectroscopic spectrum of the surface of the roll-shaped mold 20 between the following periods can be measured: when the hardened resin layer 44 is peeled off from the roll-shaped mold 20 together with the film 42, until The active energy ray-curable resin composition is supplied between the film 42 and the roll mold 20.
反射型紅外分光裝置50可列舉傅立葉變換型及使用有繞射光柵之分散型等，自測定時間短之方面考慮，較佳的是傅立葉變換型紅外分光裝置。The reflection type infrared spectroscopic device 50 may be a Fourier transform type or a dispersion type using a diffraction grating, and is preferably a Fourier transform type infrared spectroscopic device from the viewpoint of a short measurement time.
(判定機構)(judging agency)
判定機構60例如具有：抽出部(圖示略)，自紅外分光光譜中抽出源自特定之化學結構的預定波數附近之峰值 的強度或面積；算出部(圖示略)，視需要算出2種峰值之強度或面積之比；判定部(圖示略)，於峰值之強度、面積或該些之比等為預先設定之臨限值以上(視情況為臨限值以下)時，將輥狀模具20之表面的脫模劑之狀態判定為良好；儲存部(圖示略)，儲存自外部輸入之臨限值等；傳遞部，於判定部將輥狀模具20之表面的脫模劑之狀態判定為不良之情形時，將其信息傳遞至控制裝置62。The judging means 60 has, for example, an extracting portion (not shown) for extracting a peak near a predetermined wave number derived from a specific chemical structure from the infrared spectroscopic spectrum. Strength or area; calculation unit (not shown), the ratio of the intensity or area of the two kinds of peaks is calculated as needed; the determination unit (not shown), the intensity, the area, or the ratio of the peaks are preset. When the threshold value is equal to or greater than the threshold value (below the limit value), the state of the release agent on the surface of the roll mold 20 is determined to be good; the storage portion (not shown) is stored, and the threshold value for external input is stored; When the determination unit determines that the state of the release agent on the surface of the roll-shaped mold 20 is defective, the transmission unit transmits the information to the control device 62.
判定部較佳的是於源自脫模劑之化學結構的波數附近的峰值之吸光度面積(A)、或者所述吸光度面積(A)與源自輥狀模具20之表面所存在之化學結構的波數附近之峰值的吸光度面積(B)之面積比((A)/(B))為預先設定之臨限值以上時，將模具之表面的脫模劑之狀態判定為良好。The determining portion is preferably an absorbance area (A) of a peak near the wave number of the chemical structure derived from the release agent, or a chemical structure of the absorbance area (A) and a surface derived from the roll-shaped mold 20. When the area ratio ((A)/(B)) of the absorbance area (B) of the peak near the wave number is equal to or greater than the predetermined threshold value, the state of the release agent on the surface of the mold is judged to be good.
於使用具有水解性矽烷基或矽醇基之氟化合物作為脫模劑，使用在鋁基材之表面具有陽極氧化鋁(所述陽極氧化鋁具有2個以上細孔)的模具作為輥狀模具20之情形時，判定機構60之各部具體而言較佳的是如下者。A fluorine compound having a hydrolyzable alkylene group or a decyl group is used as a mold release agent, and a mold having an anodized aluminum (the anodized aluminum has two or more fine pores) on the surface of the aluminum substrate is used as the roll mold 20 In the case of the case, each of the determination means 60 is specifically preferably as follows.
抽出部較佳的是自紅外分光光譜中抽出源自具有水解性矽烷基或矽醇基之氟化合物之化學結構的波數為1080cm-1 ~1290cm-1 附近之峰值的吸光度面積(A)、以及源自陽極氧化鋁之化學結構的波數為730cm-1 ~1080cm-1 附近之峰值的吸光度面積(B)。此時之基線是連結在預定之波數處具有峰值之吸收曲線之始點與終點的線。另外，該些波數存在由於脫模劑或陽極氧化鋁之狀態而變化之情形， 可根據出現之峰值位置而適宜變更。The extracting portion is preferably an absorbance area (A) obtained by extracting a peak having a chemical structure of a fluorine compound having a hydrolyzable alkylene group or a sterol group from a peak of 1080 cm -1 to 1290 cm -1 from the infrared spectroscopic spectrum, And an absorbance area (B) of a peak derived from a 730 cm -1 to 1080 cm -1 wave number derived from the chemical structure of the anodized aluminum. The baseline at this time is a line connecting the start point and the end point of the absorption curve having a peak at a predetermined wave number. Further, these wave numbers may vary depending on the state of the release agent or the anodized aluminum, and may be appropriately changed depending on the peak position where they occur.
算出部較佳的是算出於抽出部所抽出之面積(A)、或者面積(A)與面積(B)之面積比((A)/(B))。Preferably, the calculation unit calculates the area ratio (A) or the area ratio (A)/(B) of the area (A) and the area (B) extracted by the extraction unit.
判定部較佳的是於面積(A)或面積比((A)/(B))為預先設定之臨限值以上時，將輥狀模具20之表面的脫模劑之狀態判定為良好。The determination unit preferably determines that the state of the release agent on the surface of the roll mold 20 is good when the area (A) or the area ratio ((A)/(B)) is equal to or greater than a predetermined threshold.
此處，作為判定所使用之值，若陽極氧化鋁之厚度固定，則使用面積比((A)/(B))可期待再現性，及使裝置間誤差等問題變少而進行穩定之測定，因此較適宜。然而，於陽極氧化鋁之厚度並不固定等情形時，亦可僅僅藉由峰值(A)之面積而判斷。When the thickness of the anodized aluminum is fixed as the value used for the determination, the area ratio ((A)/(B)) can be expected to be reproducible, and the problem such as an error between devices can be reduced to stabilize the measurement. Therefore, it is more suitable. However, when the thickness of the anodized aluminum is not fixed, it may be judged only by the area of the peak (A).
另外，判定機構60可為藉由專用之硬體而實現者，而且判定機構60亦可由記憶體及中央處理器(CPU)而構成，於記憶體中載入用以實現判定機構60之功能的程式而實行，藉此而實現其功能者。In addition, the determining unit 60 can be implemented by a dedicated hardware, and the determining unit 60 can also be constituted by a memory and a central processing unit (CPU), and the memory is loaded with the function of the determining unit 60. The program is implemented to realize its function.
而且，於判定機構60中連接輸入裝置及顯示裝置等而作為周邊設備。此處，所謂輸入裝置是指顯示器觸控面板、開關面板、及鍵盤等輸入裝置，所謂顯示裝置是指陰極射線管(CRT)及液晶顯示裝置等。Further, an input device, a display device, and the like are connected to the determination unit 60 as peripheral devices. Here, the input device refers to an input device such as a display touch panel, a switch panel, and a keyboard, and the display device refers to a cathode ray tube (CRT), a liquid crystal display device, or the like.
(控制裝置)(control device)
控制裝置62具備處理部(圖示略)、界面部(圖示略)、儲存部(圖示略)。The control device 62 includes a processing unit (not shown), an interface unit (not shown), and a storage unit (not shown).
界面部將構成製造裝置之各機器等與處理部之間電性連接。The interface unit electrically connects each device or the like constituting the manufacturing device to the processing unit.
處理部基於儲存部中所儲存之各種設定以及來自判定機構60之判定信息等而控制所述各機器等之運轉等。例如，於判定機構60中將輥狀模具20之表面的脫模劑之狀態判定為不良時，停止薄膜42之移動、輥狀模具20之旋轉、及自貯槽22供給活性能量線硬化性樹脂組成物等，且停止將輥狀模具20之表面的微細凹凸結構轉印至薄膜42之表面。The processing unit controls the operation of the respective devices and the like based on various settings stored in the storage unit, determination information from the determination unit 60, and the like. For example, when the state of the release agent on the surface of the roll-shaped mold 20 is determined to be defective in the determination means 60, the movement of the film 42 is stopped, the rotation of the roll mold 20, and the active energy ray-curable resin are supplied from the storage tank 22. The material or the like is stopped and the fine uneven structure on the surface of the roll mold 20 is stopped from being transferred to the surface of the film 42.
另外，處理部可為藉由專用之硬體而實現者，而且處理部亦可由記憶體及中央處理器(CPU)而構成，於記憶體中載入用以實現處理部之功能的程式而實行，藉此而實現其功能者。Further, the processing unit may be implemented by a dedicated hardware, and the processing unit may be configured by a memory and a central processing unit (CPU), and a program for realizing the function of the processing unit may be loaded in the memory. In order to achieve its function.
而且，於控制裝置62中連接輸入裝置及顯示裝置等而作為周邊設備。此處，所謂輸入裝置是指顯示器觸控面板、開關面板、及鍵盤等輸入裝置，所謂顯示裝置是指陰極射線管(CRT)及液晶顯示裝置等。Further, an input device, a display device, and the like are connected to the control device 62 as peripheral devices. Here, the input device refers to an input device such as a display touch panel, a switch panel, and a keyboard, and the display device refers to a cathode ray tube (CRT), a liquid crystal display device, or the like.
而且，作為控制裝置62，可使用兼具所述判定機構60之功能者，亦可省略與控制裝置62分開設置之所述判定機構60。Further, as the control device 62, the function of the determination mechanism 60 may be used, and the determination mechanism 60 provided separately from the control device 62 may be omitted.
(活性能量線照射裝置)(active energy ray irradiation device)
活性能量線照射裝置28可列舉高壓水銀燈、金屬鹵素燈、及熔融燈等。Examples of the active energy ray irradiation device 28 include a high pressure mercury lamp, a metal halide lamp, a melting lamp, and the like.
(模具)(mold)
模具是於模具基材之表面具有微細凹凸結構，且所述表面經脫模劑處理者。The mold has a fine uneven structure on the surface of the mold substrate, and the surface is treated by a release agent.
模具基材之材料可列舉金屬(包括於表面形成有氧化皮膜之金屬)、石英、玻璃、樹脂、及陶瓷等。Examples of the material of the mold base material include metal (including a metal having an oxide film formed on the surface), quartz, glass, resin, ceramics, and the like.
模具基材之形狀除了輥狀以外，可列舉圓筒狀、平板狀、及薄板狀等。The shape of the mold base material may be, in addition to a roll shape, a cylindrical shape, a flat plate shape, a thin plate shape, or the like.
模具之製作方法例如可列舉下述之方法(I-1)及方法(I-2)，自可大面積化、且製作簡便之方面考慮，特佳的是方法(I-1)。Examples of the method for producing the mold include the following methods (I-1) and (I-2), and the method (I-1) is particularly preferable in terms of being large in area and easy to produce.
(I-1)於鋁基材之表面形成具有2個以上細孔(凹部)之陽極氧化鋁的方法。(I-1) A method of forming anodized aluminum having two or more pores (concave portions) on the surface of an aluminum substrate.
(I-2)藉由微影術等而於模具基材之表面直接形成微細凹凸結構的方法。(I-2) A method of directly forming a fine uneven structure on the surface of a mold base by lithography or the like.
方法(I-1)較佳的是具有下述步驟(a)~步驟(f)之方法。The method (I-1) preferably has the following steps (a) to (f).
(a)將鋁基材於電解液中、恆定電壓下進行陽極氧化而於鋁基材之表面形成氧化皮膜的步驟。(a) A step of forming an oxide film on the surface of the aluminum substrate by anodizing the aluminum substrate in an electrolytic solution at a constant voltage.
(b)除去氧化皮膜，於鋁基材之表面形成陽極氧化之細孔產生點的步驟。(b) A step of removing the oxide film and forming an anode-oxidized pore generating point on the surface of the aluminum substrate.
(c)將鋁基材於電解液中再次進行陽極氧化，形成於細孔產生點具有細孔之氧化皮膜的步驟。(c) a step of anodizing the aluminum substrate again in the electrolytic solution to form an oxide film having fine pores at the point where the pores are generated.
(d)使細孔之直徑擴大的步驟。(d) a step of expanding the diameter of the pores.
(e)於步驟(d)之後，於電解液中再次進行陽極氧化的步驟。(e) a step of performing anodization again in the electrolytic solution after the step (d).
(f)反覆進行步驟(d)與步驟(e)，獲得於鋁基材之表面形成有具有2個以上細孔的陽極氧化鋁之模具的步 驟。(f) Steps (d) and (e) are repeatedly carried out to obtain a step of forming an anodized aluminum mold having two or more fine pores on the surface of the aluminum substrate. Step.
步驟(a)：Step (a):
如圖2所示，對鋁基材10進行陽極氧化，則形成具有細孔12之氧化皮膜14。As shown in FIG. 2, the aluminum substrate 10 is anodized to form an oxide film 14 having pores 12.
鋁基材之形狀可列舉輥狀、圓筒狀、平板狀、及薄板狀等。Examples of the shape of the aluminum base material include a roll shape, a cylindrical shape, a flat plate shape, and a thin plate shape.
而且，為了使表面狀態平滑化，較佳的是藉由機械研磨、拋光布研磨、化學研磨、及電解研磨處理(蝕刻處理)等而對鋁基材進行研磨。而且，鋁基材可能附著有加工為預定形狀時所使用之油，因此較佳的是於陽極氧化之前預先進行脫脂處理。Further, in order to smooth the surface state, it is preferred to polish the aluminum substrate by mechanical polishing, polishing cloth polishing, chemical polishing, and electrolytic polishing treatment (etching treatment). Further, the aluminum substrate may have an oil used for processing into a predetermined shape, and therefore it is preferred to perform degreasing treatment in advance before anodization.
鋁之純度較佳的是99%以上，更佳的是99.5%以上，特佳的是99.8%以上。若鋁之純度低，則存在如下之現象：於進行陽極氧化時，由於雜質之偏析而形成可散射可見光之大小的凹凸結構，或者藉由陽極氧化而所得之細孔的規則性降低。The purity of aluminum is preferably 99% or more, more preferably 99.5% or more, and particularly preferably 99.8% or more. When the purity of aluminum is low, there is a phenomenon in which, when anodization is performed, a concavo-convex structure capable of scattering visible light due to segregation of impurities or a regularity of pores obtained by anodization is lowered.
電解液可列舉硫酸、草酸、以及磷酸等。Examples of the electrolytic solution include sulfuric acid, oxalic acid, and phosphoric acid.
於使用草酸作為電解液之情形時：When using oxalic acid as the electrolyte:
草酸之濃度較佳的是0.7M以下。若草酸之濃度超過0.7M，則存在電流值變得過高而導致氧化皮膜之表面變粗之現象。The concentration of oxalic acid is preferably 0.7 M or less. If the concentration of oxalic acid exceeds 0.7 M, there is a phenomenon that the current value becomes too high and the surface of the oxide film becomes thick.
於化成電壓(formation voltage)為30V~60V時，可獲得具有週期為100nm之規則性高的細孔的陽極氧化鋁。無論化成電壓較該範圍更高還是更低，均存在規則性 降低之傾向。When the formation voltage is 30 V to 60 V, anodized aluminum having regular pores having a periodicity of 100 nm can be obtained. Regularity exists regardless of whether the formation voltage is higher or lower than the range Reduce the tendency.
電解液之溫度較佳的是60℃以下，更佳的是45℃以下。若電解液之溫度超過60℃，則存在如下之現象：產生所謂之「風化」之現象，細孔被破壞，或表面熔化而導致細孔之規則性變亂。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 exceeds 60 ° C, there is a phenomenon in which so-called "weathering" occurs, pores are broken, or the surface is melted to cause regularity of pores.
於使用硫酸作為電解液之情形時：When using sulfuric acid as the electrolyte:
硫酸之濃度較佳的是0.7M以下。若硫酸之濃度超過0.7M，則存在如下之現象：電流值變得過高而變得無法維持恆定電壓。The concentration of sulfuric acid is preferably 0.7 M or less. When the concentration of sulfuric acid exceeds 0.7 M, there is a phenomenon that the current value becomes too high and the constant voltage cannot be maintained.
於化成電壓為25V~30V時，可獲得具有週期為63nm之規則性高的細孔的陽極氧化鋁。無論化成電壓較該範圍更高還是更低，均存在規則性降低之傾向。When the formation voltage is 25 V to 30 V, anodized aluminum having a regular fine pore having a period of 63 nm can be obtained. Regardless of whether the formation voltage is higher or lower than the range, there is a tendency for the regularity to decrease.
電解液之溫度較佳的是30℃以下，更佳的是20℃以下。若電解液之溫度超過30℃，則存在如下之現象：產生所謂之「風化」之現象，細孔被破壞，或表面熔化而導致細孔之規則性變亂。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 exceeds 30 ° C, there is a phenomenon in which so-called "weathering" occurs, pores are broken, or the surface is melted to cause regularity of pores.
步驟(b)：Step (b):
如圖2所示，將氧化皮膜14暫時除去，將其作為陽極氧化之細孔產生點16，藉此可提高細孔之規則性。As shown in Fig. 2, the oxide film 14 is temporarily removed, and this is used as an anodized pore generating point 16, whereby the regularity of the pores can be improved.
將氧化皮膜除去之方法可列舉：使其溶解於並不溶解鋁而是選擇性地溶解氧化皮膜之溶液中而將其除去的方法。此種溶液例如可列舉鉻酸/磷酸混合液等。The method of removing the oxide film is a method of dissolving it in a solution which does not dissolve aluminum but selectively dissolves the oxide film and removes it. Examples of such a solution include a chromic acid/phosphoric acid mixed solution.
步驟(c)：Step (c):
如圖2所示，對除去了氧化皮膜之鋁基材10再次進行 陽極氧化，則形成具有圓柱狀細孔12之氧化皮膜14。As shown in FIG. 2, the aluminum substrate 10 from which the oxide film is removed is again subjected to Upon anodization, an oxide film 14 having cylindrical pores 12 is formed.
陽極氧化於與步驟(a)同樣之條件下進行即可。陽極氧化之時間越長則越可以獲得深的細孔。The anodization may be carried out under the same conditions as in the step (a). The longer the anodization time, the deeper the pores can be obtained.
步驟(d)：Step (d):
如圖2所示，進行使細孔12之直徑擴大之處理(以下記為細孔徑擴大處理)。細孔徑擴大處理是浸漬於溶解氧化皮膜之溶液中，使藉由陽極氧化而所得之細孔之直徑擴大的處理。此種溶液例如可列舉5wt%左右之磷酸水溶液等。As shown in Fig. 2, a process of expanding the diameter of the pores 12 (hereinafter referred to as a pore diameter expansion process) is performed. The pore diameter enlargement treatment is a treatment of immersing in a solution in which an oxide film is dissolved, and expanding the diameter of pores obtained by anodization. Examples of such a solution include a 5 wt% aqueous phosphoric acid solution.
細孔徑擴大處理之時間越長，則細孔徑變得越大。The longer the pore diameter enlargement treatment, the larger the pore diameter becomes.
步驟(e)：Step (e):
如圖2所示，再次進行陽極氧化，則進一步形成自圓柱狀細孔12之底部向下延伸的直徑小的圓柱狀細孔12。As shown in Fig. 2, anodization is performed again, and further, cylindrical small pores 12 having a small diameter extending downward from the bottom of the cylindrical pores 12 are formed.
陽極氧化於與步驟(a)同樣之條件下進行即可。陽極氧化之時間越長則越可以獲得深的細孔。The anodization may be carried out under the same conditions as in the step (a). The longer the anodization time, the deeper the pores can be obtained.
步驟(f)：Step (f):
如圖2所示，反覆進行步驟(d)之細孔徑擴大處理、與步驟(e)之陽極氧化，則形成具有細孔12(所述細孔12具有直徑自開口部向深度方向連續性減少的形狀)的氧化皮膜14，從而獲得於鋁基材10之表面形成有陽極氧化鋁(鋁之多孔質氧化皮膜(alumite，防蝕鋁))的模具18。較佳的是最後以步驟(d)結束。As shown in FIG. 2, the pore diameter expansion treatment of the step (d) and the anodization of the step (e) are repeated to form the pores 12 (the pores 12 have a diameter which decreases in continuity from the opening portion in the depth direction). The oxide film 14 of the shape) is obtained by a mold 18 having an anodized aluminum (aluminum porous oxide film) formed on the surface of the aluminum substrate 10. Preferably, it ends with step (d).
反覆次數較佳的是合計3次以上，更佳的是5次以上。若反覆次數為2次以下，則細孔之直徑非連續性地減少，因此使用具有此種細孔之陽極氧化鋁而形成的蛾眼結構的 反射率減低效果並不充分。The number of repetitions is preferably 3 or more times in total, and more preferably 5 or more times. When the number of times of the repetition is two or less, the diameter of the pores is discontinuously reduced, and therefore the moth-eye structure formed using the anodized aluminum having such pores is used. The effect of reducing the reflectance is not sufficient.
細孔12之形狀可列舉略圓錐形狀、角錐形狀、及圓柱形狀等，較佳的是如圓錐形狀以及角錐形狀等這樣的與深度方向正交之方向的細孔截面積自最表面向深度方向連續性減少之形狀。The shape of the pores 12 may be a slightly conical shape, a pyramid shape, a cylindrical shape or the like. It is preferable that the cross-sectional area of the pores in the direction orthogonal to the depth direction such as a conical shape and a pyramid shape is from the outermost surface to the depth direction. The shape of continuity is reduced.
細孔12間之平均間隔為可見光之波長以下，亦即400nm以下。細孔12間之平均間隔較佳的是20nm以上。The average interval between the pores 12 is below the wavelength of visible light, that is, below 400 nm. The average interval between the pores 12 is preferably 20 nm or more.
細孔12間之平均間隔之範圍較佳的是20nm以上400nm以下，更佳的是50nm以上300nm以下，進一步更佳的是90nm以上250nm以下。The range of the average interval between the pores 12 is preferably 20 nm or more and 400 nm or less, more preferably 50 nm or more and 300 nm or less, still more preferably 90 nm or more and 250 nm or less.
細孔12間之平均間隔是藉由電子顯微鏡觀察而測定50點鄰接之細孔12間之間隔(自細孔12之中心至鄰接之細孔12之中心的距離)，將該些值加以平均而所得的值。The average interval between the pores 12 is determined by an electron microscope to measure the interval between the adjacent pores 12 of 50 points (the distance from the center of the pores 12 to the center of the adjacent pores 12), and the values are averaged. And the resulting value.
細孔12之深度於平均間隔為100nm之情形時，較佳的是80nm~500nm，更佳的是120nm~400nm，特佳的是150nm~300nm。When the depth of the pores 12 is at an average interval of 100 nm, it is preferably 80 nm to 500 nm, more preferably 120 nm to 400 nm, and particularly preferably 150 nm to 300 nm.
細孔12之深度是藉由電子顯微鏡觀察而以30000倍之倍率進行觀察時，測定細孔12之最底部與存在於細孔12間之凸部的最頂部之間的距離而所得的值。The depth of the pores 12 is a value obtained by measuring the distance between the bottommost portion of the pores 12 and the topmost portion of the convex portion existing between the pores 12 when observed by an electron microscope at a magnification of 30,000 times.
細孔12之縱橫比(細孔之深度/細孔間之平均間隔)較佳的是0.8~5.0，更佳的是1.2~4.0，特佳的是1.5~3.0。The aspect ratio of the pores 12 (the depth of the pores/the average interval between the pores) is preferably from 0.8 to 5.0, more preferably from 1.2 to 4.0, and particularly preferably from 1.5 to 3.0.
(脫模劑)(release agent)
其次，藉由脫模劑對模具之形成有微細凹凸結構之側的表面進行處理。Next, the surface of the mold on the side where the fine uneven structure is formed is treated by a releasing agent.
脫模劑較佳的是具有可與鋁基材之陽極氧化鋁形成化學鍵之官能基的脫模劑。The release agent is preferably a release agent having a functional group capable of forming a chemical bond with the anodized aluminum of the aluminum substrate.
脫模劑可列舉矽氧樹脂、氟樹脂、及氟化合物等，自脫模性優異之方面以及與模具之密接性優異之方面考慮，較佳的是具有矽醇基或水解性矽烷基，其中特佳的是具有水解性矽烷基之氟化合物。具有水解性矽烷基之氟化合物的市售品可列舉氟烷基矽烷、KBM-7803(信越化學工業公司製造)、「OPTOOL(註冊商標)」系列(大金工業公司製造)、以及Novec EGC-1720(住友3M公司製造)等。Examples of the release agent include a fluorinated resin, a fluororesin, and a fluorine compound. The oxime group or the hydrolyzable decyl group is preferred because it is excellent in mold release property and excellent in adhesion to a mold. Particularly preferred are fluorine compounds having a hydrolyzable decyl group. The commercially available product of the hydrolyzable decyl group-containing fluorine compound is fluoroalkyl decane, KBM-7803 (manufactured by Shin-Etsu Chemical Co., Ltd.), "OPTOOL (registered trademark)" series (manufactured by Daikin Industries, Ltd.), and Novec EGC- 1720 (manufactured by Sumitomo 3M) and so on.
利用脫模劑之處理方法可列舉下述方法(II-1)及方法(II-2)，自可藉由脫模劑對模具之形成有微細凹凸結構之側的表面並無不均地進行處理之方面考慮，特佳的是方法(II-1)。The following methods (II-1) and (II-2) can be used as the treatment method of the release agent, and the surface on the side where the mold has a fine uneven structure can be formed by the release agent without unevenness. In terms of handling, it is particularly preferable to use method (II-1).
(II-1)於脫模劑之稀釋溶液中浸漬模具之方法。(II-1) A method of immersing a mold in a diluted solution of a release agent.
(II-2)將脫模劑或其稀釋溶液塗佈於模具之形成有微細凹凸結構之側的表面的方法。(II-2) A method of applying a release agent or a diluted solution thereof to a surface of a mold on a side where a fine uneven structure is formed.
方法(II-1)較佳的是具有下述步驟(g)~步驟(l)之方法。The method (II-1) preferably has the following steps (g) to (l).
(g)對模具進行水洗之步驟。(g) A step of washing the mold with water.
(h)對模具吹空氣，將附著於模具之表面的水滴除去的步驟。(h) a step of blowing air to the mold to remove water droplets adhering to the surface of the mold.
(i)將模具浸漬於以溶劑將具有水解性矽烷基之氟化合物稀釋而成之稀釋溶液中的步驟。(i) a step of immersing the mold in a diluted solution obtained by diluting a fluorine compound having a hydrolyzable decyl group in a solvent.
(j)將所浸漬之模具緩緩地自溶液中拉出的步驟。(j) a step of slowly pulling the impregnated mold out of the solution.
(k)視需要於步驟(j)之更後段，對模具進行加熱加濕的步驟。(k) a step of heating and humidifying the mold as needed in the later stage of the step (j).
(l)使模具乾燥的步驟。(l) A step of drying the mold.
<表面具有微細凹凸結構的物品的製造方法><Method for Producing Article with Fine Concavo-Concave Structure on Surface>
本發明之表面具有微細凹凸結構的物品的製造方法是將表面經脫模劑處理之模具之表面的微細凹凸結構轉印至物品本體之表面，製造表面具有微細凹凸結構的物品的方法，是將微細凹凸結構轉印至物品本體之表面，測定將所述物品本體自模具剝離之後的模具之表面的紅外分光光譜，基於所述紅外分光光譜而判定模具之表面的脫模劑之狀態之良否的方法。The method for producing an article having a fine uneven structure on the surface of the present invention is a method of transferring a fine uneven structure on the surface of a mold subjected to a release agent treatment to the surface of the article body to produce an article having a fine uneven structure on the surface, The fine concavo-convex structure is transferred onto the surface of the article body, and an infrared spectroscopic spectrum of the surface of the mold after the article body is peeled from the mold is measured, and the state of the release agent on the surface of the mold is determined based on the infrared spectroscopic spectrum. method.
將模具之表面的微細凹凸結構轉印至物品本體之表面的方法例如可列舉具有下述步驟(i)~步驟(iii)的方法。A method of transferring the fine uneven structure on the surface of the mold to the surface of the article body may, for example, be a method having the following steps (i) to (iii).
(i)於表面具有微細凹凸結構且所述表面經脫模劑處理之模具、與物品本體之間，夾持活性能量線硬化性樹脂組成物的步驟。(i) a step of sandwiching an active energy ray-curable resin composition between a mold having a fine uneven structure on its surface and having the surface treated with a release agent and a body of the article.
(ii)對活性能量線硬化性樹脂組成物照射活性能量線，使所述活性能量線硬化性樹脂組成物硬化而形成具有微細凹凸結構之硬化樹脂層的步驟。(ii) a step of irradiating the active energy ray-curable resin composition with an active energy ray to cure the active energy ray-curable resin composition to form a cured resin layer having a fine uneven structure.
(iii)使模具自物品本體之表面的硬化樹脂層脫模，獲得表面具有微細凹凸結構的物品的步驟。(iii) A step of releasing the mold from the hardened resin layer on the surface of the article body to obtain an article having a fine uneven structure on the surface.
(物品本體)(object body)
作為物品本體之材料，為了隔著物品本體而進行活性能量線之照射，較佳的是透明性高之材料，例如可列舉丙 烯酸系樹脂、聚對苯二甲酸乙二酯、聚碳酸酯、及三乙酸纖維素等。As the material of the article body, in order to irradiate the active energy ray through the article body, a material having high transparency is preferable, and for example, C can be cited. An olefinic resin, polyethylene terephthalate, polycarbonate, cellulose triacetate or the like.
物品本體之形狀可列舉薄膜、薄板、射出成形品、及擠壓成形品等。Examples of the shape of the article main body include a film, a sheet, an injection molded article, and an extrusion molded article.
(活性能量線硬化性樹脂組成物)(Active energy ray curable resin composition)
活性能量線硬化性樹脂組成物包含聚合性化合物及聚合起始劑。The active energy ray-curable resin composition contains a polymerizable compound and a polymerization initiator.
聚合性化合物可列舉於分子中具有自由基聚合性鍵及/或陽離子聚合性鍵之單體、寡聚物、及反應性聚合物等。Examples of the polymerizable compound include a monomer having a radical polymerizable bond and/or a cationic polymerizable bond in the molecule, an oligomer, and a reactive polymer.
活性能量線硬化性樹脂組成物亦可包含非反應性之聚合物、及活性能量線溶膠-凝膠反應性組成物。The active energy ray-curable resin composition may also contain a non-reactive polymer and an active energy ray sol-gel reactive composition.
具有自由基聚合性鍵之單體可列舉單官能單體及多官能單體。The monomer having a radical polymerizable bond may, for example, be a monofunctional monomer or a polyfunctional monomer.
單官能單體可列舉(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸月桂基酯、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸硬脂基酯等(甲基)丙烯酸烷基酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸苄基酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸四氫呋喃甲基酯、(甲基)丙烯酸烯丙基酯、(甲基)丙烯酸-2-羥基乙酯、(甲基)丙烯酸羥基丙酯、(甲基)丙烯酸-2-甲氧基乙酯、及(甲基)丙烯酸-2-乙氧基乙酯等(甲基)丙烯酸酯衍生物；(甲基)丙烯 酸、(甲基)丙烯腈；苯乙烯、及α-甲基苯乙烯等苯乙烯衍生物；以及(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N,N-二乙基(甲基)丙烯醯胺、及二甲基胺基丙基(甲基)丙烯醯胺等(甲基)丙烯醯胺衍生物等。該些化合物可單獨使用1種，亦可併用2種以上。Examples of the monofunctional monomer include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate. Base) butyl acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate And alkyl (meth)acrylate such as stearyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, ( Isobornyl methyl methacrylate, glycidyl (meth) acrylate, tetrahydrofuran methyl (meth) acrylate, allyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, ( (meth) acrylate derivatives such as hydroxypropyl methacrylate, 2-methoxyethyl (meth) acrylate, and 2-ethoxyethyl (meth) acrylate; (methyl) Propylene Acid, (meth)acrylonitrile; styrene, and styrene derivatives such as α-methylstyrene; and (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N A (meth) acrylamide derivative such as N-diethyl(meth)acrylamide or dimethylaminopropyl(meth)acrylamide. These compounds may be used alone or in combination of two or more.
多官能單體可列舉乙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、異三聚氰酸環氧乙烷改性二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,5-戊二醇二(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、聚丁二醇二(甲基)丙烯酸酯、2,2-雙(4-(甲基)丙烯醯氧基聚乙氧基苯基)丙烷、2,2-雙(4-(甲基)丙烯醯氧基乙氧基苯基)丙烷、2,2-雙(4-(3-(甲基)丙烯醯氧基-2-羥基丙氧基)苯基)丙烷、1,2-雙(3-(甲基)丙烯醯氧基-2-羥基丙氧基)乙烷、1,4-雙(3-(甲基)丙烯醯氧基-2-羥基丙氧基)丁烷、二羥甲基三環癸烷二(甲基)丙烯酸酯、雙酚A之環氧乙烷加成物二(甲基)丙烯酸酯、雙酚A之環氧丙烷加成物二(甲基)丙烯酸酯、羥基特戊酸新戊二醇二(甲基)丙烯酸酯、二乙烯苯、及亞甲雙丙烯醯胺等二官能性單體；季戊四醇三(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、三羥甲基丙烷環氧乙烷改性三(甲基)丙烯酸酯、三羥甲基丙烷環氧丙烷改性三丙烯酸酯、三羥甲基丙烷環氧乙烷改性三丙烯酸酯、異三聚氰酸環氧乙烷改性三(甲基)丙烯酸酯等三官能單體；琥珀酸/三羥甲基乙烷/丙烯酸之縮合反 應混合物、二季戊四醇六(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二-三羥甲基丙烷四丙烯酸酯、及四羥甲基甲烷四(甲基)丙烯酸酯等四官能以上之單體；以及二官能以上之丙烯酸胺基甲酸酯、及二官能以上之聚酯丙烯酸酯等。該些化合物可單獨使用1種，亦可併用2種以上。Examples of the polyfunctional monomer include ethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, isomeric cyanuric acid ethylene oxide-modified di(meth)acrylate, and triethylene glycol. Di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,5 - pentanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, polybutylene glycol di(meth)acrylate, 2,2-bis(4-(methyl) Acetyleneoxypolyethoxyphenyl)propane, 2,2-bis(4-(methyl)propenyloxyethoxyphenyl)propane, 2,2-bis(4-(3-() Methyl)propenyloxy-2-hydroxypropoxy)phenyl)propane, 1,2-bis(3-(methyl)propenyloxy-2-hydroxypropoxy)ethane, 1,4 - bis(3-(methyl)propenyloxy-2-hydroxypropoxy)butane, dimethylol tricyclodecane di(meth)acrylate, bisphenol A ethylene oxide addition Di(meth)acrylate, propylene oxide adduct di(meth)acrylate of bisphenol A, hydroxypivalic acid neopentyl glycol di(meth)acrylate, divinylbenzene, and methylene Bisacrylamide Energy monomer; pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethylene oxide modified tri(meth)acrylate, trimethylol a trifunctional monomer such as propane propylene oxide modified triacrylate, trimethylolpropane ethylene oxide modified triacrylate, isomeric cyanuric acid ethylene oxide modified tri(meth)acrylate; amber Acid/trimethylolethane/acrylic acid condensation Should be a mixture of dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, di-trimethylolpropane tetraacrylate, and tetramethylol methane tetra(meth) acrylate The above monomers; and difunctional or higher urethane acrylates, and difunctional or higher polyester acrylates. These compounds may be used alone or in combination of two or more.
具有陽離子聚合性鍵之單體可列舉具有環氧基、氧雜環丁基、噁唑基、乙烯基氧基等之單體，特佳的是具有環氧基之單體。The monomer having a cationically polymerizable bond may, for example, be a monomer having an epoxy group, an oxetanyl group, an oxazolyl group or a vinyloxy group, and particularly preferably a monomer having an epoxy group.
寡聚物或反應性聚合物可列舉不飽和二羧酸與多元醇之縮合物等不飽和聚酯類；聚酯(甲基)丙烯酸酯、聚醚(甲基)丙烯酸酯、多元醇(甲基)丙烯酸酯、(甲基)丙烯酸環氧酯、(甲基)丙烯酸胺基甲酸酯、陽離子聚合型環氧化合物、及於側鏈具有自由基聚合性鍵之上述單體的均聚物或共聚物等。Examples of the oligomer or the reactive polymer include unsaturated polyesters such as a condensate of an unsaturated dicarboxylic acid and a polyhydric alcohol; polyester (meth) acrylate, polyether (meth) acrylate, and polyhydric alcohol (A) a acrylate, a (meth)acrylic acid epoxy ester, a (meth)acrylic acid urethane, a cationically polymerized epoxy compound, and a homopolymer of the above monomer having a radical polymerizable bond in a side chain Or copolymers, etc.
非反應性聚合物可列舉丙烯酸系樹脂、苯乙烯系樹脂、聚胺基甲酸酯、纖維素系樹脂、聚乙烯丁醛、聚酯、及熱塑性彈性體等。Examples of the non-reactive polymer include an acrylic resin, a styrene resin, a polyurethane, a cellulose resin, a polyvinyl butyral, a polyester, and a thermoplastic elastomer.
活性能量線溶膠-凝膠反應性組成物可列舉烷氧基矽烷化合物、及矽酸烷基酯化合物等。The active energy ray sol-gel reactive composition may, for example, be an alkoxydecane compound or an alkyl phthalate compound.
烷氧基矽烷化合物可列舉下述式(1)之化合物。The alkoxydecane compound is exemplified by the compound of the following formula (1).
R11 x Si(OR12 )y (1)R 11 x Si(OR 12 ) y (1)
其中，R11 、R12 分別表示碳數為1~10之烷基，x、y 表示滿足x+y=4之關係的整數。Here, R 11 and R 12 each represent an alkyl group having a carbon number of 1 to 10, and x and y represent an integer satisfying the relationship of x + y = 4.
烷氧基矽烷化合物可列舉四甲氧基矽烷、四異丙氧基矽烷、四正丙氧基矽烷、四正丁氧基矽烷、四第二丁氧基矽烷、四第三丁氧基矽烷、甲基三乙氧基矽烷、甲基三丙氧基矽烷、甲基三丁氧基矽烷、二甲基二甲氧基矽烷、二甲基二乙氧基矽烷、三甲基乙氧基矽烷、三甲基甲氧基矽烷、三甲基丙氧基矽烷、及三甲基丁氧基矽烷等。The alkoxy decane compound may, for example, be tetramethoxy decane, tetraisopropoxy decane, tetra-n-propoxy decane, tetra-n-butoxy decane, tetra-butoxy decane or tetra-butoxy decane. Methyl triethoxy decane, methyl tripropoxy decane, methyl tributoxy decane, dimethyl dimethoxy decane, dimethyl diethoxy decane, trimethyl ethoxy decane, Trimethyl methoxy decane, trimethyl propoxy decane, and trimethyl butoxy decane.
矽酸烷基酯化合物可列舉下述式(2)之化合物。The alkyl phthalate compound is exemplified by the compound of the following formula (2).
R21 O[Si(OR23 )(OR24 )O]z R22 (2)R 21 O[Si(OR 23 )(OR 24 )O] z R 22 (2)
其中，R21 ~R24 分別表示碳數為1~5之烷基，z表示3~20之整數。Wherein R 21 to R 24 each represent an alkyl group having a carbon number of 1 to 5, and z represents an integer of 3 to 20.
矽酸烷基酯化合物可列舉矽酸甲酯、矽酸乙酯、矽酸異丙酯、矽酸正丙酯、矽酸正丁酯、矽酸正戊酯、及乙醯基矽酸酯等。Examples of the alkyl phthalate compound include methyl decanoate, ethyl decanoate, isopropyl citrate, n-propyl decanoate, n-butyl decanoate, n-amyl decanoate, and ethyl decanoate. .
利用光硬化反應之情形時，光聚合起始劑例如可列舉安息香、安息香甲醚、安息香***、安息香異丙醚、安息香異丁醚、二苯乙二酮(benzil)、二苯甲酮、對甲氧基二苯甲酮、2,2-二乙氧基苯乙酮、α,α-二甲氧基-α-苯基苯乙酮、苯甲醯甲酸甲酯、苯甲醯甲酸乙酯、4,4'-雙(二甲基胺基)二苯甲酮、及2-羥基-2-甲基-1-苯基丙烷-1-酮等羰基化合物；一硫化四甲基秋蘭姆、及二硫化四甲基秋蘭姆等硫化合物；以及2,4,6-三甲基苯甲醯基二苯基膦氧化物、及 苯甲醯基二乙氧基膦氧化物等。該些化合物可單獨使用1種，亦可併用2種以上。In the case of photohardening reaction, examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzil, benzophenone, and Methoxybenzophenone, 2,2-diethoxyacetophenone, α,α-dimethoxy-α-phenylacetophenone, methyl benzhydrazide, ethyl benzhydrazide a carbonyl compound such as 4,4'-bis(dimethylamino)benzophenone and 2-hydroxy-2-methyl-1-phenylpropan-1-one; tetramethylthiuram monosulfide And sulfur compounds such as tetramethylthiuram disulfide; and 2,4,6-trimethylbenzhydryldiphenylphosphine oxide, and Benzopyridyldiethoxyphosphine oxide and the like. These compounds may be used alone or in combination of two or more.
利用電子束硬化反應之情形時，聚合起始劑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、2,4-二乙基噻噸酮、異丙基噻噸酮、及2,4-二氯噻噸酮等噻噸酮；二乙氧基苯乙酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、苯偶醯二甲基縮酮(benzil dimethyl ketal)、1-羥基環己基-苯基酮、2-甲基-2-N-嗎啉基(4-硫甲基苯基)丙烷-1-酮、及2-苄基-2-二甲基胺基-1-(4-N-嗎啉基苯基)-丁酮等苯乙酮；安息香甲醚、安息香***、安息香異丙醚、及安息香異丁醚等安息香醚；2,4,6-三甲基苯甲醯基二苯基膦氧化物、雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基戊基膦氧化物、及雙(2,4,6-三甲基苯甲醯基)-苯基膦氧化物等醯基膦氧化物；以及苯甲醯甲酸甲酯、1,7-雙吖啶基庚烷、及9-苯基吖啶等。該些化合物可單獨使用1種，亦可併用2種以上。In the case of the electron beam hardening reaction, examples of the polymerization initiator include benzophenone, 4,4-bis(diethylamino)benzophenone, and 2,4,6-trimethylbenzophenone. Ketone, methyl phthalyl benzoate, 4-phenyl benzophenone, tert-butyl hydrazine, 2-ethyl hydrazine, 2,4-diethyl thioxanthone, isopropyl Thiophenones such as thioxanthone and 2,4-dichlorothioxanthone; diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzoin Benzil dimethyl ketal, 1-hydroxycyclohexyl-phenyl ketone, 2-methyl-2-N-morpholinyl (4-thiomethylphenyl)propan-1-one, and 2 Acetophenone such as -benzyl-2-dimethylamino-1-(4-N-morpholinylphenyl)-butanone; benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether Benzoin ether; 2,4,6-trimethylbenzimidyl diphenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethylpentane a phosphine oxide, and a mercaptophosphine oxide such as bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide; and methyl benzoguanidinecarboxylate, 1,7-biacene Heptane, and 9-phenyl acridine. These compounds may be used alone or in combination of two or more.
利用熱硬化反應之情形時，熱聚合起始劑例如可列舉過氧化甲基乙基酮、過氧化苯甲醯、過氧化二異丙苯、第三丁基過氧化氫、氫過氧化異丙苯、第三丁基過氧基辛酸酯、第三丁基過氧基苯甲酸酯、及過氧化月桂醯等有機過氧化物；偶氮雙異丁腈等偶氮系化合物；以及於所述有機過氧化物中組合N,N-二甲基苯胺、以及N,N-二甲基對甲苯胺等胺而成之氧化還原聚合起始劑等。In the case of using a thermosetting reaction, examples of the thermal polymerization initiator include methyl ethyl ketone peroxide, benzamidine peroxide, dicumyl peroxide, t-butyl hydroperoxide, and isopropyl hydroperoxide. An organic peroxide such as benzene, t-butylperoxyoctanoate, tert-butylperoxybenzoate, and laurel, and an azo compound such as azobisisobutyronitrile; A redox polymerization initiator which is obtained by combining an amine such as N,N-dimethylaniline or N,N-dimethyl-p-toluidine with the organic peroxide.
聚合起始劑之量較佳的是相對於聚合性化合物100重量份為0.1重量份~10重量份。若聚合起始劑之量不足0.1重量份，則難以進行聚合。若聚合起始劑之量超過10重量份，則存在硬化膜著色、機械強度降低之現象。The amount of the polymerization initiator is preferably from 0.1 part by weight to 10 parts by weight per 100 parts by weight of the polymerizable compound. If the amount of the polymerization initiator is less than 0.1 part by weight, it is difficult to carry out polymerization. When the amount of the polymerization initiator exceeds 10 parts by weight, the cured film may be colored and the mechanical strength may be lowered.
活性能量線硬化性樹脂組成物亦可視需要含有靜電防止劑、脫模劑、用以提高防污性之氟化合物等添加劑；微粒子、及少量之溶劑。The active energy ray-curable resin composition may optionally contain an antistatic agent, a release agent, an additive such as a fluorine compound for improving antifouling properties, fine particles, and a small amount of a solvent.
(疏水性材料)(hydrophobic material)
為了使硬化樹脂層的微細凹凸結構之表面的水接觸角為90°以上，較佳的是使用含有含氟化合物或聚矽氧系化合物的組成物作為可形成疏水性材料之活性能量線硬化性樹脂組成物。In order to make the water contact angle of the surface of the fine concavo-convex structure of the cured resin layer 90° or more, it is preferred to use a composition containing a fluorine-containing compound or a polyfluorene-based compound as active energy ray hardenability capable of forming a hydrophobic material. Resin composition.
含氟化合物：Fluorine-containing compounds:
含氟化合物較佳的是具有下述式(3)所表示之氟烷基的化合物。The fluorine-containing compound is preferably a compound having a fluoroalkyl group represented by the following formula (3).
-(CF2 )n -X (3)-(CF 2 ) n -X (3)
其中，X表示氟原子或氫原子，n表示1以上之整數，較佳的是1~20，更佳的是3~10，特佳的是4~8。Here, X represents a fluorine atom or a hydrogen atom, and n represents an integer of 1 or more, preferably 1 to 20, more preferably 3 to 10, and particularly preferably 4 to 8.
含氟化合物可列舉含氟單體、含氟矽烷偶合劑、含氟界面活性劑、及含氟聚合物等。Examples of the fluorine-containing compound include a fluorine-containing monomer, a fluorine-containing decane coupling agent, a fluorine-containing surfactant, and a fluorine-containing polymer.
含氟單體可列舉經氟烷基取代之乙烯系單體、及經氟烷基取代之開環聚合性單體等。Examples of the fluorine-containing monomer include a vinyl monomer substituted with a fluoroalkyl group and a ring-opening polymerizable monomer substituted with a fluoroalkyl group.
經氟烷基取代之乙烯系單體可列舉經氟烷基取代之(甲基)丙烯酸酯、經氟烷基取代之(甲基)丙烯醯胺、經氟烷基取代之乙烯醚、及經氟烷基取代之苯乙烯等。The fluoroalkyl-substituted vinyl monomer may, for example, be a fluoroalkyl-substituted (meth) acrylate, a fluoroalkyl-substituted (meth) acrylamide, a fluoroalkyl-substituted vinyl ether, or a Fluoroalkyl substituted styrene and the like.
經氟烷基取代之開環聚合性單體可列舉經氟烷基取代之環氧化合物、經氟烷基取代之環氧丙烷化合物、及經氟烷基取代之噁唑啉化合物等。The ring-opening polymerizable monomer substituted with a fluoroalkyl group may, for example, be a fluoroalkyl-substituted epoxy compound, a fluoroalkyl-substituted propylene oxide compound, or a fluoroalkyl-substituted oxazoline compound.
含氟單體較佳的是經氟烷基取代之(甲基)丙烯酸酯，特佳的是下述式(4)之化合物。The fluorine-containing monomer is preferably a fluoroalkyl-substituted (meth) acrylate, and particularly preferably a compound of the following formula (4).
CH2 =C(R41 )C(O)O-(CH2 )m -(CF2 )n -X (4)CH 2 =C(R 41 )C(O)O-(CH 2 ) m -(CF 2 ) n -X (4)
其中，R41 表示氫原子或甲基，X表示氫原子或氟原子，m表示1~6之整數，較佳的是1~3，更佳的是1或2，n表示1~20之整數，較佳的是3~10，更佳的是4~8。Wherein R 41 represents a hydrogen atom or a methyl group, X represents a hydrogen atom or a fluorine atom, m represents an integer of 1 to 6, preferably 1 to 3, more preferably 1 or 2, and n represents an integer of 1 to 20 Preferably, it is 3~10, and more preferably 4~8.
含氟矽烷偶合劑較佳的是經氟烷基取代之矽烷偶合劑，特佳的是下述式(5)之化合物。The fluorine-containing decane coupling agent is preferably a fluoroalkyl-substituted decane coupling agent, and particularly preferably a compound of the following formula (5).
(Rf )a R51 b SiYc (5)(R f ) a R 51 b SiY c (5)
Rf 表示亦可含有1個以上醚鍵或酯鍵之碳數為1~20之經氟取代之烷基。Rf 可列舉3,3,3-三氟丙基、十三氟-1,1,2,2-四氫辛基、3-三氟甲氧基丙基、及3-三氟乙醯氧基丙基等。R f represents a fluorine-substituted alkyl group having 1 or more carbon atoms which may further contain one or more ether bonds or ester bonds. R f may, for example, be 3,3,3-trifluoropropyl, decafluoro-1,1,2,2-tetrahydrooctyl, 3-trifluoromethoxypropyl, and 3-trifluoroacetoxy Base propyl and the like.
R51 表示碳數為1~10之烷基。R51 可列舉甲基、乙基、 及環己基等。R 51 represents an alkyl group having 1 to 10 carbon atoms. Examples of R 51 include a methyl group, an ethyl group, a cyclohexyl group and the like.
Y表示羥基或水解性基。Y represents a hydroxyl group or a hydrolyzable group.
水解性基可列舉烷氧基、及鹵素原子、R52 C(O)O(其中，R52 表示氫原子或碳數為1~10之烷基)等。Examples of the hydrolyzable group include an alkoxy group, a halogen atom, and R 52 C(O)O (wherein R 52 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms).
烷氧基可列舉甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、異丁氧基、第三丁氧基、戊氧基、己氧基、環己氧基、庚氧基、辛氧基、2-乙基己氧基、壬氧基、癸氧基、3,7-二甲基辛氧基、及月桂基氧基等。The alkoxy group may, for example, be a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a third butoxy group, a pentyloxy group, a hexyloxy group or a cyclohexyloxy group. Heptyloxy, octyloxy, 2-ethylhexyloxy, decyloxy, decyloxy, 3,7-dimethyloctyloxy, and lauryloxy.
鹵素原子可列舉Cl、Br、及I等。Examples of the halogen atom include Cl, Br, and I.
R52 C(O)O可列舉CH3 C(O)O、及C2 H5 C(O)O等。Examples of R 52 C(O)O include CH 3 C(O)O, and C 2 H 5 C(O)O.
a、b、及c表示a+b+c=4且滿足a≧1、及c≧1之整數，較佳的是a=1、b=0、及c=3。a, b, and c represent a+b+c=4 and satisfy the integers of a≧1 and c≧1, and preferably a=1, b=0, and c=3.
含氟矽烷偶合劑可列舉3,3,3-三氟丙基三甲氧基矽烷、3,3,3-三氟丙基三乙醯氧基矽烷、二甲基-3,3,3-三氟丙基甲氧基矽烷、及十三氟-1,1,2,2-四氫辛基三乙氧基矽烷等。The fluorine-containing decane coupling agent may, for example, be 3,3,3-trifluoropropyltrimethoxydecane, 3,3,3-trifluoropropyltriethoxydecane, or dimethyl-3,3,3-tri Fluoropropyl methoxy decane, and tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxydecane, and the like.
含氟界面活性劑可列舉含有氟烷基之陰離子系界面活性劑、含有氟烷基之陽離子系界面活性劑等。Examples of the fluorine-containing surfactant include an anionic surfactant containing a fluoroalkyl group, a cationic surfactant containing a fluoroalkyl group, and the like.
含有氟烷基之陰離子系界面活性劑可列舉碳數為2~10之氟烷基羧酸或其金屬鹽、全氟辛磺醯基麩胺酸二鈉、3-[ω-氟烷基(C6 ~C11 )氧基]-1-烷基(C3 ~C4 )磺酸鈉、3-[ω-氟烷醯基(C6 ~C8 )-N-乙基胺基]-1-丙磺酸鈉、氟烷基(C11 ~C20 )羧酸或其金屬鹽、全氟烷基羧酸(C7 ~C13 )或其金屬鹽、全氟烷基(C4 ~C12 )磺酸或其金屬鹽、全氟辛磺酸二乙 醇胺、N-丙基-N-(2-羥基乙基)全氟辛磺醯胺、全氟烷基(C6 ~C10 )磺醯胺丙基三甲基銨鹽、全氟烷基(C6 ~C10 )-N-乙磺醯基甘胺酸鹽、及單全氟烷基(C6 ~C16 )乙基磷酸酯等。Examples of the fluoroalkyl group-containing anionic surfactant include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonyl glutamate, and 3-[ω-fluoroalkyl ( C 6 ~C 11 )oxy]-1-alkyl (C 3 ~C 4 ) sodium sulfonate, 3-[ω-fluoroalkyl fluorenyl (C 6 -C 8 )-N-ethylamino group]- Sodium 1-propane sulfonate, fluoroalkyl (C 11 ~ C 20 ) carboxylic acid or metal salt thereof, perfluoroalkyl carboxylic acid (C 7 ~ C 13 ) or a metal salt thereof, perfluoroalkyl group (C 4 ~ C 12 ) sulfonic acid or its metal salt, perfluorooctane sulfonic acid diethanolamine, N-propyl-N-(2-hydroxyethyl) perfluorooctanesulfonamide, perfluoroalkyl (C 6 ~C 10 ) Sulfaguanidinium trimethylammonium salt, perfluoroalkyl (C 6 ~C 10 )-N-ethanesulfonylglycine, and monoperfluoroalkyl (C 6 ~C 16 )ethyl phosphate Ester and the like.
含有氟烷基之陽離子系界面活性劑可列舉含有氟烷基之脂肪族一級、二級或三級醯胺酸、全氟烷基(C6 ~C10 )磺醯胺丙基三甲基銨鹽等脂肪族四級銨鹽、苯二甲烴銨(benzalkonium)鹽、苄索氯銨(benzethonium chloride)、吡啶鎓鹽、及咪唑啉鎓鹽等。The fluoroalkyl group-containing cationic surfactant may, for example, be a fluoroalkyl group-containing aliphatic primary, secondary or tertiary phthalic acid, or a perfluoroalkyl (C 6 to C 10 ) sulfoxime propyltrimethylammonium salt. An aliphatic quaternary ammonium salt such as a salt, a benzalkonium salt, a benzothonium chloride, a pyridinium salt, an imidazolinium salt or the like.
含氟聚合物可列舉含有氟烷基之單體之聚合物、含有氟烷基之單體與含有聚(氧基亞烷基)基之單體的共聚物、及含有氟烷基之單體與含有交聯反應性基之單體的共聚物等。含氟聚合物亦可為與可共聚之其他單體之共聚物。The fluoropolymer may, for example, be a polymer of a fluoroalkyl group-containing monomer, a fluoroalkyl group-containing monomer and a poly(oxyalkylene) group-containing monomer copolymer, and a fluoroalkyl group-containing monomer. A copolymer or the like with a monomer having a crosslinking reactive group. The fluoropolymer may also be a copolymer with other monomers copolymerizable.
含氟聚合物較佳的是含有氟烷基之單體與含有聚(氧基亞烷基)基之單體的共聚物。The fluoropolymer is preferably a copolymer of a fluoroalkyl group-containing monomer and a poly(oxyalkylene) group-containing monomer.
聚(氧基亞烷基)基較佳的是下述式(6)所表示基。The poly(oxyalkylene) group is preferably a group represented by the following formula (6).
-(OR61 )p - (6)-(OR 61 ) p - (6)
其中，R61 表示碳數為2~4之亞烷基，p表示2以上之整數。Wherein R 61 represents an alkylene group having 2 to 4 carbon atoms, and p represents an integer of 2 or more.
R61 可列舉-CH2 CH2 -、-CH2 CH2 CH2 -、-CH(CH3 )CH2 -、-CH(CH3 )CH(CH3 )-等。R 61 may, for example, be -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(CH 3 )CH 2 -, -CH(CH 3 )CH(CH 3 )- or the like.
聚(氧基亞烷基)基可為由同一氧基亞烷基單元(OR61 )所構成，亦可為由2種以上氧基亞烷基單元(OR61 )所構成。 2種以上之氧基亞烷基單元(OR61 )之排列可為嵌段亦可為無規。The poly(oxyalkylene) group may be composed of the same oxyalkylene unit (OR 61 ) or may be composed of two or more kinds of oxyalkylene units (OR 61 ). The arrangement of two or more kinds of oxyalkylene units (OR 61 ) may be a block or a random.
聚矽氧系化合物：Polyoxane compounds:
聚矽氧系化合物可列舉(甲基)丙烯酸改性聚矽氧、矽氧樹脂、及聚矽氧系矽烷偶合劑等。Examples of the polyoxymethylene-based compound include (meth)acryl-modified polyfluorene oxide, an anthracene-oxygen resin, and a polyfluorene-based decane coupling agent.
(甲基)丙烯酸改性聚矽氧可列舉聚矽氧(二)(甲基)丙烯酸酯等。Examples of the (meth)acrylic acid-modified polyfluorene oxide include polyfluorene (di)(meth)acrylate.
(親水性材料)(hydrophilic material)
為了使硬化樹脂層之微細凹凸結構之表面的水接觸角為25°以下，較佳的是使用至少含有親水性單體之組成物作為可形成親水性材料之活性能量線硬化性樹脂組成物。而且，自賦予耐擦傷性或耐水性之觀點考慮，更佳的是含有可交聯之多官能單體的組成物。另外，親水性單體與可交聯之多官能單體亦可相同(即，親水性多官能單體)。另外，活性能量線硬化性樹脂組成物亦可含有其他單體。In order to make the water contact angle of the surface of the fine uneven structure of the cured resin layer 25 or less, it is preferable to use a composition containing at least a hydrophilic monomer as an active energy ray-curable resin composition capable of forming a hydrophilic material. Further, from the viewpoint of imparting scratch resistance or water resistance, a composition containing a crosslinkable polyfunctional monomer is more preferable. Further, the hydrophilic monomer may be the same as the crosslinkable polyfunctional monomer (ie, a hydrophilic polyfunctional monomer). Further, the active energy ray-curable resin composition may contain other monomers.
作為可形成親水性材料之活性能量線硬化性樹脂組成物，更佳的是使用含有下述聚合性化合物之組成物。As the active energy ray-curable resin composition capable of forming a hydrophilic material, it is more preferred to use a composition containing the following polymerizable compound.
所述聚合性化合物由4官能以上之多官能(甲基)丙烯酸酯10wt%~50wt%、2官能以上之親水性(甲基)丙烯酸酯30wt%~80wt%、及單官能單體0wt%~20wt%The polymerizable compound is composed of a tetrafunctional or higher polyfunctional (meth) acrylate of 10% by weight to 50% by weight, a bisfunctional or higher hydrophilic (meth) acrylate of 30% by weight to 80% by weight, and a monofunctional monomer of 0% by weight. 20wt%
合計100wt%而構成。It is composed of a total of 100% by weight.
4官能以上之多官能(甲基)丙烯酸酯可列舉二-三羥甲基丙烷四(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、季戊四醇乙氧基四(甲基)丙烯酸酯、二季戊四醇羥基五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、琥珀酸/三羥甲基乙烷/丙烯酸之莫耳比為1：2：4之縮合反應混合物、丙烯酸胺基甲酸酯類(DAICEL-CYTEC Company,Ltd.製造：EBECRYL220、EBECRYL1290、EBECRYL1290K、EBECRYL5129、EBECRYL8210、EBECRYL8301、及KRM8200)、聚醚丙烯酸酯類(DAICEL-CYTEC Company,Ltd.製造：EBECRYL81)、改性丙烯酸環氧酯類(DAICEL-CYTEC Company,Ltd.製造：EBECRYL3416)、及聚酯丙烯酸酯類(DAICEL-CYTEC Company,Ltd.製造：EBECRYL450、EBECRYL657、EBECRYL800、EBECRYL810、EBECRYL811、EBECRYL812、EBECRYL1830、EBECRYL845、EBECRYL846、及EBECRYL1870)等。該些化合物可單獨使用1種，亦可併用2種以上。Examples of the polyfunctional (meth) acrylate having four or more functional groups include di-trimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, and pentaerythritol ethoxytetra(meth)acrylate. Dipentaerythritol hydroxypenta(meth) acrylate, dipentaerythritol hexa(meth) acrylate, succinic acid/trimethylolethane/acrylic acid molar ratio of 1:2:4 condensation reaction mixture, amide group Formate (manufactured by DAICEL-CYTEC Company, Ltd.: EBECRYL220, EBECRYL1290, EBECRYL1290K, EBECRYL5129, EBECRYL8210, EBECRYL8301, and KRM8200), polyether acrylate (DAICEL-CYTEC Company, Ltd.: EBECRYL81), modified acrylic acid Epoxy esters (manufactured by DAICEL-CYTEC Company, Ltd.: EBECRYL 3416), and polyester acrylates (manufactured by DAICEL-CYTEC Company, Ltd.: EBECRYL450, EBECRYL 657, EBECRYL 800, EBECRYL810, EBECRYL811, EBECRYL812, EBECRYL1830, EBECRYL845, EBECRYL846 , and EBECRYL1870) and so on. These compounds may be used alone or in combination of two or more.
4官能以上之多官能(甲基)丙烯酸酯更佳的是5官能以上之多官能(甲基)丙烯酸酯。More preferably, the polyfunctional (meth) acrylate having 4 or more functional groups is a polyfunctional (meth) acrylate having 5 or more functional groups.
4官能以上之多官能(甲基)丙烯酸酯之比例較佳的是10wt%~50wt%，自耐水性、及耐化學品性之方面考慮，更佳的是20wt%~50wt%，特佳的是30wt%~50wt%。若4官能以上之多官能(甲基)丙烯酸酯之比例為10wt%以上，則彈性模數變高而耐擦傷性提高。若4官能以上之多 官能(甲基)丙烯酸酯之比例為50wt%以下，則難以於表面產生小的龜裂，難以變得外觀不良。The ratio of the polyfunctional (meth) acrylate having 4 or more functional groups is preferably 10% by weight to 50% by weight, more preferably 20% by weight to 50% by weight, particularly preferably from 20% by weight to 50% by weight. It is 30wt%~50wt%. When the ratio of the tetrafunctional or higher polyfunctional (meth) acrylate is 10% by weight or more, the elastic modulus is increased and the scratch resistance is improved. If there are more than 4 functional groups When the ratio of the functional (meth) acrylate is 50% by weight or less, it is difficult to cause small cracks on the surface, and it is difficult to cause poor appearance.
2官能以上之親水性(甲基)丙烯酸酯可列舉ARONIX(註冊商標)M-240、ARONIX(註冊商標)M260(東亞合成公司製造)、NK Ester AT-20E、NK Ester ATM-35E(新中村化學公司製造)等具有長鏈聚乙二醇之多官能丙烯酸酯，以及聚乙二醇二甲基丙烯酸酯等。該些化合物可單獨使用1種，亦可併用2種以上。Examples of the hydrophilic (meth) acrylate having a bifunctional or higher functional group include ARONIX (registered trademark) M-240, ARONIX (registered trademark) M260 (manufactured by Toagosei Co., Ltd.), NK Ester AT-20E, and NK Ester ATM-35E (Xin Nakamura). A polyfunctional acrylate having a long-chain polyethylene glycol, such as a chemical company, and polyethylene glycol dimethacrylate. These compounds may be used alone or in combination of two or more.
於聚乙二醇二甲基丙烯酸酯中，於一分子內所存在之聚乙二醇鏈之平均重複單元之合計較佳的是6~40，更佳的是9~30，特佳的是12~20。若聚乙二醇鏈之平均重複單元為6以上，則親水性變充分，防污性提高。若聚乙二醇鏈之平均重複單元為40以下，則與4官能以上之多官能(甲基)丙烯酸酯之相溶性變良好，活性能量線硬化性樹脂組成物難以分離。In the polyethylene glycol dimethacrylate, the total repeating unit of the polyethylene glycol chain present in one molecule is preferably from 6 to 40, more preferably from 9 to 30, particularly preferably 12~20. When the average repeating unit of the polyethylene glycol chain is 6 or more, the hydrophilicity is sufficient and the antifouling property is improved. When the average repeating unit of the polyethylene glycol chain is 40 or less, compatibility with a tetrafunctional or higher polyfunctional (meth) acrylate is improved, and the active energy ray-curable resin composition is difficult to separate.
2官能以上之親水性(甲基)丙烯酸酯之比例較佳的是30wt%~80wt%，更佳的是40wt%~70wt%。若2官能以上之親水性(甲基)丙烯酸酯之比例為30wt%以上，則親水性變充分，防污性提高。若2官能以上之親水性(甲基)丙烯酸酯之比例為80wt%以下，則彈性模數變高且耐擦傷性提高。The proportion of the hydrophilic (meth) acrylate having two or more functional groups is preferably from 30% by weight to 80% by weight, more preferably from 40% by weight to 70% by weight. When the ratio of the hydrophilic (meth) acrylate having two or more functional groups is 30% by weight or more, the hydrophilicity is sufficient and the antifouling property is improved. When the ratio of the hydrophilic (meth) acrylate having two or more functional groups is 80% by weight or less, the elastic modulus is increased and the scratch resistance is improved.
單官能單體較佳的是親水性單官能單體。The monofunctional monomer is preferably a hydrophilic monofunctional monomer.
親水性單官能單體可列舉M-20G、M-90G、及M-230G(新中村化學公司製造)等於酯基具有聚乙二醇鏈之單官 能(甲基)丙烯酸酯；(甲基)丙烯酸羥基烷基酯等於酯基具有羥基之單官能(甲基)丙烯酸酯；單官能丙烯醯胺類；以及甲基丙烯醯胺丙基三甲基銨甲基硫酸鹽、及甲基丙烯醯氧基乙基三甲基銨甲基硫酸鹽等陽離子性單體類等。Examples of the hydrophilic monofunctional monomer include M-20G, M-90G, and M-230G (manufactured by Shin-Nakamura Chemical Co., Ltd.), which is equivalent to an ester group having a polyethylene glycol chain. a (meth) acrylate; a hydroxyalkyl (meth) acrylate equal to a monofunctional (meth) acrylate having an hydroxy group; a monofunctional acrylamide; and a methacrylamide propyl trimethyl methacrylate A cationic monomer such as ammonium methyl sulfate or methacryloxyethyl trimethyl ammonium methyl sulfate.
而且，單官能單體亦可使用丙烯醯基嗎啉、及乙烯基吡咯啶酮等黏度調整劑；以及使對物品本體之密接性提高的丙烯醯基異氰酸酯類等密接性提高劑等。Further, as the monofunctional monomer, a viscosity adjusting agent such as acryloylmorpholine or vinylpyrrolidone; and an adhesion improving agent such as acrylonitrile-based isocyanate which improves the adhesion to the article body can be used.
單官能單體之比例較佳的是0wt%~20wt%，更佳的是5wt%~15wt%。藉由使用單官能單體，可提高物品本體與硬化樹脂之密接性。若單官能單體之比例為20wt%以下，則並無4官能以上之多官能(甲基)丙烯酸酯或2官能以上之親水性(甲基)丙烯酸酯不足之現象，從而可充分地表現出防污性或耐擦傷性。The proportion of the monofunctional monomer is preferably from 0% by weight to 20% by weight, more preferably from 5% by weight to 15% by weight. By using a monofunctional monomer, the adhesion between the article body and the hardening resin can be improved. When the ratio of the monofunctional monomer is 20% by weight or less, there is no shortage of a tetrafunctional or higher polyfunctional (meth) acrylate or a bifunctional or higher hydrophilic (meth) acrylate, so that it can be sufficiently exhibited. Antifouling or scratch resistance.
單官能單體亦可製成使1種或2種以上(共)聚合而成之低聚合度聚合物而以0重量份~35重量份調配於活性能量線硬化性樹脂組成物中。低聚合度聚合物可列舉M-230G(新中村化學公司製造)等於酯基具有聚乙二醇鏈之單官能(甲基)丙烯酸酯類、與甲基丙烯醯胺丙基三甲基銨甲基硫酸鹽之40/60共聚合寡聚物(MRC Unitec公司製造，MG聚合物)等。The monofunctional monomer may be prepared by dispersing one or two or more (co)polymerized low-polymerization polymers in an active energy ray-curable resin composition in an amount of from 0 to 35 parts by weight. The polymer of low polymerization degree is exemplified by M-230G (manufactured by Shin-Nakamura Chemical Co., Ltd.), which is a monofunctional (meth) acrylate having an ester group having a polyethylene glycol chain, and methacrylamidopropyltrimethylammonium 40/60 copolymerized oligomer of sulfate (manufactured by MRC Unitec, MG polymer) and the like.
(製造方法之具體例)(Specific example of manufacturing method)
對使用圖1所示之製造裝置的本發明之表面具有微細凹凸結構的物品的製造方法之具體例加以說明。A specific example of a method for producing an article having a fine uneven structure on the surface of the present invention using the manufacturing apparatus shown in Fig. 1 will be described.
將活性能量線硬化性樹脂組成物自貯槽22供給至表 面具有微細凹凸結構(圖示略)之輥狀模具20、與輥狀模具20之旋轉同步而沿輥狀模具20之表面移動之帶狀薄膜42(物品本體)之間。The active energy ray-curable resin composition is supplied from the storage tank 22 to the watch The roll-shaped mold 20 having a fine uneven structure (not shown) is placed between the strip-shaped film 42 (article body) which moves along the surface of the roll-shaped mold 20 in synchronization with the rotation of the roll-shaped mold 20.
於輥狀模具20、與藉由氣壓缸24而調整夾持壓之軋輥26之間，夾持薄膜42及活性能量線硬化性樹脂組成物，使活性能量線硬化性樹脂組成物均勻地遍布於薄膜42與輥狀模具之間，同時填充於輥狀模具20之微細凹凸結構的凹部內。The film 42 and the active energy ray-curable resin composition are sandwiched between the roll mold 20 and the roll 26 for adjusting the nip pressure by the pneumatic cylinder 24, and the active energy ray-curable resin composition is uniformly distributed. The film 42 and the roll mold are simultaneously filled in the concave portion of the fine uneven structure of the roll mold 20.
自設置於輥狀模具20下方之活性能量線照射裝置28，通過薄膜42而對活性能量線硬化性樹脂組成物照射活性能量線，使活性能量線硬化性樹脂組成物硬化，藉此形成轉印了輥狀模具20之表面的微細凹凸結構的硬化樹脂層44。自活性能量線照射裝置28之光照射能量之量較佳的是100mJ/cm2 ~10000mJ/cm2 。The active energy ray-curable resin composition 28 is irradiated with an active energy ray by the active energy ray-curable resin composition, and the active energy ray-curable resin composition is cured by the film 42 to form a transfer. The hardened resin layer 44 of the fine uneven structure on the surface of the roll-shaped mold 20 is used. The amount of light irradiation energy from the active energy ray irradiation device 28 is preferably from 100 mJ/cm 2 to 10000 mJ/cm 2 .
利用剝離輥30將於表面形成有硬化樹脂層44之薄膜42自輥狀模具20剝離，藉此獲得如圖3所示之物品40。The film 42 on which the hardened resin layer 44 is formed on the surface is peeled off from the roll-shaped mold 20 by the peeling roller 30, whereby the article 40 as shown in Fig. 3 is obtained.
其次，藉由反射型紅外分光裝置50，測定薄膜42剝離之後的輥狀模具20之表面的紅外分光光譜。自即時地掌握模具表面之脫模劑之狀態之方面考慮，較佳的是連續地或者空開預定間隔而斷續地測定模具之表面的紅外分光光譜。反射型紅外分光裝置50可為固定式亦可為掃描式。Next, the infrared spectroscopic spectrum of the surface of the roll-shaped mold 20 after peeling of the film 42 is measured by the reflective infrared spectroscopic device 50. From the viewpoint of immediately grasping the state of the release agent on the surface of the mold, it is preferred to intermittently measure the infrared spectrum of the surface of the mold continuously or at a predetermined interval. The reflective infrared spectroscopic device 50 can be either fixed or scanning.
其次，於判定機構60中，藉由抽出部，自於反射型紅外分光裝置50中所測定之紅外分光光譜而抽出源自特定之化學結構之預定波數附近的峰值之強度或面積；於算出 部中，視需要算出2種峰值之強度或面積之比；於判定部中，於峰值之強度、面積或者該些之比等為預先設定之臨限值以上(視情況為臨限值以下)時，將輥狀模具20之表面的脫模劑之狀態判定為良好；於判定部中將輥狀模具20之表面的脫模劑之狀態判定為不良之情形時，將該信息自傳遞部傳遞至控制裝置62。Next, in the determining unit 60, the intensity or area of the peak near the predetermined wave number from the specific chemical structure is extracted from the infrared spectral spectrum measured by the reflective infrared spectroscopic device 50 by the extracting unit; In the part, the ratio of the intensity or the area of the two types of peaks is calculated as needed. In the determination unit, the intensity, the area, or the ratio of the peaks are equal to or greater than a predetermined threshold (as the case may be below the threshold). In the case where the state of the release agent on the surface of the roll-shaped mold 20 is judged to be good, and the state of the release agent on the surface of the roll-shaped mold 20 is judged to be defective in the determination unit, the information is transmitted from the transmission unit. To control device 62.
於判定部中，自判定之精度比較高之方面考慮，較佳的是於源自脫模劑之化學結構的波數附近之峰值的吸光度面積(A)、或者源自脫模劑之化學結構的波數附近之峰值的吸光度面積(A)與源自輥狀模具20之表面所存在之化學結構的波數附近之峰值的吸光度面積(B)之面積比((A)/(B))為預先設定之臨限值以上時，將模具之表面的脫模劑之狀態判定為良好。In the determination unit, it is preferable that the absorbance area (A) of the peak near the wave number of the chemical structure derived from the release agent or the chemical structure derived from the release agent is preferable from the viewpoint of high accuracy of the determination. Area ratio of the absorbance area (A) of the peak near the wave number to the absorbance area (B) of the peak near the wave number of the chemical structure present on the surface of the roll mold 20 ((A)/(B)) When it is more than the preset threshold value, the state of the mold release agent on the surface of the mold is judged to be good.
於判定機構60中，具體而言，於使用具有水解性矽烷基或矽醇基之氟化合物作為脫模劑，使用在鋁基材之表面具有陽極氧化鋁(所述陽極氧化鋁具有2個以上細孔)的模具而作為輥狀模具20之情形時，較佳的是進行以下之處理。In the determination means 60, specifically, a fluorine compound having a hydrolyzable alkylene group or a decyl group is used as a release agent, and an anodized aluminum is used on the surface of the aluminum substrate (the anodized aluminum has two or more In the case of the mold of the fine pores as the roll mold 20, it is preferred to carry out the following treatment.
於抽出部中，自紅外分光光譜而抽出源自具有水解性矽烷基或矽醇基之氟化合物之化學結構的波數為1080cm-1 ~1290cm-1 附近之峰值的吸光度面積(A)、以及源自陽極氧化鋁之化學結構的波數為730cm-1 ~1080cm-1 附近之峰值的吸光度面積(B)。此時之基線是連結在預定之波數處具有峰值之吸收曲線之始點與終點的虛線。將具體例 表示於圖5中。In the extraction portion, an absorbance area (A) of a peak having a wave number of from about 1080 cm -1 to 1290 cm -1 derived from a chemical structure of a fluorine compound having a hydrolyzable alkylene group or a sterol group is extracted from the infrared spectroscopic spectrum, and The absorbance area (B) of the peak of the chemical structure derived from the anodized aluminum is 730 cm -1 to 1080 cm -1 . The baseline at this time is a broken line connecting the start point and the end point of the absorption curve having a peak at a predetermined wave number. A specific example is shown in FIG.
於算出部中，算出抽出部中所抽出之面積(A)與面積(B)，進一步算出兩者之面積比((A)/(B))。In the calculation unit, the area (A) and the area (B) extracted in the extraction unit are calculated, and the area ratio ((A)/(B)) of the two is further calculated.
於判定部中，於面積(A)或面積比((A)/(B))為預先設定之臨限值以上時，將輥狀模具20之表面的脫模劑之狀態判定為良好。In the determination unit, when the area (A) or the area ratio ((A)/(B)) is equal to or greater than the predetermined threshold value, the state of the release agent on the surface of the roll mold 20 is judged to be good.
面積(A)或面積比((A)/(B))之臨限值可使用與實際之製造中所使用相同之製造裝置及相同之材料而預先實施預備實驗，確定輥狀模具20變得不能自硬化樹脂層44脫模之前或者於一部分產生由於脫模不良所造成之缺陷之時間點的面積(A)或面積比((A)/(B))，由此而設定即可。本發明者等人藉由反覆實施預備實驗而確認：於使用具有水解性矽烷基或矽醇基之氟化合物(大金工業公司製造、OPTOOL(註冊商標)DSX)作為脫模劑、使用在鋁基材之表面具有陽極氧化鋁(所述陽極氧化鋁具有2個以上細孔)之模具作為輥狀模具20之情形時，若面積(A)為0.13或面積比((A)/(B))為0.047以上，則並不產生脫模不良；若面積(A)為0.15或面積比((A)/(B))為0.070以上，則可更穩定地進行轉印。面積(A)或面積比((A)/(B))之上限並無特別之限制，若脫模劑之量變多則產生無法正確地轉印輥狀模具20之微細凹凸結構等問題，因此面積(A)較佳的是1以下，更佳的是0.8以下。而且，面積比((A)/(B))較佳的是10以下，更佳的是5以下。The margin of the area (A) or the area ratio ((A)/(B)) can be preliminarily carried out using the same manufacturing apparatus and the same material as used in the actual manufacturing, and it is determined that the roll mold 20 becomes It is not possible to set the area (A) or the area ratio ((A)/(B)) at a time point before the mold is released from the hardened resin layer 44 or a part of the defect due to the mold release failure. The present inventors confirmed by repeated preliminary experiments that a fluorine compound having a hydrolyzable alkyl or decyl group (manufactured by Daikin Industries, Ltd., OPTOOL (registered trademark) DSX) was used as a release agent, and it was used in aluminum. When the surface of the substrate has a mold of anodized aluminum (the anodized aluminum has two or more fine pores) as the roll mold 20, the area (A) is 0.13 or the area ratio ((A)/(B). When it is 0.047 or more, mold release failure does not occur; and when the area (A) is 0.15 or the area ratio ((A)/(B)) is 0.070 or more, transfer can be performed more stably. The upper limit of the area (A) or the area ratio ((A)/(B)) is not particularly limited. When the amount of the release agent is increased, problems such as the fine uneven structure of the roll mold 20 cannot be accurately transferred. The area (A) is preferably 1 or less, more preferably 0.8 or less. Further, the area ratio ((A)/(B)) is preferably 10 or less, more preferably 5 or less.
於使用所述氟化合物(大金工業公司製造、OPTOOL(註冊商標)DSX)作為脫模劑、使用在鋁基材之表面具有陽極氧化鋁(所述陽極氧化鋁具有2個以上細孔)之模具作為輥狀模具20之情形時，面積(A)較佳的是0.13以上1以下，更佳的是0.15以上0.8以下。The fluorine compound (manufactured by Daikin Industries, Ltd., OPTOOL (registered trademark) DSX) is used as a mold release agent, and an anodized aluminum (the anodized aluminum has two or more fine pores) is used on the surface of the aluminum substrate. When the mold is used as the roll mold 20, the area (A) is preferably 0.13 or more and 1 or less, more preferably 0.15 or more and 0.8 or less.
於使用所述氟化合物作為脫模劑、使用所述模具作為輥狀模具20之情形時，面積比((A)/(B))較佳的是0.047以上10以下，更佳的是0.070以上5以下。When the fluorine compound is used as the release agent and the mold is used as the roll mold 20, the area ratio ((A)/(B)) is preferably 0.047 or more and 10 or less, and more preferably 0.070 or more. 5 or less.
於控制裝置62中，例如於判定機構60中將輥狀模具20之表面的脫模劑之狀態判定為不良時，停止薄膜42之移動、輥狀模具20之旋轉、及自貯槽22供給活性能量線硬化性樹脂組成物等，停止將輥狀模具20之表面的微細凹凸結構轉印至薄膜42之表面。於停止後亦可將模具取出而塗佈脫模劑。而且，控制裝置62亦可以根據判定機構60之輸出而於輥狀模具20之表面塗佈脫模劑之方式構成。In the control device 62, for example, when the state of the release agent on the surface of the roll-shaped mold 20 is determined to be defective in the determination unit 60, the movement of the film 42 is stopped, the rotation of the roll mold 20, and the supply of the active energy from the storage tank 22 are stopped. The linear curable resin composition or the like stops the transfer of the fine uneven structure on the surface of the roll mold 20 to the surface of the film 42. After the cessation, the mold can also be taken out to apply a release agent. Further, the control device 62 may be configured to apply a release agent to the surface of the roll mold 20 in accordance with the output of the determination mechanism 60.
(物品)(article)
圖3是表示藉由本發明的製造方法而所得之表面具有微細凹凸結構的物品40之一例的剖面圖。Fig. 3 is a cross-sectional view showing an example of an article 40 having a fine uneven structure on the surface obtained by the production method of the present invention.
薄膜42是透光性薄膜。薄膜之材料可列舉聚碳酸酯、聚苯乙烯系樹脂、聚酯、聚胺基甲酸酯、丙烯酸系樹脂、聚醚碸、聚碸、聚醚酮、纖維素系樹脂(三乙酸纖維素等)、聚烯烴、及脂環族聚烯烴等。The film 42 is a light transmissive film. Examples of the material of the film include polycarbonate, polystyrene resin, polyester, polyurethane, acrylic resin, polyether oxime, polyfluorene, polyether ketone, and cellulose resin (cellulose triacetate, etc.). ), polyolefins, and alicyclic polyolefins.
硬化樹脂層44是由活性能量線硬化性樹脂組成物之硬化物所構成之膜，於表面具有微細凹凸結構。The cured resin layer 44 is a film composed of a cured product of an active energy ray-curable resin composition, and has a fine uneven structure on the surface.
於使用陽極氧化鋁的模具之情形時的物品40之表面的微細凹凸結構是藉由轉印陽極氧化鋁之表面的微細凹凸結構而形成的，具有由活性能量線硬化性樹脂組成物之硬化物所構成之2個以上凸部46。The fine concavo-convex structure on the surface of the article 40 in the case of using an anodized aluminum mold is formed by transferring a fine uneven structure on the surface of an anodized alumina, and has a cured product of an active energy ray-curable resin composition. Two or more convex portions 46 formed.
微細凹凸結構較佳的是排列有2個以上略圓錐形狀或者角錐形狀等之突起(凸部)的所謂之蛾眼結構。已知突起間之間隔為可見光之波長以下的蛾眼結構，由於折射率自空氣之折射率連續地增大至材料之折射率，從而成為有效之抗反射機構。The fine concavo-convex structure is preferably a so-called moth-eye structure in which two or more protrusions (convex portions) such as a slightly conical shape or a pyramid shape are arranged. It is known that the moth-eye structure in which the interval between the protrusions is equal to or less than the wavelength of visible light is an effective anti-reflection mechanism because the refractive index continuously increases from the refractive index of the air to the refractive index of the material.
凸部間之平均間隔為可見光之波長以下，亦即400nm以下。於使用陽極氧化鋁的模具而形成凸部之情形時，凸部間之平均間隔成為100nm~200nm左右，因此特佳的是250nm以下。The average interval between the convex portions is below the wavelength of visible light, that is, below 400 nm. When a convex portion is formed using a mold of an anodized aluminum, the average interval between the convex portions is about 100 nm to 200 nm, and therefore it is particularly preferably 250 nm or less.
自凸部形成之容易性之方面考慮，凸部間之平均間隔較佳的是20nm以上。The average interval between the convex portions is preferably 20 nm or more from the viewpoint of easiness in forming the convex portions.
凸部間之平均間隔之範圍較佳的是20nm~400nm，更佳的是50nm~300nm，進一步更佳的是90nm~250nm。The average interval between the convex portions is preferably 20 nm to 400 nm, more preferably 50 nm to 300 nm, still more preferably 90 nm to 250 nm.
凸部間之平均間隔是藉由電子顯微鏡觀察而測定50點鄰接之凸部間之間隔(自凸部之中心至鄰接之凸部之中心的距離)，將該些值加以平均而所得的值。The average interval between the convex portions is obtained by observing the interval between the convex portions at 50 points (the distance from the center of the convex portion to the center of the adjacent convex portion) by observation with an electron microscope, and averaging the values. .
於平均間隔為100nm之情形時，凸部之高度較佳的是80nm~500nm，更佳的是120nm~400nm，特佳的是150nm~300nm。若凸部之高度為80nm以上，則反射率 變得充分低，且反射率之波長依存性(wavelength dependence)少。若凸部之高度為500nm以下，則凸部之耐擦傷性變良好。When the average interval is 100 nm, the height of the convex portion is preferably 80 nm to 500 nm, more preferably 120 nm to 400 nm, and particularly preferably 150 nm to 300 nm. If the height of the convex portion is 80 nm or more, the reflectance It becomes sufficiently low, and the wavelength dependence of the reflectance is small. When the height of the convex portion is 500 nm or less, the scratch resistance of the convex portion is improved.
凸部之高度是於藉由電子顯微鏡以30000倍之倍率進行觀察時，測定凸部之最頂部與存在於凸部間之凹部的最底部之間的距離而所得的值。The height of the convex portion is a value obtained by measuring the distance between the topmost portion of the convex portion and the bottommost portion of the concave portion existing between the convex portions when observed by an electron microscope at a magnification of 30,000 times.
凸部之縱橫比(凸部之高度/凸部間之平均間隔)較佳的是0.8~5.0，更佳的是1.2~4.0，特佳的是1.5~3.0。若凸部之縱橫比為0.8以上，則反射率充分變低。若凸部之縱橫比為5.0以下，則凸部之耐擦傷性變良好。The aspect ratio of the convex portion (the height of the convex portion/the average interval between the convex portions) is preferably 0.8 to 5.0, more preferably 1.2 to 4.0, and particularly preferably 1.5 to 3.0. When the aspect ratio of the convex portion is 0.8 or more, the reflectance is sufficiently lowered. When the aspect ratio of the convex portion is 5.0 or less, the scratch resistance of the convex portion is improved.
凸部之形狀較佳的是與高度方向正交之方向的凸部截面積自最表面向深度方向連續性增加的形狀，亦即凸部之高度方向之剖面形狀為三角形、梯形、及鐘形等形狀。The shape of the convex portion is preferably a shape in which the cross-sectional area of the convex portion in the direction orthogonal to the height direction increases from the outermost surface to the depth direction, that is, the cross-sectional shape of the convex portion in the height direction is a triangle, a trapezoid, and a bell shape. And other shapes.
硬化樹脂層44之折射率與薄膜42之折射率之差較佳的是0.2以下，更佳的是0.1以下，特佳的是0.05以下。若折射率差為0.2以下，則硬化樹脂層44與薄膜42之界面的反射得到抑制。The difference between the refractive index of the cured resin layer 44 and the refractive index of the film 42 is preferably 0.2 or less, more preferably 0.1 or less, and particularly preferably 0.05 or less. When the refractive index difference is 0.2 or less, reflection at the interface between the cured resin layer 44 and the film 42 is suppressed.
已知於表面具有微細凹凸結構之情形時，若該表面由疏水性材料而形成則由於蓮花效應而獲得超斥水性，若該表面由親水性材料而形成則獲得超親水性。When it is known that the surface has a fine uneven structure, if the surface is formed of a hydrophobic material, super-repellency is obtained due to the lotus effect, and if the surface is formed of a hydrophilic material, superhydrophilicity is obtained.
硬化樹脂層44之材料為疏水性之情形時的微細凹凸結構之表面的水接觸角較佳的是90°以上，更佳的是110°以上，特佳的是120°以上。若水接觸角為90°以上，則變得難以附著水污，因此發揮出充分之防污性。而且， 由於難以附著水，因此可期待防止結冰。The water contact angle of the surface of the fine uneven structure in the case where the material of the cured resin layer 44 is hydrophobic is preferably 90 or more, more preferably 110 or more, and particularly preferably 120 or more. When the water contact angle is 90° or more, it becomes difficult to adhere to water stains, so that sufficient antifouling properties are exhibited. and, Since it is difficult to adhere to water, it is expected to prevent icing.
硬化樹脂層44之材料為疏水性之情形時的微細凹凸結構之表面之水接觸角之範圍較佳的是90°以上180°以下，更佳的是110°以上180°以下，特佳的是120°以上180°以下。The water contact angle of the surface of the fine uneven structure in the case where the material of the cured resin layer 44 is hydrophobic is preferably 90° or more and 180° or less, more preferably 110° or more and 180° or less, and particularly preferably 120° or more and 180° or less.
硬化樹脂層44之材料為親水性之情形時的微細凹凸結構之表面的水接觸角較佳的是25°以下，更佳的是23°以下，特佳的是21°以下。若水接觸角為25°以下，則附著於表面之污垢可用水沖洗去，且變得難以附著油污，因此發揮出充分之防污性。自抑制硬化樹脂層44由於吸水而造成微細凹凸結構變形、以及伴隨於此之反射率上升之方面考慮，所述水接觸角較佳的是3°以上。The water contact angle of the surface of the fine uneven structure in the case where the material of the cured resin layer 44 is hydrophilic is preferably 25 or less, more preferably 23 or less, and particularly preferably 21 or less. When the water contact angle is 25 or less, the dirt adhering to the surface can be washed with water, and it becomes difficult to adhere to the oil stain, so that sufficient antifouling property is exerted. The water contact angle is preferably 3° or more from the viewpoint that the fine concavo-convex structure is deformed by water absorption due to water absorption and the reflectance is increased.
硬化樹脂層44之材料為親水性之情形時的微細凹凸結構之表面的水接觸角之範圍較佳的是3°以上30°以下，更佳的是3°以上23°以下，特佳的是3°以上21°以下。When the material of the cured resin layer 44 is hydrophilic, the water contact angle of the surface of the fine uneven structure is preferably 3° or more and 30° or less, more preferably 3° or more and 23° or less, and particularly preferably 3° or more and 21° or less.
(用途)(use)
物品40之用途可列舉抗反射物品、防霧性物品、防污性物品、及斥水性物品，更具體而言可列舉顯示器用抗反射膜、汽車儀錶蓋、汽車鏡、汽車窗、有機或無機電致發光之光出射效率提高部件、及太陽電池部件等。Examples of the use of the article 40 include an antireflection article, an antifogging article, an antifouling article, and a water repellent article, and more specifically, an antireflection film for a display, an automobile instrument cover, a car mirror, a car window, an organic or a non- An electroluminescence light-emitting efficiency improving member, and a solar cell member.
(作用效果)(Effect)
於以上所說明的本發明之表面具有微細凹凸結構的物品的製造方法及製造裝置中，將微細凹凸結構轉印至物品 本體之表面，測定將所述物品本體自模具上剝離之後的模具之表面的紅外分光光譜，基於所述紅外分光光譜而判定模具之表面的脫模劑之狀態的良否，因此可在線簡易地監控模具表面之脫模劑之狀態。其結果，可事先掌握模具之脫模不良，可抑制表面具有微細凹凸結構的物品之生產性之降低。In the method and apparatus for producing an article having a fine uneven structure on the surface of the present invention described above, the fine uneven structure is transferred to an article. On the surface of the body, an infrared spectroscopic spectrum of the surface of the mold after the article body is peeled off from the mold is measured, and the state of the release agent on the surface of the mold is determined based on the infrared spectroscopic spectrum, so that it can be easily monitored online The state of the release agent on the surface of the mold. As a result, the mold release failure of the mold can be grasped in advance, and the productivity of the article having the fine uneven structure on the surface can be suppressed from being lowered.
即，藉由本發明可非接觸及非破壞地判定模具之表面的脫模劑之狀態，因此可於物品之製造中在線地進行判定。因此，可事先預測脫模不良，可於脫模不良之前中止物品之製造。其結果，可於脫模不良之前製造物品，因此可有效率地使用模具，可防止由於脫模不良所造成之硬化樹脂之附著，因此模具之清洗變容易。而且，可回避脫模不良之困擾，因此可更安全地製造物品。That is, according to the present invention, the state of the release agent on the surface of the mold can be determined non-contactly and non-destructively, so that the determination can be made online in the manufacture of the article. Therefore, the mold release failure can be predicted in advance, and the manufacture of the article can be stopped before the mold release failure. As a result, since the article can be manufactured before the mold release failure, the mold can be used efficiently, and the adhesion of the cured resin due to the mold release failure can be prevented, so that the cleaning of the mold becomes easy. Moreover, the trouble of mold release can be avoided, so that articles can be manufactured more safely.
另外，於本發明中，採用反射紅外分光法之理由如下所述。Further, in the present invention, the reason for using the reflection infrared spectroscopy is as follows.
如上所述，若將模具之表面的微細凹凸結構連續地轉印至物品本體之表面，則不久後脫模性開始惡化。認為其原因是脫模劑自模具脫落、及由於活性能量線(紫外線等)或熱等所造成之脫模劑變質等。因此，查明使用具有水解性矽烷基之氟化合物作為脫模劑之情形時的脫模不良之原因，故而可對初始之模具與變為脫模不良之模具之表面進行分析，估計脫模劑之量。通常情況下，為了將脫模劑極薄地塗佈於模具上，需要使用表面感光度優異之方法。例如考慮使用TOF-SIMS、XPS及IR法等。因此，藉由XPS 及TOF-SIMS進行分析之結果，例如由XPS所求出之脫模劑之量(原子數比F/Al)自初始之8.3，於脫模不良時降低至2.1。而且，未發現模具上所殘存之脫模劑之結構變化。根據該結果可知脫模不良之原因是脫模劑脫落。因此，藉由掌握模具之表面的脫模劑之量，可事先預測脫模不良。As described above, when the fine uneven structure on the surface of the mold is continuously transferred onto the surface of the article body, the mold release property starts to deteriorate soon. The reason for this is considered to be that the release agent is detached from the mold, and the release agent is deteriorated due to an active energy ray (such as ultraviolet rays) or heat. Therefore, the cause of mold release failure in the case of using a fluorine compound having a hydrolyzable alkylene group as a mold release agent is ascertained, so that the surface of the initial mold and the mold which becomes a mold release defect can be analyzed, and the release agent can be estimated. The amount. In general, in order to apply a mold release agent to a mold extremely thinly, it is necessary to use a method excellent in surface sensitivity. For example, it is considered to use TOF-SIMS, XPS, and IR methods. Therefore, with XPS As a result of analysis by TOF-SIMS, for example, the amount of the releasing agent (atomic ratio F/Al) determined by XPS was 8.3 from the initial, and was decreased to 2.1 at the time of mold release. Moreover, no structural change of the release agent remaining on the mold was found. From this result, it is understood that the cause of the mold release failure is that the release agent is peeled off. Therefore, by grasping the amount of the release agent on the surface of the mold, it is possible to predict the mold release failure in advance.
然而，於TOF-SIMS或XPS中存在如下之問題：由於裝置構成上之問題，無法測定一定大小以上之模具，因此於物品之製造中難以進行測定，無法在線地進行監控。而且，於紅外分光法中表面感光度優異之ATR法無法非接觸地進行測定，會傷及模具之表面，因此無法於物品之製造中進行測定。另外，於該些方法中，由於模具之表面具有微細凹凸結構，因此亦難以判別對哪個部分進行測定。因此，藉由進行利用反射紅外分光法之測定，可解決上述問題，可無論模具之大小且非接觸地掌握脫模劑之量。However, in TOF-SIMS or XPS, there is a problem in that it is impossible to measure a mold having a certain size or more due to a problem in device configuration, and thus it is difficult to perform measurement in the manufacture of an article, and it is impossible to perform monitoring on-line. Further, the ATR method which is excellent in surface sensitivity in the infrared spectroscopy cannot be measured in a non-contact manner, and the surface of the mold is damaged, so that measurement cannot be performed in the production of the article. Further, in these methods, since the surface of the mold has a fine uneven structure, it is difficult to determine which portion is to be measured. Therefore, the above problem can be solved by performing measurement by reflection infrared spectroscopy, and the amount of the release agent can be grasped irrespectively regardless of the size of the mold.
於此，對反射紅外分光法加以說明。若對模具照射紅外線，則紅外線透過表面上所存在之由具有水解性矽烷基之氟化合物所構成之脫模劑或陽極氧化鋁之大部分，被鋁基材之金屬面反射。藉由對該反射光進行分光而獲得脫模劑之紅外分光光譜。於此情形時，獲得模具之微細凹凸結構之內外的所有脫模劑之信息。而且，若藉由該方法，則可不與模具接觸地進行測定，因此亦可不傷及模具地、於物品之製造中進行測定。而且，不受大型輥狀模具等之大小或形狀之制約。由於該些特徵，亦可進行直接(inline)地測定。而且，作為紅外線，可視需要而使用近紅外~遠 紅外。Here, the reflection infrared spectroscopy will be described. When the mold is irradiated with infrared rays, most of the release agent or the anodized aluminum composed of the fluorine compound having a hydrolyzable alkylene group present on the surface of the infrared ray is reflected by the metal surface of the aluminum substrate. The infrared spectroscopic spectrum of the release agent is obtained by splitting the reflected light. In this case, information on all the release agents inside and outside the fine concavo-convex structure of the mold is obtained. Further, according to this method, since the measurement can be performed without contacting the mold, it is possible to perform measurement in the production of the article without damaging the mold. Moreover, it is not restricted by the size or shape of a large roll mold or the like. Due to these features, inline measurements can also be made. Moreover, as infrared rays, near-infrared to far can be used as needed. Infrared.
[實例][Example]
以下，藉由實例對本發明進行具體之說明，但發明並不限定於該些實例。Hereinafter, the present invention will be specifically described by way of examples, but the invention is not limited to the examples.
(陽極氧化鋁之細孔)(aperture of anodized aluminum)
削去陽極氧化鋁之一部分，將鉑蒸鍍於剖面上1分鐘，使用場發射型掃描電子顯微鏡(日本電子公司製造，JSM-7400F)，於加速電壓為3.00kV之條件下觀察剖面，測定細孔之間隔以及細孔之深度。分別對50點進行各測定，求出其平均值。One part of the anodized aluminum was peeled off, and platinum was vapor-deposited on the cross section for 1 minute, and a section was observed under a condition of an acceleration voltage of 3.00 kV using a field emission type scanning electron microscope (JSM-7400F, manufactured by JEOL Ltd.). The spacing of the holes and the depth of the holes. Each measurement was performed at 50 points, and the average value was obtained.
(轉印試驗)(transfer test)
於模具之形成有微細凹凸結構之側流入活性能量線硬化性樹脂組成物，覆蓋丙烯酸膜之後，藉由UV照射機(高壓水銀燈、累計光量為400mJ/cm2 )進行硬化。繼而，使丙烯酸膜連同硬化樹脂層自模具脫模，藉此將微細凹凸結構轉印於丙烯酸膜之表面。反覆進行該操作，將產生可藉由目視而清楚地識別之脫模不良的次數作為可轉印次數。於此情形時之脫模不良是指由於硬化樹脂附著於模具上等之原因，而於模具之微細凹凸面產生樹脂殘留，從而造成模具與硬化樹脂層之脫模變困難的狀態。The active energy ray-curable resin composition was poured into the mold on the side where the fine uneven structure was formed, and after covering the acrylic film, it was cured by a UV irradiator (high-pressure mercury lamp, integrated light amount: 400 mJ/cm 2 ). Then, the acrylic film and the hardened resin layer are released from the mold, whereby the fine uneven structure is transferred onto the surface of the acrylic film. By repeating this operation, the number of times of mold release which can be clearly recognized by visual inspection is generated as the number of transferable times. In this case, the mold release failure is a state in which the resin is left on the fine uneven surface of the mold due to adhesion of the cured resin to the mold or the like, and the mold and the cured resin layer are difficult to release from the mold.
(活性能量線硬化性樹脂組成物)(Active energy ray curable resin composition)
將琥珀酸/三羥甲基乙烷/丙烯酸之莫耳比為1：2：4之縮合反應混合物45重量份、 1,6-己二醇二丙烯酸酯(大阪有機化學公司製造)45 重量份、自由基聚合性聚矽氧油(信越化學工業公司製造、X-22-1602)10重量份、及1-羥基環己基苯基酮(汽巴精化股份有限公司製造、Irgacure 184)3重量份45 parts by weight of a condensation reaction mixture of succinic acid/trimethylolethane/acrylic acid having a molar ratio of 1:2:4, 1,6-hexanediol diacrylate (manufactured by Osaka Organic Chemical Co., Ltd.) 45 10 parts by weight, and 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals Co., Ltd., Irgacure 184), by weight fraction, radically polymerizable polyoxyxene oil (manufactured by Shin-Etsu Chemical Co., Ltd., X-22-1602) 3 parts by weight
加以混合，調製活性能量線硬化性樹脂組成物。The active energy ray-curable resin composition is prepared by mixing.
(模具之製作方法)(manufacturing method of the mold)
準備將50mm×50mm×厚0.3mm之鋁板(純度99.99%)於過氯酸/乙醇混合溶液(1/4體積比)中進行電解研磨而成者。An aluminum plate (purity: 99.99%) of 50 mm × 50 mm × 0.3 mm thick was prepared by electrolytic polishing in a perchloric acid/ethanol mixed solution (1/4 volume ratio).
步驟(a)：Step (a):
關於所述鋁板，於0.3M草酸水溶液中，於直流40V、溫度16℃之條件下進行6小時之陽極氧化。The aluminum plate 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 6 hours.
步驟(b)：Step (b):
將形成有氧化皮膜之鋁板於6wt%磷酸/1.8wt%鉻酸混合水溶液中浸漬3小時，除去氧化皮膜。The aluminum plate on which the oxide film was formed was immersed in a 6 wt% phosphoric acid/1.8 wt% chromic acid mixed aqueous solution for 3 hours to remove the oxide film.
步驟(c)：Step (c):
關於所述鋁板，於0.3M草酸水溶液中，於直流40V、溫度16℃之條件下進行30秒之陽極氧化。The aluminum plate 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)：Step (d):
將形成有氧化皮膜之鋁板，於32℃之5wt%磷酸水溶液中浸漬8分鐘，進行細孔徑擴大處理。The aluminum plate on which the oxide film was formed was immersed in a 5 wt% phosphoric acid aqueous solution at 32 ° C for 8 minutes to carry out a pore diameter expansion treatment.
步驟(e)：Step (e):
關於所述鋁板，於0.3M草酸水溶液中，於直流40V、 溫度16℃之條件下進行30秒之陽極氧化。Regarding the aluminum plate, in a 0.3 M aqueous solution of oxalic acid, at a direct current of 40 V, Anodization was carried out for 30 seconds at a temperature of 16 °C.
步驟(f)：Step (f):
反覆進行所述步驟(d)及步驟(e)合計4次，最後進行步驟(d)，獲得於表面形成有陽極氧化鋁的模具，所述陽極氧化鋁具有平均間隔為100nm、深度為240nm之略圓錐形狀的細孔。The steps (d) and (e) are repeated four times in total, and finally the step (d) is performed to obtain a mold having anodized aluminum formed on the surface, the anodized aluminum having an average interval of 100 nm and a depth of 240 nm. A slightly conical shaped pore.
步驟(g)：Step (g):
使用噴水器將模具之表面的磷酸水溶液輕輕沖洗去，然後將模具浸漬於流水中10分鐘。The aqueous phosphoric acid solution on the surface of the mold was gently rinsed using a water sprayer, and then the mold was immersed in running water for 10 minutes.
步驟(h)：Step (h):
自***(air gun)對模具吹空氣，除去附著於模具之表面的水滴。Air is blown from the air gun to remove water droplets attached to the surface of the mold.
步驟(i)：Step (i):
將模具於室溫下，於以稀釋劑HD-ZV(HARVES Co.,Ltd.製造)將OPTOOL(註冊商標)DSX(大金化成品販賣公司製造)稀釋為0.1wt%而得之溶液中浸漬10分鐘。The mold was immersed in a solution obtained by diluting OPTOOL (registered trademark) DSX (manufactured by Daikin Chemicals Sales Co., Ltd.) to 0.1 wt% with a diluent HD-ZV (manufactured by HARVES Co., Ltd.) at room temperature. 10 minutes.
步驟(j)：Step (j):
將模具以3mm/sec緩緩地自稀釋溶液中拉出。The mold was slowly pulled out of the diluted solution at 3 mm/sec.
步驟(l)：Step (l):
對模具進行15分鐘之風乾，獲得以脫模劑進行了處理之模具。The mold was air-dried for 15 minutes to obtain a mold which was treated with a release agent.
[實例1][Example 1]
使用傅立葉變換紅外分光裝置(ThermoFisher Scientific公司製造、Nicolet380/Continum)測定模具之表 面的紅外分光光譜。將結果示於圖4。於1080cm-1 ~1290cm-1 處所見之峰值A源自脫模劑，於730cm-1 ~1080cm-1 處所見之峰值B源自陽極氧化鋁。峰值A之吸光度面積(A)為0.43，峰值之吸光度之面積比((A)/(B))為0.18，使用所述模具進行1次轉印試驗時，脫模性良好。The infrared spectroscopic spectrum of the surface of the mold was measured using a Fourier transform infrared spectroscope (manufactured by Thermo Fisher Scientific Co., Ltd., Nicolet 380/Continum). The results are shown in Fig. 4. The peak A seen at 1080 cm -1 to 1290 cm -1 is derived from a release agent, and the peak B seen at 730 cm -1 to 1080 cm -1 is derived from anodized aluminum. The absorbance area (A) of the peak A was 0.43, and the area ratio of the absorbance of the peak ((A)/(B)) was 0.18. When the transfer test was performed using the mold, the mold release property was good.
[實例2][Example 2]
繼實例1之後，進行100次轉印試驗，測定模具之表面的紅外分光光譜。其結果，峰值A之吸光度面積(A)為0.21，峰值之吸光度之面積比((A)/(B))為0.089，使用所述模具進行1次轉印試驗時，脫模性良好。After the example 1, 100 transfer tests were carried out to measure the infrared spectrum of the surface of the mold. As a result, the absorbance area (A) of the peak A was 0.21, and the area ratio of the absorbance of the peak ((A)/(B)) was 0.089. When the primary transfer test was performed using the mold, the mold release property was good.
[實例3][Example 3]
測定藉由與實例1同樣之方法而製作之其他模具表面之紅外分光光譜。其結果，峰值A之吸光度面積(A)為0.35，峰值之吸光度之面積比((A)/(B))為0.14。另外，使用所述模具進行1次轉印試驗時，脫模性良好。The infrared spectroscopic spectrum of the surface of the other molds produced by the same method as in Example 1 was measured. As a result, the absorbance area (A) of the peak A was 0.35, and the area ratio of the absorbance of the peak ((A)/(B)) was 0.14. Further, when the primary transfer test was carried out using the mold, the mold release property was good.
[實例4][Example 4]
自實例3起反覆進行19次轉印(其間，脫模性良好)後，測定模具表面之紅外分光光譜。其結果，峰值A之吸光度面積(A)為0.29，峰值之吸光度之面積比((A)/(B))為0.12。另外，使用所述模具而進一步進行1次轉印試驗時，脫模性良好。The infrared spectroscopy spectrum of the surface of the mold was measured after 19 transfer operations were repeated from Example 3 (where the mold release property was good). As a result, the absorbance area (A) of the peak A was 0.29, and the area ratio of the absorbance of the peak ((A)/(B)) was 0.12. Further, when the transfer test was further carried out using the mold, the mold release property was good.
[實例5][Example 5]
自實例4起反覆進行19次轉印(其間，脫模性良好)後，測定模具表面之紅外分光光譜。其結果，峰值A之吸 光度之面積(A)為0.22，峰值之吸光度之面積比((A)/(B))為0.085。另外，使用所述模具而進一步進行1次轉印試驗時，脫模性良好。The infrared spectroscopy spectrum of the surface of the mold was measured after 19 transfer operations were repeated from Example 4 (where the mold release property was good). As a result, the peak A is sucked The area of luminosity (A) was 0.22, and the area ratio of absorbance at the peak ((A)/(B)) was 0.085. Further, when the transfer test was further carried out using the mold, the mold release property was good.
[實例6][Example 6]
自實例5起反覆進行19次轉印(其間，脫模性良好)後，測定模具表面之紅外分光光譜。其結果，峰值A之吸光度之面積(A)為0.18，峰值之吸光度之面積比((A)/(B))為0.074。另外，使用所述模具而進一步進行1次轉印試驗時，脫模性良好。The infrared spectroscopy spectrum of the surface of the mold was measured after 19 transfer operations were repeated from Example 5 (where the mold release property was good). As a result, the area (A) of the absorbance of the peak A was 0.18, and the area ratio of the absorbance of the peak ((A)/(B)) was 0.074. Further, when the transfer test was further carried out using the mold, the mold release property was good.
[實例7][Example 7]
自實例6起反覆進行19次轉印(其間，脫模性良好)後，測定模具表面之紅外分光光譜。其結果，峰值A之吸光度之面積(A)為0.13，峰值之吸光度之面積比((A)/(B))為0.056。另外，使用所述模具而進一步進行1次轉印試驗時，需要稍稍用力但可脫模。The infrared spectroscopy spectrum of the surface of the mold was measured after 19 transfer operations were repeated from Example 6 (where the mold release property was good). As a result, the area (A) of the absorbance of the peak A was 0.13, and the area ratio of the absorbance of the peak ((A)/(B)) was 0.056. Further, when the transfer test was further carried out using the mold, it is necessary to apply a little force but release the mold.
[比較例1][Comparative Example 1]
自實例7起反覆進行9次轉印。其間剝離所需要之力增加，於自實例7起第10次轉印時，於所製作之具有微細凹凸結構之薄膜上產生裂痕(脫模性不良)。測定該時間點之模具表面的紅外分光光譜，結果是峰值A之吸光度面積(A)為0.12，峰值之吸光度之面積比((A)/(B))為0.045。9 transfers were repeated from Example 7. The force required for the peeling therebetween was increased, and cracks were formed on the film having the fine uneven structure (defective mold release property) at the 10th transfer from Example 7. The infrared spectrum of the surface of the mold at this time point was measured, and as a result, the absorbance area (A) of the peak A was 0.12, and the area ratio of the absorbance of the peak ((A)/(B)) was 0.045.
[實例8][Example 8]
與前述製作方法同樣地再次以脫模劑對比較例1中所 使用之模具進行處理。測定該模具表面之紅外分光光譜。其結果，峰值A之吸光度面積(A)為0.26，峰值之吸光度之面積比((A)/(B))為0.11。另外，使用所述模具進行1次轉印試驗時，脫模性良好。In the same manner as the above production method, the release agent was again used in Comparative Example 1. The mold is used for processing. The infrared spectroscopic spectrum of the surface of the mold was measured. As a result, the absorbance area (A) of the peak A was 0.26, and the area ratio of the absorbance of the peak ((A)/(B)) was 0.11. Further, when the primary transfer test was carried out using the mold, the mold release property was good.
[實例9][Example 9]
自實例8起反覆進行19次轉印(其間，脫模性良好)後，測定模具表面之紅外分光光譜。其結果，峰值A之吸光度面積(A)為0.22，峰值之吸光度之面積比((A)/(B))為0.090。另外，使用所述模具而進一步進行1次轉印試驗時，脫模性良好。The infrared spectroscopy spectrum of the surface of the mold was measured after 19 transfer operations were repeated from Example 8 (where the mold release property was good). As a result, the absorbance area (A) of the peak A was 0.22, and the area ratio of the absorbance of the peak ((A)/(B)) was 0.090. Further, when the transfer test was further carried out using the mold, the mold release property was good.
[實例10][Example 10]
自實例9起反覆進行19次轉印(其間，脫模性良好)後，測定模具表面之紅外分光光譜。其結果，峰值A之吸光度面積(A)為0.18，峰值之吸光度之面積比((A)/(B))為0.078。另外，使用所述模具而進一步進行1次轉印試驗時，脫模性良好。The infrared spectroscopy spectrum of the surface of the mold was measured after 19 times of transfer from the ninth step (where the mold release property was good). As a result, the absorbance area (A) of the peak A was 0.18, and the area ratio of the absorbance of the peak ((A)/(B)) was 0.078. Further, when the transfer test was further carried out using the mold, the mold release property was good.
[實例11][Example 11]
自實例10起反覆進行19次轉印(其間，脫模性良好)後，測定模具表面之紅外分光光譜。其結果，峰值A之吸光度面積(A)為0.14，峰值之吸光度之面積比((A)/(B))為0.062。另外，使用所述模具而進一步進行1次轉印試驗時，需要稍稍用力但可脫模。The infrared spectroscopy spectrum of the surface of the mold was measured after 19 times of transfer from the example 10 (where the mold release property was good). As a result, the absorbance area (A) of the peak A was 0.14, and the area ratio of the absorbance of the peak ((A)/(B)) was 0.062. Further, when the transfer test was further carried out using the mold, it is necessary to apply a little force but release the mold.
[實例12][Example 12]
自實例11起反覆進行9次轉印(其間，脫模性良好) 後，測定模具表面之紅外分光光譜。其結果，峰值A之吸光度面積(A)為0.13，峰值之吸光度之面積比((A)/(B))為0.055。另外，使用所述模具而進一步進行1次轉印試驗時，需要稍稍用力但可脫模。9 transfers were repeated from Example 11 (during which the mold release property was good) Thereafter, the infrared spectrum of the surface of the mold was measured. As a result, the absorbance area (A) of the peak A was 0.13, and the area ratio of the absorbance of the peak ((A)/(B)) was 0.055. Further, when the transfer test was further carried out using the mold, it is necessary to apply a little force but release the mold.
[比較例2][Comparative Example 2]
自實例12起反覆進行8次轉印。其間剝離所需要之力增加，於自實例12起第9次轉印時，於所製作之具有微細凹凸結構之薄膜上產生裂痕(脫模性不良)。測定該時間點之模具表面的紅外分光光譜，結果是峰值A之吸光度面積(A)為0.11，峰值之吸光度之面積比((A)/(B))為0.041。The transfer was repeated 8 times from Example 12. The force required for the peeling therebetween was increased, and cracks were formed on the film having the fine uneven structure (defective mold release property) at the time of the ninth transfer from Example 12. The infrared spectrum of the surface of the mold at this time point was measured, and as a result, the absorbance area (A) of the peak A was 0.11, and the area ratio of the absorbance of the peak ((A)/(B)) was 0.041.
[產業上之可利用性][Industrial availability]
本發明之表面具有微細凹凸結構的物品的製造方法及製造裝置可用以有效率地量產抗反射物品、防霧性物品、防污性物品、及斥水性物品。The method and apparatus for producing an article having a fine uneven structure on the surface of the present invention can be used to efficiently mass-produce an antireflection article, an antifogging article, an antifouling article, and a water repellent article.
雖然本發明已以較佳實施例揭露如上，然其並非用以限定本發明，任何熟習此技藝者，在不脫離本發明之精神和範圍內，當可作些許之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application.
10‧‧‧鋁基材10‧‧‧Aluminum substrate
12‧‧‧細孔12‧‧‧Pore
14‧‧‧氧化皮膜14‧‧‧Oxide film
16‧‧‧細孔產生點16‧‧‧Pore generation points
18‧‧‧模具18‧‧‧Mold
20‧‧‧輥狀模具20‧‧‧Roll mold
22‧‧‧貯槽22‧‧‧storage tank
24‧‧‧氣壓缸24‧‧‧ pneumatic cylinder
26‧‧‧軋輥26‧‧‧ Rolls
28‧‧‧活性能量線照射裝置28‧‧‧Active energy line irradiation device
30‧‧‧剝離輥30‧‧‧ peeling roller
40‧‧‧物品40‧‧‧ Items
42‧‧‧薄膜42‧‧‧film
44‧‧‧硬化樹脂層44‧‧‧ hardened resin layer
46‧‧‧凸部46‧‧‧ convex
50‧‧‧反射型紅外分光裝置50‧‧‧Reflective infrared spectroscopic device
52‧‧‧光源52‧‧‧Light source
54‧‧‧檢測器54‧‧‧Detector
56‧‧‧操作控制機器56‧‧‧Operation Control Machine
60‧‧‧判定機構60‧‧‧Determining body
62‧‧‧控制裝置62‧‧‧Control device
圖1是表示本發明之表面具有微細凹凸結構之物品的製造裝置之一例的構成圖。Fig. 1 is a configuration diagram showing an example of a manufacturing apparatus for an article having a fine uneven structure on the surface of the present invention.
圖2是表示表面具有陽極氧化鋁之模具的製造步驟之剖面圖。Fig. 2 is a cross-sectional view showing a manufacturing step of a mold having anodized aluminum on its surface.
圖3是表示本發明之表面具有微細凹凸結構的物品之一例的剖面圖。Fig. 3 is a cross-sectional view showing an example of an article having a fine uneven structure on the surface of the present invention.
圖4是表示表面經具有水解性矽烷基之氟化合物處理、且表面具有陽極氧化鋁之模具之表面的紅外分光光譜之一例的圖。4 is a view showing an example of an infrared spectroscopic spectrum of a surface of a mold having an anodized aluminum surface treated with a fluorine compound having a hydrolyzable alkylene group.
圖5是表示抽出吸光度面積(A)及吸光度面積(B)時之基線(連結各個吸收曲線之始點與終點之虛線)之一例的圖。5 is a view showing an example of a baseline (a broken line connecting the start point and the end point of each absorption curve) when the absorbance area (A) and the absorbance area (B) are extracted.
20‧‧‧輥狀模具20‧‧‧Roll mold
22‧‧‧貯槽22‧‧‧storage tank
24‧‧‧氣壓缸24‧‧‧ pneumatic cylinder
26‧‧‧軋輥26‧‧‧ Rolls
28‧‧‧活性能量線照射裝置28‧‧‧Active energy line irradiation device
30‧‧‧剝離輥30‧‧‧ peeling roller
40‧‧‧物品40‧‧‧ Items
42‧‧‧薄膜42‧‧‧film
44‧‧‧硬化樹脂層44‧‧‧ hardened resin layer
50‧‧‧反射型紅外分光裝置50‧‧‧Reflective infrared spectroscopic device
52‧‧‧光源52‧‧‧Light source
54‧‧‧檢測器54‧‧‧Detector
56‧‧‧操作控制機器56‧‧‧Operation Control Machine
60‧‧‧判定機構60‧‧‧Determining agency
62‧‧‧控制裝置62‧‧‧Control device
Claims (5)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010090456 | 2010-04-09 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201200328A TW201200328A (en) | 2012-01-01 |
| TWI418454B true TWI418454B (en) | 2013-12-11 |
Family
ID=44762979
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW100112046A TWI418454B (en) | 2010-04-09 | 2011-04-07 | Method of manufacturing product having micro protrusion and recess face structure on surface thereof and manufacturing device thereof |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4856785B2 (en) |
| CN (1) | CN102933363B (en) |
| TW (1) | TWI418454B (en) |
| WO (1) | WO2011126044A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5673088B2 (en) * | 2010-12-27 | 2015-02-18 | 三菱レイヨン株式会社 | Manufacturing method and manufacturing apparatus for article having fine uneven structure on surface |
| CN107148335B (en) * | 2014-11-06 | 2019-04-30 | 夏普株式会社 | The manufacturing method of mold and the manufacturing method of antireflection film |
| US10408812B2 (en) * | 2016-10-12 | 2019-09-10 | General Electric Company | Characterization and control system and method for a resin |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4656049A (en) * | 1986-03-10 | 1987-04-07 | General Dynamics Corp. Space Systems Division | Method and apparatus for the proper quantized application of a mold release agent onto a mold surface |
| JPH02234092A (en) * | 1989-03-08 | 1990-09-17 | Tokyo Keiki Co Ltd | Detecting method for residue in forming die |
| JP2007069217A (en) * | 2005-09-02 | 2007-03-22 | Toyota Motor Corp | Method and apparatus for detecting spreading-state of releasing agent |
| JP2007253410A (en) * | 2006-03-22 | 2007-10-04 | Toppan Printing Co Ltd | Imprinting mold and its manufacturing method |
| JP2010005841A (en) * | 2008-06-25 | 2010-01-14 | Mitsubishi Rayon Co Ltd | Mold manufacturing method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100798172B1 (en) * | 2000-08-18 | 2008-01-24 | 리플렉사이트 코포레이션 | Differentially cured materials and process for forming same |
| WO2007091593A1 (en) * | 2006-02-07 | 2007-08-16 | Dai Nippon Printing Co., Ltd. | Original sheet of embossed release sheet, embossed release sheet, method for producing original sheet of embossed release sheet, method for producing embossed release sheet, apparatus for producing embossed release sheet, synthetic leather, and method for producing synthetic leather |
| CN101484614B (en) * | 2006-06-30 | 2011-09-07 | 三菱丽阳株式会社 | Mold, process for manufacturing mold, and process for producing sheet |
| WO2011078265A1 (en) * | 2009-12-24 | 2011-06-30 | 三菱レイヨン株式会社 | Method for evaluating performance of organic release agent, process for producing mold, and process for producing transparent film with finely roughened structure on surface |
-
2011
- 2011-04-06 JP JP2011518097A patent/JP4856785B2/en not_active Expired - Fee Related
- 2011-04-06 WO PCT/JP2011/058698 patent/WO2011126044A1/en active Application Filing
- 2011-04-06 CN CN201180028379.1A patent/CN102933363B/en not_active Expired - Fee Related
- 2011-04-07 TW TW100112046A patent/TWI418454B/en not_active IP Right Cessation
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4656049A (en) * | 1986-03-10 | 1987-04-07 | General Dynamics Corp. Space Systems Division | Method and apparatus for the proper quantized application of a mold release agent onto a mold surface |
| JPH02234092A (en) * | 1989-03-08 | 1990-09-17 | Tokyo Keiki Co Ltd | Detecting method for residue in forming die |
| JP2007069217A (en) * | 2005-09-02 | 2007-03-22 | Toyota Motor Corp | Method and apparatus for detecting spreading-state of releasing agent |
| JP2007253410A (en) * | 2006-03-22 | 2007-10-04 | Toppan Printing Co Ltd | Imprinting mold and its manufacturing method |
| JP2010005841A (en) * | 2008-06-25 | 2010-01-14 | Mitsubishi Rayon Co Ltd | Mold manufacturing method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4856785B2 (en) | 2012-01-18 |
| CN102933363A (en) | 2013-02-13 |
| WO2011126044A1 (en) | 2011-10-13 |
| JPWO2011126044A1 (en) | 2013-07-11 |
| TW201200328A (en) | 2012-01-01 |
| CN102933363B (en) | 2015-05-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI444279B (en) | Method for producing product having uneven microstructure on surface thereof, mold releasing method, and active energy line curable resin composition for mold surface release | |
| TWI569947B (en) | Active energy beam-curable resin composition and method of manufacturing product having micro protrusion and recess face structure on surface thereof | |
| TWI476088B (en) | Method for manufacturing article having fine uneven structure on surface thereof | |
| TWI415737B (en) | Method for producing product having uneven microstructure on surface thereof | |
| TWI465498B (en) | Method of producing film | |
| TWI491909B (en) | Anti-reflection product and display device | |
| TWI607857B (en) | Structure body and manufacturing method for the same, and article having the structure body | |
| TWI490375B (en) | Mold, manufacturing method therefor product having fine uneven structure on its surface, manufacturing method therefor and display device | |
| TWI436879B (en) | Method for producing light transmissive film, active energy ray-hardenable composition, and light transmissive film | |
| JP2010005841A (en) | Mold manufacturing method | |
| JP5549943B2 (en) | Method for producing mold and method for producing article having fine uneven structure on surface | |
| TWI411511B (en) | Performance evaluation method of an organic release agent, production method of a mold and production method of a transparent film having fine uneven structure on the surface | |
| TWI418454B (en) | Method of manufacturing product having micro protrusion and recess face structure on surface thereof and manufacturing device thereof | |
| JP2011025683A (en) | Method of manufacturing mold | |
| TWI453108B (en) | Active energy ray-hardenable composition, and method for producing light transmissive film having fine concavo-convex structure on the surface | |
| JP2012108502A (en) | Method for manufacturing article having fine relief structure on surface | |
| JP2011194848A (en) | Method of removing acrylic photocurable resin attached to fine rugged mold | |
| JP2015223725A (en) | Production method of article having fine uneven structure on surface | |
| JP2013182007A (en) | Method and device for manufacturing article having fine rugged structure on front face | |
| JP5751535B2 (en) | Mold cleaning method and article manufacturing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | Annulment or lapse of patent due to non-payment of fees |