CN102933363B - 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
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- CN102933363B CN102933363B CN201180028379.1A CN201180028379A CN102933363B CN 102933363 B CN102933363 B CN 102933363B CN 201180028379 A CN201180028379 A CN 201180028379A CN 102933363 B CN102933363 B CN 102933363B
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- China
- Prior art keywords
- convex structure
- minute concave
- releasing agent
- mould
- die surface
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- NGMNTLCQDNNBNT-UHFFFAOYSA-N C(C=C)(=O)OC.C(CS)(=O)OCCOC(CS)=O Chemical compound C(C=C)(=O)OC.C(CS)(=O)OCCOC(CS)=O NGMNTLCQDNNBNT-UHFFFAOYSA-N 0.000 description 1
- SXNICUVVDOTUPD-UHFFFAOYSA-N CC1=CC(C)=CC(C)=C1C(=O)P(=O)C1=CC=CC=C1 Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)C1=CC=CC=C1 SXNICUVVDOTUPD-UHFFFAOYSA-N 0.000 description 1
- 239000004129 EU approved improving agent Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- NQSMEZJWJJVYOI-UHFFFAOYSA-N Methyl 2-benzoylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 NQSMEZJWJJVYOI-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
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- 239000005864 Sulphur Substances 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- VHVGFEDTMPYCSX-UHFFFAOYSA-N [1-[[2,2-dimethyl-3-[[4-(oxoazaniumylmethylidene)pyridin-1-yl]methoxy]propoxy]methyl]pyridin-4-ylidene]methyl-oxoazanium;dichloride Chemical compound [Cl-].[Cl-].C1=CC(=C[NH+]=O)C=CN1COCC(C)(C)COCN1C=CC(=C[NH+]=O)C=C1 VHVGFEDTMPYCSX-UHFFFAOYSA-N 0.000 description 1
- REUQOSNMSWLNPD-UHFFFAOYSA-N [2-(diethylamino)phenyl]-phenylmethanone Chemical compound CCN(CC)C1=CC=CC=C1C(=O)C1=CC=CC=C1 REUQOSNMSWLNPD-UHFFFAOYSA-N 0.000 description 1
- RVWADWOERKNWRY-UHFFFAOYSA-N [2-(dimethylamino)phenyl]-phenylmethanone Chemical compound CN(C)C1=CC=CC=C1C(=O)C1=CC=CC=C1 RVWADWOERKNWRY-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
- WSPIYYDSNOUIAS-QTNFYWBSSA-N [Na].[Na].N[C@H]1CCC(=O)OS(=O)(=O)OC1=O Chemical compound [Na].[Na].N[C@H]1CCC(=O)OS(=O)(=O)OC1=O WSPIYYDSNOUIAS-QTNFYWBSSA-N 0.000 description 1
- FQHXTZQPGLEOMW-UHFFFAOYSA-N [O].C1(CCCCC1)OCCCCCCC Chemical compound [O].C1(CCCCC1)OCCCCCCC FQHXTZQPGLEOMW-UHFFFAOYSA-N 0.000 description 1
- DRWYONGJPZHQOD-UHFFFAOYSA-N [diacetyloxy(3,3,3-trifluoropropyl)silyl] acetate Chemical class CC(=O)O[Si](OC(C)=O)(OC(C)=O)CCC(F)(F)F DRWYONGJPZHQOD-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- UREZNYTWGJKWBI-UHFFFAOYSA-M benzethonium chloride Chemical compound [Cl-].C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 UREZNYTWGJKWBI-UHFFFAOYSA-M 0.000 description 1
- 229960001950 benzethonium chloride Drugs 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
- 229960002130 benzoin Drugs 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- XIWFQDBQMCDYJT-UHFFFAOYSA-M benzyl-dimethyl-tridecylazanium;chloride Chemical class [Cl-].CCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 XIWFQDBQMCDYJT-UHFFFAOYSA-M 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- XWQLYVIMMBLXPY-UHFFFAOYSA-N butan-2-yloxysilane Chemical compound CCC(C)O[SiH3] XWQLYVIMMBLXPY-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- YTJUXOIAXOQWBV-UHFFFAOYSA-N butoxy(trimethyl)silane Chemical compound CCCCO[Si](C)(C)C YTJUXOIAXOQWBV-UHFFFAOYSA-N 0.000 description 1
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 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 1
- 230000007812 deficiency Effects 0.000 description 1
- TZAMQIAPGYOUKF-UHFFFAOYSA-N diethoxyphosphoryl(phenyl)methanone Chemical compound CCOP(=O)(OCC)C(=O)C1=CC=CC=C1 TZAMQIAPGYOUKF-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
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- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 238000002454 metastable transfer emission spectrometry Methods 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- QRLCLBZGWYJTHP-UHFFFAOYSA-N methoxy-dimethyl-(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](C)(C)CCC(F)(F)F QRLCLBZGWYJTHP-UHFFFAOYSA-N 0.000 description 1
- RJMRIDVWCWSWFR-UHFFFAOYSA-N methyl(tripropoxy)silane Chemical compound CCCO[Si](C)(OCCC)OCCC RJMRIDVWCWSWFR-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification 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
- QENDLNJWYIFMIM-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]-n-methylprop-2-enamide Chemical compound CN(C)CCCN(C)C(=O)C=C QENDLNJWYIFMIM-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [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
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005447 octyloxy 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])O* 0.000 description 1
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 1
- 229960003493 octyltriethoxysilane Drugs 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound 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 YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- 238000001259 photo etching Methods 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- YOSXAXYCARLZTR-UHFFFAOYSA-N prop-2-enoyl isocyanate Chemical compound C=CC(=O)N=C=O YOSXAXYCARLZTR-UHFFFAOYSA-N 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- ZMYXZXUHYAGGKG-UHFFFAOYSA-N propoxysilane Chemical compound CCCO[SiH3] ZMYXZXUHYAGGKG-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 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
- FQFILJKFZCVHNH-UHFFFAOYSA-N tert-butyl n-[3-[(5-bromo-2-chloropyrimidin-4-yl)amino]propyl]carbamate Chemical compound CC(C)(C)OC(=O)NCCCNC1=NC(Cl)=NC=C1Br FQFILJKFZCVHNH-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 239000010409 thin film Substances 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
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- YHLJHYMNIZNTGJ-UHFFFAOYSA-N trihydroxy(pentoxy)silane Chemical compound CCCCCO[Si](O)(O)O YHLJHYMNIZNTGJ-UHFFFAOYSA-N 0.000 description 1
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000010792 warming 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
Landscapes
- Mechanical Engineering (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Shaping Of Tube Ends By Bending Or Straightening (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
Abstract
The present invention relates to a method of manufacturing a product having a micro protrusion and recess face structure, including: when manufacturing a product having micro protrusion and recess face structure on a surface by transferring the micro protrusion and recess face structure on the surface of a roll mold, the surface of which is treated by a demolding agent, to a surface of a film (main body of the product): transferring the micro recess face structure to the surface of the film, measuring the infrared spectrum of the surface of the roll mold just after the film is demolded from the mold, and determining whether the condition of the demolding agent on the roll mold is good or bad based on the infrared spectrum of the surface of the roll mold. The present invention provides a method of manufacturing a product having a micro protrusion and recess face structure which can easily monitor the condition of a demolding agent on a surface of a mold online and can suppress a decline in productivity; and a manufacturing device thereof.
Description
Technical field
The present invention relates to surface surface being transferred to main body of articles by the minute concave-convex structure on the surface of the mould of releasing agent process, thus manufacture method and device that surface has the article of minute concave-convex structure.
Its content based on the Japanese Patent Application 2010-090456 CLAIM OF PRIORITY of on April 9th, 2010 in Japanese publication, and is quoted so far by the application.
Background technology
In recent years, because the article of the minute concave-convex structure having found the cycle of below the surperficial wavelength with visible ray have anti-reflection effect, lotus leaf effect etc., therefore its serviceability receives publicity.Especially be called as the concaveconvex structure of moth eye (Moth-Eye) structure, because refractive index increases continuously from the refractive index of air to the refractive index of the material of article, thus become the means of effective antireflection.
There is as surface the manufacture method of the article of minute concave-convex structure, such as, there will be a known have following operation (i) ~ method (such as, patent document 1) (iii).
(i) there is on surface the inversion structures of minute concave-convex structure and described surface is clamped the operation of ultra-violet solidified resin composition between the mould of releasing agent process and the base film as main body of articles.
(ii), to ultra-violet solidified resin composition irradiation ultraviolet radiation, make described ultra-violet solidified resin composition be solidified to form the operation of the curing resin layer with minute concave-convex structure.
(iii), by the curing resin layer demoulding of mould from base film surface, obtain the operation that surface has the article of minute concave-convex structure.
With the mould of releasing agent process usually because replicated fine concaveconvex structure and performance reduces repeatedly, thus mould become cannot from the demoulding curing resin layer.During for aforesaid state, die surface attachment cured resin, and make washing become difficulty, manufacture in base film fracture etc.Therefore, interruption, productivity ratio significantly reduce for a long time in manufacture.In order to solve foregoing problems, seeking can the method for the online and easily state of the releasing agent on supervision molding surface.
Prior art document
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2007-326367 publication
Summary of the invention
the problem that invention will solve
The invention provides can online and easily the releasing agent on supervision molding surface state and can suppress that productivity ratio reduces, manufacture method and manufacturing installation that surface has the article of minute concave-convex structure.
for the scheme of dealing with problems
The feature that surface of the present invention has the manufacture method of the article of minute concave-convex structure is, it surface is transferred to the surface of main body of articles by the minute concave-convex structure on the surface of the mould of releasing agent process thus manufactures the manufacture method that surface has the article of minute concave-convex structure, minute concave-convex structure is transferred to the surface of main body of articles, after items main body is peeled off from mould, measure the infrared spectroscopy spectrum of die surface, based on aforementioned infrared spectroscopy spectrum, judge the state quality of the releasing agent of die surface.
Have in the manufacture method of the article of minute concave-convex structure on surface of the present invention, when the state of the releasing agent of die surface is judged as bad, the surface minute concave-convex structure of die surface being transferred to main body of articles can be stopped, also releasing agent can being supplied the minute concave-convex structure of die surface in addition.
Have in the manufacture method of the article of minute concave-convex structure on surface of the present invention, preferred continuously or intermittently measures the infrared spectroscopy spectrum of die surface.
Have in the manufacture method of the article of minute concave-convex structure on surface of the present invention, preferably, the absorbance area (A) at the peak near the wave number deriving from the chemical constitution of releasing agent in infrared spectroscopy spectrum and derive from the chemical constitution that die surface exists wave number near peak absorbance area (B) area ratio ((A)/(B)) for more than the threshold value that presets time, judge the state of the releasing agent of die surface as well.
The feature that surface of the present invention has the manufacturing installation of the article of minute concave-convex structure is, it is surface surface being transferred to main body of articles by the minute concave-convex structure on the surface of the mould of releasing agent process, thus manufacture surface there is the device of the article of minute concave-convex structure, this manufacturing installation has: surface there is minute concave-convex structure and described surface by the mould of releasing agent process; Measure the reflection-type infrared spectroscopy device of the infrared spectroscopy spectrum of die surface, described die surface is surface minute concave-convex structure being transferred to main body of articles, and peels off the die surface after described main body of articles from mould; The identifying unit of the state quality of the releasing agent of die surface is judged based on described infrared spectroscopy spectrum.
That is, the present invention relates to following content.
(1) a kind of surface has the manufacture method of the article of minute concave-convex structure, the minute concave-convex structure of die surface is transferred to the surface of main body of articles by it, thus manufacture described article, described die surface is by releasing agent process, and this manufacture method comprises: surface minute concave-convex structure being transferred to main body of articles; After being peeled off from mould by described main body of articles, measure the infrared spectroscopy spectrum of die surface; And, according to the state quality of the releasing agent of die surface, determine whether to continue to manufacture.
(2) surface recorded according to (1) has the manufacture method of the article of minute concave-convex structure, wherein, it also comprises: when the state of the releasing agent of die surface is judged as bad, stop the surface minute concave-convex structure of die surface being transferred to main body of articles, and/or, again with releasing agent process die surface.
(3) surface recorded according to (1) or (2) has the manufacture method of the article of minute concave-convex structure, and wherein, the infrared spectroscopy spectrum of described mensuration die surface comprises continuously or measures the infrared spectroscopy spectrum of described die surface discontinuously.
(4) surface recorded any one of (1) ~ (3) has the manufacture method of the article of minute concave-convex structure, it comprises: the absorbance area (A) at the peak near the wave number deriving from the chemical constitution of releasing agent in infrared spectroscopy spectrum or derive from releasing agent chemical constitution wave number near peak absorbance area (A) and derive from the chemical constitution that die surface exists wave number near peak absorbance area (B) area ratio ((A)/(B)) for more than the threshold value that presets time, judge the state of the releasing agent of die surface as well.
(5) surface recorded according to (4) has the manufacture method of the article of minute concave-convex structure, and wherein, described mould is formed by aluminium oxide; Described releasing agent is fluorine compounds; The threshold value of described absorbance area (A) is 0.13, and the threshold value of the area ratio of described absorbance ((A)/(B)) is 0.047.
(6) surface recorded according to (5) has the manufacture method of the article of minute concave-convex structure, and wherein, described absorbance area (A) is less than more than 0.13 1, and the area ratio of described absorbance ((A)/(B)) is more than 0.047 and less than 10.
(7) a kind of surface has the manufacturing installation of the article of minute concave-convex structure, the minute concave-convex structure of die surface is transferred to the surface of main body of articles by it, thus manufacture the article that surface has minute concave-convex structure, described die surface is by releasing agent process, and this manufacturing installation has: surface there is minute concave-convex structure and described surface by the mould of releasing agent process; Measure the reflection-type infrared spectroscopy device of the infrared spectroscopy spectrum of die surface, described die surface is surface minute concave-convex structure being transferred to main body of articles, and the die surface after described main body of articles being peeled off from mould; The identifying unit of the state quality of the releasing agent of die surface is judged based on described infrared spectroscopy spectrum.
the effect of invention
Adopt surface of the present invention to have the manufacture method of the article of minute concave-convex structure, can online and easily the releasing agent on supervision molding surface state, productivity ratio can be suppressed to reduce.
Adopt surface of the present invention to have the manufacturing installation of the article of minute concave-convex structure, can online and easily the releasing agent on supervision molding surface state, productivity ratio can be suppressed to reduce.
Accompanying drawing explanation
Fig. 1 represents that surface of the present invention has the structure chart of an example of the manufacturing installation of the article of minute concave-convex structure.
Fig. 2 is the profile that presentation surface has the manufacturing process of the mould of anodised aluminium.
Fig. 3 represents that surface of the present invention has the profile of an example of the article of minute concave-convex structure.
Fig. 4 be presentation surface by have the fluorine compounds process of hydrolyzable silyl group, surface has the figure of an example of the infrared spectroscopy spectrum of the die surface of anodised aluminium.
Fig. 5 represents to extract absorbance area (A) and the figure of an example of the baseline (being connected the dotted line of the Origin And Destination of each absorption curve) time absorbance area (B).
Detailed description of the invention
In this manual, (methyl) acrylate refers to acrylate or methacrylate.In addition, the transparent light referred to through at least wavelength 400 ~ 1170nm.In addition, active energy beam refers to luminous ray, ultraviolet, electron ray, plasma and hot line (infrared ray etc.) etc.
< surface has the manufacturing installation > of the article of minute concave-convex structure
The manufacturing installation that surface of the present invention has the article of minute concave-convex structure has: surface there is minute concave-convex structure and described surface by the mould of releasing agent process; Measure the reflection-type infrared spectroscopy device of the infrared spectroscopy spectrum of die surface, described die surface is surface minute concave-convex structure being transferred to main body of articles, and the die surface after just described main body of articles being peeled off from mould; The identifying unit of the state quality of the releasing agent of die surface is judged based on described infrared spectroscopy spectrum.
Fig. 1 represents that surface of the present invention has the brief configuration figure of an example of the manufacturing installation of the article of minute concave-convex structure.Aforementioned manufacturing installation has: surface there is minute concave-convex structure (diagram omit) and described surface by the roll mould 20 of releasing agent process; To the rotation of roll mould 20 synchronously along the band-like film 42(main body of articles of roll mould 20 surface movement) and roll mould 20 between supply the container 22 of actinic energy ray curable resion composition; And clamp the roll 26 of film 42 and actinic energy ray curable resion composition between roll mould 20; Regulate the air pressure cylinder 24 of the clamping pressure of roll 26; Be arranged at below roll mould 20, irradiate active energy beam through film 42 pairs of actinic energy ray curable resion compositions active energy beam irradiation unit 28; From roll mould 20, stripper surface is formed with the stripper roll 30 of the film 42 of curing resin layer 44; Measure the reflection-type infrared spectroscopy device 50 of the infrared spectroscopy spectrum on roll mould 20 surface after just being peeled off together with curing resin layer 44 by film 42; The identifying unit 60 of the state quality of the releasing agent of die surface is judged based on infrared spectroscopy spectrum; Control the control device 62 that manufacturing installation runs.In addition, in the present invention, " just peeling off afterwards " when the main body of articles referring to surface to have minute concave-convex structure is peeled off from mould to described mould contacts with ensuing main body of articles.Specifically, when referring to film 42 to peel off from roll mould 20 together with curing resin layer 44 to actinic energy ray curable resion composition being supplied film 42 and roll mould 20.
(reflection-type infrared spectroscopy device)
Reflection-type infrared spectroscopy device 50 has: irradiate ultrared light source 52 to roll mould 20 surface; Receive the infrared ray of roll mould 20 surface reflection and carry out light splitting and infrared ray after detecting light splitting and obtain the detector 54 of infrared spectroscopy spectrum; Control light source 52 and detector 54 and the infrared spectroscopy spectra convey that detector 54 is obtained to the operation control machine 56 of identifying unit 60.Reflection-type infrared spectroscopy device 50 is arranged on and can measures when being peeled off from roll mould 20 together with curing resin layer 44 by film 42 to actinic energy ray curable resion composition being supplied film 42 and roll mould 20 during the position of infrared spectroscopy spectrum on roll mould 20 surface.
As reflection-type infrared spectroscopy device 50, Fourier transform type can be listed and employ the decentralized etc. of diffraction grating, because minute is short, therefore preferred Fourier transform type infrared spectroscopy device.
(identifying unit)
Identifying unit 60, such as, have: extract the intensity at the peak near the regulation wave number deriving from specified chemical structure in infrared spectroscopy spectrum or the extraction unit (diagram is omitted) of area; As required, the intensity at 2 kinds of peaks or the calculating section (diagram is omitted) of area ratio is calculated; When the intensity at peak, area or their ratio etc. are for more than the threshold value that presets (according to circumstances for below threshold value), judge the state detection unit as well (diagram is omitted) of the releasing agent on roll mould 20 surface; Store the storage part (diagram is omitted) of the threshold value inputted from outside etc.; Detection unit judge roll mould 20 surface releasing agent out of order time, by this communicating information to the communication portion of control device 62.
The absorbance area (A) at the peak of detection unit preferably near the wave number of chemical constitution deriving from releasing agent or described absorbance area (A) and derive from the chemical constitution that roll mould 20 surface exists wave number near peak absorbance area (B) area ratio ((A)/(B)) for more than the threshold value that presets time, the state of the releasing agent of judgement die surface is as well.
As releasing agent, use the fluorine compounds with hydrolyzable silyl group or silicone hydroxyl, as roll mould 20, use aluminium base surface to have the mould of anodised aluminium and described anodised aluminium has the pore of more than 2 when, each portion of identifying unit 60 is specifically preferably as follows.
The preferred following extraction unit of extraction unit: the wave number 1080 ~ 1290cm deriving from the chemical constitution of the fluorine compounds with hydrolyzable silyl group or silicone hydroxyl can be extracted from infrared spectroscopy spectrum
-1near peak absorbance area (A) and derive from the wave number 730 ~ 1080cm of chemical constitution of anodised aluminium
-1the absorbance area (B) at neighbouring peak.Baseline now has the line of the Origin And Destination of the absorption curve at peak under being set to and being connected to regulation wave number.In addition, the situation that the existence of these wave numbers changes according to the state of releasing agent, anodised aluminium also suitably can change according to the peak position occurred.
Calculating section preferably can calculate the calculating section of the area ratio ((A)/(B)) of area (A) or area (A) and the area (B) extracted by extraction unit.
The preferred following detection unit of detection unit: area (A) or area ratio ((A)/(B)) for more than the threshold value that presets time, judge the state of the releasing agent on roll mould 20 surface as well.
Wherein, as the value for judging, usable floor area ratio ((A)/(B)) when the thickness of anodised aluminium is fixed, because the problems such as error between repeatability and device are less and can expect stable mensuration, thus preferably.But, also can only judge with the area of peak (A) not under fixing situation etc. at the thickness of anodised aluminium.
In addition, identifying unit 60 also can adopt special hardware to realize, in addition identifying unit 60 also can be made up of memory and central processing unit (CPU), by being used for the program load and execution in memory of the function realizing identifying unit 60, thus realizes this function.
In addition, identifying unit 60 can connect input unit and display unit as periphery machine.Wherein, input unit refers to the input equipments such as display touch panel, switch panel and keyboard, and indication device refers to CRT and liquid crystal indicator etc.
(control device)
Control device 62 possesses handling part (diagram is omitted), interface portion (diagram is omitted) and storage part (diagram is omitted).
Interface portion is the part be electrically connected to form between each machine etc. of manufacturing installation and handling part.
Handling part controls the operation etc. of aforementioned each machine etc. according to the various setting stored in storage part and the determination information that comes from identifying unit 60 etc.Such as, judge in identifying unit 60 that the state of the releasing agent on roll mould 20 surface is as time bad, stop the movement of film 42, the rotation of roll mould 20 and come from the supply etc. of actinic energy ray curable resion composition of container 22, stop the surface minute concave-convex structure on roll mould 20 surface being transferred to film 42.
In addition, handling part also can adopt special hardware to realize, and handling part also can be made up of memory and central processing unit (CPU) in addition, by being used for the program load and execution in memory of the function realizing handling part, thus realizes this function.
In addition, control device 62 can connect input unit and display unit as periphery machine.Wherein, input unit refers to the input equipments such as display touch panel, switch panel and keyboard, and indication device refers to CRT and liquid crystal indicator etc.
In addition, as control device 62, also can use the device of the function having both aforementioned identifying unit 60, thus omit the aforementioned identifying unit 60 be provided separately with control device 62.
(active energy beam irradiation unit)
As active energy beam irradiation unit 28, high-pressure sodium lamp, metal halide lamp and melting tube (fusion lamp) etc. can be listed.
(mould)
Mould be the surface of mould base material there is minute concave-convex structure and described surface by the mould of releasing agent process.
As the material of mould base material, metal can be listed and (comprise the metal that surface is formed with oxidation overlay film.), quartz, glass, resin and pottery etc.
As the shape of mould base material, beyond roll, circular tube shaped, tabular and sheet etc. can be enumerated.
As the preparation method of mould, such as, following method (I-1) and method (I-2) can be listed, from the viewpoint of can large area and simple for production, particularly preferably method (I-1).
(I-1) method with the anodised aluminium of more than 2 pores (recess) is formed on the surface of aluminium base.
(I-2) employing photoetching process etc. directly form the method for minute concave-convex structure on the surface of mould base material.
As method (I-1), preferably there is the method for following operation (a) ~ (f).
A () in the electrolytic solution, carry out anodic oxidation to aluminium base under constant voltage, thus forms the operation of oxidation overlay film on the surface of aluminium base.
B () removes oxidation overlay film, form the operation that anodised pore produces point on the surface of aluminium base.
C () carries out anodic oxidation again to aluminium base in the electrolytic solution, produce at pore the operation that point forms the punctulate oxidation overlay film of tool.
D () makes the operation of the borehole enlargement of pore.
E (), after operation (d), carries out anodised operation in the electrolytic solution again.
F () repeats operation (d) and operation (e), obtain the operation being formed with the mould of the anodised aluminium with more than 2 pores on the surface of aluminium base.
Operation (a):
As shown in Figure 2, when anodic oxidation is carried out to aluminium base 10, form the oxidation overlay film 14 with pore 12.
As the shape of aluminium base, roll, circular tube shaped, tabular and sheet etc. can be listed.
In addition, in order to make surface state smoothing, preferably adopt the grinding aluminium bases such as mechanical lapping, polishing grinding, chemical grinding and electrolytic polishing process (etch processes).In addition, for aluminium base, due to the oil used when regulation shape is processed in attachment sometimes, therefore before anodic oxidation, preferably implement ungrease treatment in advance.
The purity of aluminium is preferably more than 99%, is more preferably more than 99.5%, is particularly preferably more than 99.8%.When the purity of aluminium is low, when carrying out anodic oxidation, the systematicness forming the pore making the concaveconvex structure of the size of visible ray scattering or obtained by anodic oxidation sometimes because of the segregation of impurity is reduced.
As electrolyte, sulfuric acid, oxalic acid and phosphoric acid etc. can be listed.
When using oxalic acid as electrolyte:
The concentration of oxalic acid is preferably below 0.7M.When the concentration of oxalic acid is more than 0.7M, current value becomes too high and to be oxidized the surface of overlay film roughening sometimes.
When formation voltage is 30 ~ 60V, can obtain having the anodised aluminium that the cycle is the pore that the systematicness of 100nm is high.When formation voltage is more high or low than this scope, the tendency that all regular property reduces.
The temperature of electrolyte is preferably less than 60 DEG C, is more preferably less than 45 DEG C.When the temperature of electrolyte is more than 60 DEG C, produce the phenomenon being called as so-called " coating gloomy and spottiness ", the systematicness of pore destruction, surface dissolution, pore is upset sometimes.
When using sulfuric acid as electrolyte:
The concentration of sulfuric acid is preferably below 0.7M.When the concentration of sulfuric acid is more than 0.7M, current value becomes too high and cannot maintain constant voltage sometimes.
When formation voltage is 25 ~ 30V, can obtain having the anodised aluminium that the cycle is the pore that the systematicness of 63nm is high.When formation voltage is more high or low than this scope, the tendency that all regular property reduces.
The temperature of electrolyte is preferably less than 30 DEG C, is more preferably less than 20 DEG C.When the temperature of electrolyte is more than 30 DEG C, produce the phenomenon being called as so-called " coating gloomy and spottiness ", the systematicness of pore destruction, surface dissolution, pore is upset sometimes.
Operation (b):
As shown in Figure 2, produce point 16 by first removing oxidation overlay film 14 and being anodised pore, the systematicness of pore can be improved.
As the method removing oxidation overlay film, the method being dissolved in and removing in the solution of not dissolved aluminum and selective dissolution oxidation overlay film can be listed.As such solution, include, for example out chromic acid/phosphoric acid mixed liquor etc.
Operation (c):
As shown in Figure 2, when anodic oxidation is carried out again to the aluminium base 10 eliminating oxidation overlay film, the oxidation overlay film 14 with columned pore 12 is formed.
Anodic oxidation is carried out under the condition same with operation (a).The anodised time is longer, can obtain darker pore.
Operation (d):
As shown in Figure 2, carry out making the process of the enlarged-diameter of pore 12 (be designated as pore diameter below and expand process.）。Pore diameter expands the process being treated to the borehole enlargement making the pore obtained by anodic oxidation in the solution be immersed in for dissolved oxygen overlay film.As such solution, include, for example out the phosphate aqueous solution etc. of about 5 quality %.
The time that pore diameter expands process is longer, and pore diameter is larger.
Operation (e):
As shown in Figure 2, when again carrying out anodic oxidation, form the cylindric pore 12 that the diameter that extends from the bottom of columned pore 12 is little further downwards.
Anodic oxidation is carried out under the condition same with operation (a).The anodised time is longer, can obtain darker pore.
Operation (f):
As shown in Figure 2, when the pore diameter of repetition operation (d) expands the anodic oxidation of process and operation (e), form the oxidation overlay film 14 of the pore 12 with the shape that diameter reduces continuously from opening portion to depth direction, obtain the mould 18 on the surface of aluminium base 10 with anodised aluminium (the porous oxidation overlay film (alumite) of aluminium).Preferably finally to terminate with operation (d).
Number of repetition preferably more than totally 3 times, is more preferably more than 5 times.When number of repetition is below 2 times, the diameter noncontinuity ground of pore reduces, and therefore, the reflectance reduction effect of the moth ocular structure using the anodised aluminium with such pore to be formed is insufficient.
As the shape of pore 12, roughly conical shape, pyramidal shape and cylindrical shape etc. can be listed, the shape that the pore sectional area in the direction intersected vertically with depth direction that preferred conical shape and pyramidal shape etc. are such reduces continuously from most surface to depth direction.
Equispaced between pore 12 be visible ray wavelength below, i.e. below 400nm.Equispaced between pore 12 is preferably more than 20nm.
Equispaced between pore 12 range preferably from more than 20nm and below 400nm, be more preferably more than 50nm and below 300nm, more preferably more than 90nm and below 250nm.
Equispaced between pore 12 measures interval between pore 12 that 50 places adjoin (distance at the center of the pore 12 that the centre-to-centre spacing of pore 12 adjoins) by electron microscope observation and their value is average and value that is that obtain.
The degree of depth of pore 12 is preferably 80 ~ 500nm when being 100nm in equispaced, is more preferably 120 ~ 400nm, is particularly preferably 150 ~ 300nm.
The degree of depth of pore 12 by electron microscope observation measure observe with multiplying power 30000 times time, distance between the top of protuberance that exists between the bottommost of pore 12 and pore 12 and the value obtained.
The aspect ratio (equispaced between the degree of depth/pore of pore) of pore 12 is preferably 0.8 ~ 5.0, is more preferably 1.2 ~ 4.0, is particularly preferably 1.5 ~ 3.0.
(releasing agent)
Then, with the surface of the formation minute concave-convex structure side of releasing agent process mould.
As releasing agent, preferably there is the releasing agent that can form the functional group of chemical bond with the anodised aluminium of aluminium base.
As releasing agent, silicones, fluororesin and fluorine compounds etc. can be listed, from the excellent aspect of release property and consider that with the excellent adhesion aspect of mould preferably there is silicone hydroxyl or hydrolyzable silyl group, wherein, particularly preferably there are the fluorine compounds of hydrolyzable silyl group.As the commercially available product of fluorine compounds with hydrolyzable silyl group, fluoro alkyl-silane can be listed, chemical industrial company of KBM-7803(SHIN-ETSU HANTOTAI manufactures), " OPTOOL(registration mark) " serial (Daikin Industries, Ltd. manufacture) and the manufacture of NovecEGC-1720(Sumitomo 3M company) etc.
As the processing method utilizing releasing agent, following method (II-1) and (II-2) can be listed, carry out uniform process from the viewpoint of the surface that releasing agent can be utilized the formation minute concave-convex structure side of mould, particularly preferably method (II-1).
(II-1) mould is immersed in the method in the dilute solution of releasing agent.
(II-2) releasing agent or its dilute solution are coated on the method on the surface of the formation minute concave-convex structure side of mould.
As method (II-1), preferably there is the method for following operation (g) ~ (l).
G operation that () washes mould.
H (), to mould blow air, removes the operation of the water droplet of the surface attachment of mould.
(i) the operation of impregnation mold in the dilute solution of fluorine compounds with solvent dilution with hydrolyzable silyl group.
(j) by the mould flooded slowly from the operation that solution is mentioned.
K () as required, after operation (j), carries out the operation of warming and humidifying to mould.
L () makes the operation of mould drying.
< surface has the manufacture method > of the article of minute concave-convex structure
The manufacture method that surface of the present invention has the article of minute concave-convex structure is surface surface being transferred to main body of articles by the minute concave-convex structure of the die surface of releasing agent process, thus manufacture the method that surface has the article of minute concave-convex structure, it is surface minute concave-convex structure being transferred to main body of articles, measure the infrared spectroscopy spectrum of described main body of articles from the die surface after mould stripping, judge the method for the state quality of the releasing agent of die surface based on described infrared spectroscopy spectrum.
As the method on the surface minute concave-convex structure of die surface being transferred to main body of articles, such as, can enumerate have following operation (i) ~ method (iii).
(i) on surface, there is minute concave-convex structure and described surface is clamped the operation of actinic energy ray curable resion composition between the mould of releasing agent process and main body of articles.
(ii) active energy beam is irradiated to actinic energy ray curable resion composition, make described actinic energy ray curable resion composition be solidified to form the operation of the curing resin layer with minute concave-convex structure.
(iii), by the curing resin layer demoulding of mould from main body of articles surface, obtain the operation that surface has the article of minute concave-convex structure.
(main body of articles)
As the material of main body of articles, implement to irradiate active energy beam to cross main body of articles, the material of preferred high transparent, such as, can list acrylic acid (ester) is resin, PETG, Merlon and Triafol T etc.
As the shape of main body of articles, film, sheet, injection-molded article and compressing product etc. can be enumerated.
(actinic energy ray curable resion composition)
Actinic energy ray curable resion composition comprises polymerizable compound and polymerization initiator.
As polymerizable compound, monomer, oligomer and the reactive polymer etc. with free-radical polymerised key and/or cationically polymerizable key can be listed in molecule.
Actinic energy ray curable resion composition also can comprise non-reacted polymer and active energy beam solgel reaction composition.
As the monomer with free-radical polymerised key, monofunctional monomer and polyfunctional monomer can be listed.
As monofunctional monomer, can list: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) alkyl acrylate, (methyl) tridecyl acrylate, (methyl) stearyl acrylate ester, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, (methyl) acrylate, (methyl) isobornyl acrylate, (methyl) glycidyl acrylate, (methyl) tetrahydrofurfuryl acrylate, (methyl) allyl acrylate, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) hydroxypropyl acrylate, (methyl) acrylic acid 2-methoxy acrylate, and (methyl) acrylate derivative such as (methyl) acrylic acid 2-ethoxy ethyl ester, (methyl) acrylic acid, (methyl) acrylonitrile, the styrene derivative such as styrene and AMS, and (methyl) acrylamide derivative etc. such as (methyl) acrylamide, N-dimethyl (methyl) acrylamide, N-diethyl (methyl) acrylamide and dimethylamino-propyl (methyl) acrylamide.These monomers can be used alone a kind also can combinationally use two or more.
As polyfunctional monomer, can list: ethylene glycol bisthioglycolate (methyl) acrylate, tripropylene glycol two (methyl) acrylate, isocyanuric acid ethylene-oxide-modified two (methyl) acrylate, triethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, 1,5-PD two (methyl) acrylate, 1,3-BDO two (methyl) acrylate, polytetramethylene glycol two (methyl) acrylate, two (4-(methyl) acryloxypolyethoxyphenyl of 2,2-) propane, two (4-(methyl) acryloxy ethoxy phenyl of 2,2-) propane, two (4-(3-(methyl) acryloxy-2-hydroxy propyloxy group of 2,2-) phenyl) propane, two (3-(methyl) acryloxy-2-hydroxy propyloxy group of 1,2-) ethane, Isosorbide-5-Nitrae-bis-(3-(methyl) acryloxy-2-hydroxy propyloxy group) butane, dihydroxymethyl tristane two (methyl) acrylate, ethylene oxide adduct two (methyl) acrylate of bisphenol-A, propylene oxide adduct two (methyl) acrylate of bisphenol-A, 3-hydroxypivalic acid neopentyl glycol two (methyl) acrylate, divinylbenzene, and two functional monomers such as methylene-bisacrylamide, the trifunctional monomers such as pentaerythrite three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, trimethylolpropane ethylene-oxide-modified three (methyl) acrylate, trimethylolpropane epoxy pronane modification triacrylate, the ethylene-oxide-modified triacrylate of trimethylolpropane, isocyanuric acid ethylene-oxide-modified three (methyl) acrylate, monomers more than four senses such as butanedioic acid/trimethylolethane/acrylic acid condensation reaction mixture, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, two (trimethylolpropane) tetraacrylate and tetramethylol methane four (methyl) acrylate, and two urethane acrylate more than sense and polyester acrylates etc. more than two senses.These monomers can be used alone a kind also can combinationally use two or more.
As the monomer with cationically polymerizable key, the monomer with epoxy radicals, oxetanylmethoxy, oxazolyl, ethyleneoxy etc. can be listed, particularly preferably there is the monomer of epoxy radicals.
As oligomer or reactive polymer, can list: the unsaturated polyester (UP) classes such as the condensation product of unsaturated dicarboxylic and polyalcohol; Polyester (methyl) acrylate, polyethers (methyl) acrylate, polyalcohols (methyl) acrylate, epoxy radicals (methyl) acrylate, polyurethane (methyl) acrylate, cationic polymerization type epoxide and side chain have the homopolymers or copolymer etc. of the above-mentioned monomer of free-radical polymerised key.
As non-reacted polymer, can list acrylic acid (ester) is resin, phenylethylene resin series, polyurethane, cellulose-based resin, polyvinyl butyral resin, polyester and thermoplastic elastomer (TPE) etc.
As active energy beam solgel reaction composition, alkoxysilane compound containing trialkylsilyl group in molecular structure and alkyl silicate compound etc. can be listed.
As alkoxysilane compound containing trialkylsilyl group in molecular structure, the compound of following formula (1) can be listed.
R
11 xSi（OR
12）
y…（1）
Wherein, R
11, R
12represent the alkyl of carbon number 1 ~ 10 respectively, x, y represent the integer of the relation meeting x+y=4.
As alkoxysilane compound containing trialkylsilyl group in molecular structure, can list: tetramethoxy-silicane, tetraisopropoxysilan, four positive propoxy silane, four n-butoxy silane, four sec-butoxy silane, four tert-butoxy silane, MTES, methyl tripropoxy silane, methyl three butoxy silane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, trimethyl npropoxysilane and trimethylbutoxy silane etc.
As alkyl silicate compound, the compound of following formula (2) can be listed.
R
21O[Si（OR
23）（OR
24）O]
zR
22…（2）
Wherein, R
21~ R
24represent the alkyl of carbon number 1 ~ 5 respectively, z represents the integer of 3 ~ 20.
As alkyl silicate compound, methyl silicate, silester, isopropyl silicate, n-propyl silicate, the positive butyl ester of silicic acid, silicic acid n-pentyl ester and acetyl group esters of silicon acis (acetyl silicate) etc. can be listed.
When utilizing photocuring reaction, as Photoepolymerizationinitiater initiater, include, for example out: benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, benzoin isobutyl ether, benzil, benzophenone, to methoxy benzophenone, 2,2-diethoxy acetophenone, α, alpha, alpha-dimethyl oxygen base-α-phenyl acetophenone, methyl benzoylformate, ethyl benzoylformate, 4,4'-two carbonyls such as (dimethylamino) benzophenone and 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone; The sulphur compound such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; And 2,4,6-trimethylbenzoyl diphenyl phosphine oxide; And benzoyl diethoxy phosphine oxide etc.They can be used singly or in combination of two or more.
When utilizing electron ray curing to react, as polymerization initiator, include, for example out: benzophenone, 4, two (diethylamino) benzophenone, 2 of 4-, 4, the thioxanthones such as 6-tri-methyl benzophenone, methyl o-benzoylbenzoate, 4-phenyl benzophenone, tert-butyl group anthraquinone, 2-EAQ, 2,4-diethyl thioxanthones, isopropyl thioxanthone and 2,4-bis-clopenthixal ketone; Diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, benzil dimethyl ketal, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propane-1-ketone and 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl) acetophenone such as-butanone; The benzoin ether such as benzoin methylether, benzoin ethyl ether, benzoin iso-propylether and benzoin isobutyl ether; The acylphosphine oxides such as 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, two (2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide and two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide; And methyl benzoylformate; 1,7-bis-acridinyl heptane; And 9-phenylacridine etc.They can be used singly or in combination of two or more.
When utilizing heat cure to react, as thermal polymerization, include, for example out: the organic peroxides such as methyl-ethyl-ketone peroxide, benzoyl peroxide, dicumyl peroxide, TBHP, dicumyl peroxide, the peroxidation acid tert-butyl ester, peroxidized t-butyl perbenzoate and lauroyl peroxide; The Azo such as azodiisobutyronitrile; And in aforementioned organic peroxides, combine the redox polymerization initator etc. of the amine such as DMA and N, N-dimethyl-p-toluidine.
Relative to 100 mass parts polymerizable compounds, the amount of polymerization initiator is preferably 0.1 ~ 10 mass parts.During quantity not sufficient 0.1 mass parts of polymerization initiator, polymerization is difficult to carry out.When the amount of polymerization initiator is more than 10 mass parts, the painted or mechanical strength of cured film reduces sometimes.
Actinic energy ray curable resion composition according to circumstances can also contain antistatic agent, releasing agent, for improving additive, particulate and a small amount of solvents such as the fluorine compounds of soil resistance.
(hydrophobic material)
In order to make the water contact angle on the minute concave-convex structure surface of curing resin layer be more than 90 °, as the actinic energy ray curable resion composition that can form hydrophobic material, preferably use the composition comprising fluorochemical or silicon-type compound.
Fluorochemical:
As fluorochemical, preferably there is the compound of the fluoroalkyl shown in following formula (3).
-（CF
2）
n-X…（3）
Wherein, X represents fluorine atom or hydrogen atom, and n represents the integer of more than 1, is preferably 1 ~ 20, is more preferably 3 ~ 10, is particularly preferably 4 ~ 8.
As fluorochemical, fluorochemical monomer, fluorine containing silane coupling agent, fluorine-containing surfactant and fluoropolymer etc. can be listed.
As fluorochemical monomer, fluoroalkyl substituted ethylene base monomer and fluoroalkyl replacement ring-opening polymerisation monomer etc. can be listed.
As fluoroalkyl substituted ethylene base monomer, fluoroalkyl can be listed and replace (methyl) acrylate, fluoroalkyl replacement (methyl) acrylamide, fluoroalkyl substituted ethylene base ether and fluoroalkyl substituted phenylethylene etc.
Replace ring-opening polymerisation monomer as fluoroalkyl, fluoroalkyl substituted epoxy compound can be listed, fluoroalkyl replaces oxetane compound and fluothane base substituted oxazole quinoline compound etc.
As fluorochemical monomer, preferred fluoroalkyl replaces (methyl) acrylate, the particularly preferably compound of following formula (4).
CH
2＝C（R
41）C（O）O-（CH
2）
m-（CF
2）
n-X…（4）
Wherein, R
41represent hydrogen atom or methyl, X represents hydrogen atom or fluorine atom, and m represents the integer of 1 ~ 6, is preferably 1 ~ 3, be more preferably 1 or 2, n represent 1 ~ 20 integer, be preferably 3 ~ 10, be more preferably 4 ~ 8.
As fluorine containing silane coupling agent, preferred fluoroalkyl substituted silane coupling agent, the particularly preferably compound of following formula (5).
（R
f）
aR
51 bSiY
c…（5）
R
fexpression can contain the fluorine substituted alkyl of the carbon number 1 ~ 20 of more than 1 ehter bond or ester bond.As R
f, 3,3,3-trifluoro propyl, 13 fluoro-1,1,2,2-tetrahydrochysene octyl groups, 3-trifluoromethoxy propyl group and 3-trifluoroacetyl oxygen base propyl group etc. can be listed.
R
51represent the alkyl of carbon number 1 ~ 10.As R
51, methyl, ethyl and cyclohexyl etc. can be listed.
Y represents hydroxyl or hydrolization group.
As hydrolization group, alkoxyl and halogen atom, R can be listed
52c(O) O(wherein, R
52represent the alkyl of hydrogen atom or carbon number 1 ~ 10.) etc.
As alkoxyl, can list: methoxyl group, ethyoxyl, propoxyl group, isopropoxy, butoxy, isobutoxy, tert-butoxy, amoxy, own oxygen base, cyclohexyloxy, heptan oxygen base, octyloxy, 2-ethyl hexyl oxy, the ninth of the ten Heavenly Stems oxygen base, the last of the ten Heavenly stems oxygen base, 3,7-dimethyl octyloxies and bay oxygen base etc.
As halogen atom, Cl, Br and I etc. can be listed.
As R
52c(O) O, can list CH
3c(O) O and C
2h
5c(O) O etc.
A, b and c represent and meet a+b+c=4 and the integer of a >=1 and c >=1, preferred a=1, b=0 and c=3.
As fluorine containing silane coupling agent, 3,3,3-trifluoro propyl trimethoxy silane, 3,3,3-trifluoro propyl triacetoxysilanes, dimethyl-3,3,3-trifluoro propyl methoxy silane and 13 fluoro-1,1,2,2-tetrahydrochysene octyltri-ethoxysilane etc. can be listed.
As fluorine-containing surfactant, the anion system surfactant containing fluoroalkyl, the cation system surfactant etc. containing fluoroalkyl can be listed.
As the anion system surfactant containing fluoroalkyl, can list: the fl muoroalkyl of carbon number 2 ~ 10 or its slaine, PFO sulfonyl glutamate disodium, 3-[ω-fluothane (C
6~ C
11) oxygen base]-1-alkyl (C
3~ C
4) sodium sulfonate, 3-[ω-fluoroalkanoyl (C
6~ C
8)-N-ethylamino]-1-propane sulfonic acid sodium, fluoroalkyl (C
11~ C
20) carboxylic acid or its slaine, perfluoro carboxylic acid (C
7~ C
13) or its slaine, perfluoroalkyl (C
4~ C
12) sulfonic acid or its slaine, PFOS diglycollic amide, N-propyl group-N-(2-ethoxy) PFO sulfonamide, perfluoroalkyl (C
6~ C
10) suldonamide propyl trimethyl, perfluoroalkyl (C
6~ C
10)-N-ethylsulfonyl glycinate and single perfluoroalkyl (C
6~ C
16) ethyl phosphonic acid ester etc.
As containing the cation system surfactant of fluoroalkyl, or tertiary amine acid, perfluoroalkyl (C sour containing the Armeen acid of fluoroalkyl, secondary amine can be listed
6~ C
10) aliphatic quaternary ammonium salt, zephiran salt, benzethonium chloride, pyridiniujm and the imidazole salts etc. such as suldonamide propyl trimethyl.
As fluoropolymer, the polymer of the monomer containing fluoroalkyl can be listed, containing the monomer of fluoroalkyl and the copolymer of the monomer containing poly-(oxyalkylene) and the copolymer etc. containing the monomer of fluoroalkyl and the monomer containing cross-linking reaction group.Fluoropolymer can be the copolymer with other monomer of energy copolymerization.
As fluoropolymer, preferably contain the copolymer of the monomer of fluoroalkyl and the monomer containing poly-(oxyalkylene).
As poly-(oxyalkylene), the group shown in preferred following formula (6).
-（OR
61）
p-…（6）
Wherein, R
61represent the alkylidene of carbon number 2 ~ 4, p represents the integer of more than 2.
As R
61, can-CH be listed
2cH
2-,-CH
2cH
2cH
2-,-CH(CH
3) CH
2-and-CH(CH
3) CH(CH
3)-etc.
Poly-(oxyalkylene) can by identical oxygen alkylidene unit (OR
61) form, also can by oxygen alkylidene unit (OR of more than two kinds
61) form.Oxygen alkylidene unit (OR of more than two kinds
61) arrangement can be block, also can be random.
Silicon-type compound:
As silicon-type compound, (methyl) acryl-modified silicone resin, silicones and silicon-type silane coupler etc. can be listed.
As (methyl) acryl-modified silicone resin, organosilicon (two) (methyl) acrylate etc. can be listed.
(hydrophilic material)
In order to make the water contact angle on the minute concave-convex structure surface of curing resin layer be less than 25 °, as the actinic energy ray curable resion composition that can form hydrophilic material, preferably use the composition at least containing hydrophilic monomer.In addition, from the viewpoint of imparting marresistance, resistance to water, the polyfunctional monomer that can be cross-linked more preferably is comprised.It should be noted that, hydrophilic monomer and the polyfunctional monomer that can be cross-linked can identical (that is, hydrophily polyfunctional monomers).And then actinic energy ray curable resion composition can also comprise other monomer.
As the actinic energy ray curable resion composition that can form hydrophilic material, more preferably use the composition comprising following polymerizable compound.
By 4 officials can above multifunctional (methyl) acrylate 10 ~ 50 quality %,
2 officials can above hydrophily (methyl) acrylate 30 ~ 80 quality % and
Monofunctional monomer 0 ~ 20 quality % amounts to the polymerizable compound that 100 quality % are formed.
Can above multifunctional (methyl) acrylate as 4 officials, two (trimethylolpropane) four (methyl) acrylate can be listed, pentaerythrite four (methyl) acrylate, pentaerythrite ethyoxyl four (methyl) acrylate, dipentaerythritol hydroxyl five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, the condensation reaction mixture of butanedioic acid/trimethylolethane/acrylic acid mol ratio 1:2:4, (DAICEL-CYTEC Company LTD. manufactures urethane acrylate class: EBECRYL220, EBECRYL1290, EBECRYL1290K, EBECRYL5129, EBECRYL8210, EBECRYL8301, and KRM8200) polyether acrylate class (DAICEL-CYTEC Company LTD. manufactures, EBECRYL81), modified epoxy acrylic ester class (DAICEL-CYTEC CompanyLTD. manufactures, EBECRYL3416), and polyester acrylate class (DAICEL-CYTEC Company LTD. manufactures: EBECRYL450, EBECRYL657, EBECRYL800, EBECRYL810, EBECRYL811, EBECRYL812, EBECRYL1830, EBECRYL845, EBECRYL846, and EBECRYL1870) etc.These can be used alone one, also can be used in combination of two or more.
Can above multifunctional (methyl) acrylate as 4 officials, 5 officials can multifunctional (methyl) acrylate above be preferred.
4 officials the ratio of above multifunctional (methyl) acrylate can be preferably 10 ~ 50 quality %, from the viewpoint of resistance to water and chemically-resistant preparation, be more preferably 20 ~ 50 quality %, be particularly preferably 30 ~ 50 quality %.4 officials can the ratio of above multifunctional (methyl) acrylate when being more than 10 quality %, and elastic modelling quantity uprises, and marresistance improves.4 officials can the ratio of above multifunctional (methyl) acrylate when being below 50 quality %, and surface not easily produces little be full of cracks, not easily causes open defect.
Can above hydrophily (methyl) acrylate as 2 officials, ARONIX(registration mark can be listed) M-240, ARONIX(registration mark) M260(East Asia Synesis Company manufactures), NK ESTER AT-20E, chemical company of NK ESTER ATM-35E(Xin Zhong village manufacture) etc. there is the polyfunctional acrylic ester of longer chain polyethylene glycols; And polyethylene glycol dimethacrylate etc.These can be used alone one, also can be used in combination of two or more.
In polyethylene glycol dimethacrylate, 1 molecular memory the total amount of average repeat unit of polyglycol chain be preferably 6 ~ 40, be more preferably 9 ~ 30, be particularly preferably 12 ~ 20.If the average repeat unit of polyglycol chain is more than 6, then hydrophily becomes abundant, and soil resistance improves.If the average repeat unit of polyglycol chain is less than 40, then the compatibility of above multifunctional (methyl) acrylate can become good with 4 officials, actinic energy ray curable resion composition is not easy to be separated.
2 officials the ratio of above hydrophily (methyl) acrylate can be preferably 30 ~ 80 quality %, are more preferably 40 ~ 70 quality %.2 officials can the ratio of above hydrophily (methyl) acrylate when being more than 30 quality %, and hydrophily becomes fully, and soil resistance improves.2 officials can the ratio of above hydrophily (methyl) acrylate when being below 80 quality %, and elastic modelling quantity uprises, and marresistance improves.
As monofunctional monomer, preferred hydrophilic monofunctional monomer.
As hydrophily monofunctional monomer, chemical company of M-20G, M-90G and M-230G(Xin Zhong village can be listed and manufacture) etc. ester group has simple function (methyl) acrylate of polyglycol chain; The ester groups such as (methyl) acrylic acid hydroxy alkyl ester has simple function (methyl) acrylate of hydroxyl; Simple function acrylic amide; And Methacrylamide oxypropyl trimethyl ammonium methyl sulphate; And the cationic monomer class etc. such as methacryloxyethyl trimethylammoniumethyl sulfate.
In addition, as monofunctional monomer, the viscosity modifier such as acryloyl morpholine and vinyl pyrrolidone can be used; And raising is to adaptation improving agents etc. such as the propenoyl isocyanate classes of the adaptation of main body of articles.
The ratio of monofunctional monomer is preferably 0 ~ 20 quality %, is more preferably 5 ~ 15 quality %.By using monofunctional monomer, the adaptation of main body of articles and cured resin improves.When the ratio of monofunctional monomer is below 20 quality %, there will not be 4 officials can above multifunctional (methyl) acrylate or 2 officials can the situation of above hydrophily (methyl) acrylate deficiency, can sufficient soil resistance, marresistance be obtained.
Monofunctional monomer can be polymerized form compounding 0 ~ 35 mass parts in actinic energy ray curable resion composition of the polymer of the low polymerization degree that (copolymerization) obtains with one or more.As the polymer of low polymerization degree, chemical company of M-230G(Xin Zhong village can be listed manufacture) etc. ester group has simple function (methyl) esters of acrylic acid of polyglycol chain and 40/60 copolymerized oligomer (the MRC UNITEC Co. of Methacrylamide oxypropyl trimethyl ammonium methyl sulphate, Ltd. manufacture, MG polymer) etc.
(concrete example of manufacture method)
The concrete example surface of the present invention employing the manufacturing installation shown in Fig. 1 to the manufacture method of the article of minute concave-convex structure is described.
Surface have minute concave-convex structure (diagram omit) roll mould 20 and and the rotation of roll mould 20 synchronously along the band-like film 42(main body of articles of roll mould 20 surface movement) between, supply actinic energy ray curable resion composition by container 22.
At roll mould 20 and regulated by air pressure cylinder 24 between the roll 26 that clamps and press and clamp film 42 and actinic energy ray curable resion composition, while making actinic energy ray curable resion composition evenly spread all between film 42 and roll mould, be filled in the recess of the minute concave-convex structure of roll mould 20.
By irradiating active energy beam by the active energy beam irradiation unit 28 arranged below roll mould 20 through film 42 pairs of actinic energy ray curable resion compositions, thus actinic energy ray curable resion composition is solidified, form the curing resin layer 44 of the minute concave-convex structure transferred with roll mould 20 surface.The light irradiation energy that active energy beam irradiation unit 28 sends is preferably 100 ~ 10000mJ/cm
2.
Be formed with the film 42 of curing resin layer 44 by use stripper roll 30 from stripper surface roll mould 20, obtain article 40 as shown in Figure 3.
Then, reflection-type infrared spectroscopy device 50 is used to measure the infrared spectroscopy spectrum on roll mould 20 surface after firm stripping film 42.From the viewpoint of the state of releasing agent often grasping die surface, the mensuration of the infrared spectroscopy spectrum of die surface preferably continuously or provide predetermined distance and carry out discontinuously.Reflection-type infrared spectroscopy device 50 can be fixed also can be scan-type.
Then, about identifying unit 60: extraction unit extracts intensity or the area at the peak near the regulation wave number deriving from specified chemical structure in the infrared spectroscopy spectrum that reflection-type infrared spectroscopy device 50 measures; Calculating section calculates intensity or the area ratio at 2 kinds of peaks as required; Intensity at peak, area or their ratio etc. are for more than the threshold value that presets time (according to circumstances for below threshold value), and detection unit judges the state of the releasing agent on roll mould 20 surface as well; Detection unit judges that the state of the releasing agent on roll mould 20 surface is as time bad, by communication portion by this communicating information to control device 62.
About detection unit, relatively high from the viewpoint of judgement precision, the absorbance area (A) at the peak near the wave number preferably deriving from the chemical constitution of releasing agent or derive from releasing agent chemical constitution wave number near peak absorbance area (A) and derive from the chemical constitution that roll mould 20 surface exists wave number near peak absorbance area (B) area ratio ((A)/(B)) for more than the threshold value that presets time, the state of the releasing agent of judgement die surface is as well.
For identifying unit 60, specifically, as releasing agent, use the fluorine compounds with hydrolyzable silyl group or silicone hydroxyl, as roll mould 20, use aluminium base surface to have the mould of anodised aluminium and described anodised aluminium has the pore of more than 2 when, preferably carry out following process.
Extraction unit extracts the wave number 1080 ~ 1290cm deriving from the chemical constitution of the fluorine compounds with hydrolyzable silyl group or silicone hydroxyl from infrared spectroscopy spectrum
-1near peak absorbance area (A) and derive from the wave number 730 ~ 1080cm of chemical constitution of anodised aluminium
-1the absorbance area (B) at neighbouring peak.Baseline now has the dotted line of the Origin And Destination of the absorption curve at peak under being set to and being connected to regulation wave number.Particular instantiation is in Fig. 5.
Calculating section calculates the area (A) and area (B) that are extracted by extraction unit, and then calculates both area ratio ((A)/(B)).
Area (A) or area ratio ((A)/(B)) for more than the threshold value that presets time, detection unit judges the state of the releasing agent on roll mould 20 surface as well.
Use in advance manufactures identical manufacturing installation used with reality and preparing experiment implemented by identical material, confirm roll mould 20 become cannot from before curing resin layer 44 demoulding or the part demoulding bad and produce defect time area (A) or area ratio ((A)/(B)), thus carry out the threshold value setting of area (A) or area ratio ((A)/(B)).As releasing agent, use fluorine compounds (the Daikin Industries with hydrolyzable silyl group or silicone hydroxyl, Ltd. manufacture, OPTOOL(registration mark) DSX), as roll mould 20, use surface to have the mould of anodised aluminium and described anodised aluminium has the pore of more than 2 when, the present inventor etc. confirm by repeatedly implementing preparing experiment: area (A) is 0.13 or area ratio ((A)/(B)) when being more than 0.047, the demoulding does not occur bad; Area (A) is 0.15 or area ratio ((A)/(B)) when being more than 0.070, more stably can carry out transfer printing.Although be not particularly limited the upper limit of area (A) or area ratio ((A)/(B)), but when the amount of releasing agent increases, cannot the problem such as minute concave-convex structure of the mould of transfer printing roll exactly 20 owing to producing, thus area (A) is preferably less than 1, more preferably less than 0.8.In addition, area ratio ((A)/(B)) is preferably less than 10, is more preferably less than 5.
As releasing agent, use aforementioned fluorine compounds (Daikin Industries, Ltd. manufacture, OPTOOL(registration mark) DSX), as roll mould 20, as roll mould 20, use surface to have the mould of anodised aluminium and described anodised aluminium has the pore of more than 2 when, area (A) be preferably more than 0.13 and less than 1, be more preferably more than 0.15 and less than 0.8.
Use aforementioned fluorine compounds as releasing agent, as roll mould 20, when using foregoing mould, area ratio ((A)/(B)) be preferably more than 0.047 and less than 10, be more preferably more than 0.070 and less than 5.
For control device 62, such as, judge in identifying unit 60 that the state of the releasing agent on roll mould 20 surface is as time bad, stop the movement of film 42, the rotation of roll mould 20 and come from the supply etc. of actinic energy ray curable resion composition of container 22, stop the surface minute concave-convex structure on roll mould 20 surface being transferred to film 42.After stopping, can the agent of mold removal coated release.In addition, control device 62 can be that the output that produces according to identifying unit 60 is in the formation of the surperficial coated release agent of roll mould 20.
(article)
Fig. 3 represents that the surface obtained by manufacture method of the present invention has the profile of an example of the article 40 of minute concave-convex structure.
Film 42 is transparent thin-film.As the material of film, Merlon can be listed, polystyrene resin, polyester, polyurethane, acrylic acid (ester) is resin, polyether sulfone, polysulfones, polyether-ketone, cellulose-based resin (Triafol T etc.), polyolefin and ester ring type polyolefin etc.
Curing resin layer 44 is the films formed by the solidfied material of actinic energy ray curable resion composition, and surface has minute concave-convex structure.
The minute concave-convex structure of the minute concave-convex structure transfer printing anodized aluminum surfaces on article 40 surface when using the mould of anodised aluminium is formed, and has formed by the solidfied material of actinic energy ray curable resion composition 2 with upper convex portion 46.
As minute concave-convex structure, the so-called moth ocular structure that the projection (protuberance) more than 2 of preferred roughly conical shape or pyramidal shape etc. arranges.Because refractive index increases continuously from the refractive index of air to the refractive index of material, the moth ocular structure below the wavelength being spaced apart visible ray therefore between known projection is the means of effective antireflection.
Equispaced between protuberance be visible ray wavelength below, i.e. below 400nm.When using the mould of anodised aluminium to form protuberance, the equispaced between protuberance is about 100nm ~ 200nm, is particularly preferably below 250nm.
From the viewpoint of easily forming protuberance, the equispaced between protuberance is preferably more than 20nm.
Equispaced between protuberance range preferably from 20 ~ 400nm, be more preferably 50 ~ 300nm, more preferably 90 ~ 250nm.
Equispaced between protuberance measures interval (distance from the center of protuberance to the center of adjacent protuberance) between protuberance that 50 places adjoin by electron microscope observation, and their value is average and value that is that obtain.
The height of protuberance is preferably 80 ~ 500nm when being 100nm in equispaced, is more preferably 120 ~ 400nm, is particularly preferably 150 ~ 300nm.When the height of protuberance is more than 80nm, reflectivity is enough low, and the wavelength dependency of reflectivity is few.When the height of protuberance is below 500nm, the marresistance of protuberance is good.
The height of protuberance is distance between the top of protuberance when utilizing determination of electron microscopy to observe with multiplying power 30000 times and the bottommost being present in the recess between protuberance and the value obtained.
The aspect ratio (equispaced between the height/protuberance of protuberance) of protuberance is preferably 0.8 ~ 5.0, is more preferably 1.2 ~ 4.0, is particularly preferably 1.5 ~ 3.0.When the aspect ratio of protuberance is more than 1.0, reflectivity is enough low.When the aspect ratio of protuberance is less than 5.0, the marresistance of protuberance is good.
The cross sectional shape of the short transverse of shape, i.e. protuberance that the protuberance sectional area that the shape of protuberance is preferably the direction intersected vertically with short transverse increases continuously from most surface along depth direction is the shapes such as triangle, trapezoidal and bell.
The refractive index of curing resin layer 44 and the specific refractivity of film 42 are preferably less than 0.2, are more preferably less than 0.1, are particularly preferably less than 0.05.When refringence is less than 0.2, the reflection at the interface of curing resin layer 44 and film 42 can be suppressed.
When surface has minute concave-convex structure, known, if its surface is formed by hydrophobic material, then can obtain super-hydrophobicity because of lotus leaf effect, if its surface is formed by hydrophilic material, then obtain Superhydrophilic.
The water contact angle on the minute concave-convex structure surface when material of curing resin layer 44 is hydrophobicity is preferably more than 90 °, is more preferably more than 110 °, is particularly preferably more than 120 °.When water contact angle is more than 90 °, not easily attached water is dirty, therefore, it is possible to play sufficient soil resistance.In addition, not easily attached water, therefore expection can making ice.
The water contact angle on the minute concave-convex structure surface when material of curing resin layer 44 is hydrophobicity range preferably from more than 90 ° and less than 180 °, be more preferably more than 110 ° and less than 180 °, be particularly preferably more than 120 ° and less than 180 °.
The water contact angle on the minute concave-convex structure surface when material of curing resin layer 44 is hydrophily is preferably preferably less than 25 °, is more preferably less than 23 °, is particularly preferably less than 21 °.When water contact angle is below 25 °, the dirt of surface attachment is washed away, and not easily adheres to greasy dirt, can play sufficient soil resistance.From the viewpoint of suppress cause because of the water suction of curing resin layer 44 minute concave-convex structure distortion, with its reflectivity raise, aforementioned water contact angle is preferably more than 3 °.
The water contact angle on the minute concave-convex structure surface when material of curing resin layer 44 is hydrophily range preferably from more than 3 ° and less than 30 °, be more preferably more than 3 ° and less than 23 °, be particularly preferably more than 3 ° and less than 21 °.
(purposes)
As the purposes of article 40, can list: reflection preventing article, anti-fog properties article, soil resistance article and hydrophobicity article, more specifically, can list: display antireflection, automobile instrument (meter cover), the electroluminescent light extraction efficiency of automobile mirrors, automotive window, organic or inorganic improve parts and solar cell part etc.
(action effect)
Surface of the present invention described above has the surface that minute concave-convex structure is transferred to main body of articles by the manufacture method of the article of minute concave-convex structure and manufacturing installation, measure the infrared spectroscopy spectrum just peeling off the die surface after described main body of articles from mould, the state quality of the releasing agent of die surface is judged, so can the state of the online and easily releasing agent on supervision molding surface based on described infrared spectroscopy spectrum.Its result, the demoulding can grasping mould is in advance bad, and surface can be suppressed to have the reduction of the productivity ratio of the article of minute concave-convex structure.
That is, adopt the present invention, due to the state of the releasing agent of die surface can be judged to noncontact and non-demolition, thus can judge online in article manufacture.Therefore, can predict that the demoulding is bad in advance, article manufacture can be stopped before the demoulding is bad.Its result, owing to manufacturing article until the demoulding bad before, so effectively mould can be used, and because preventing by the attachment of the cured resin of the bad generation of the demoulding, so make the washing of mould become easy.In addition, due to the bad trouble caused of the demoulding can be avoided, thus more safely article can be manufactured.
In addition, in the present invention, adopt the reason of reflective infrared optical spectroscopy as described below.
As mentioned above, when the minute concave-convex structure of die surface being transferred to constantly main body of articles surperficial, release property will worsen soon.As its reason, think the sex change etc. of the releasing agent coming off and caused by active energy beam (ultraviolet etc.), heat etc. of releasing agent on mould.Therefore, use the fluorine compounds with hydrolyzable silyl group as the bad reason of demoulding during releasing agent to understand fully, and initial die surface and the die surface that becomes the demoulding bad are analyzed, the amount of estimation releasing agent.Usually, because releasing agent is coated on mould thinly, so need the method using surface sensitivity excellence.Such as, consider to use TOF-SIMS, XPS and IR method etc.So analyze with XPS and TOF-SIMS, result, the amount (atomicity is than F/Al) of the releasing agent such as obtained by XPS from initial 8.3 be reduced to the demoulding bad time 2.1.In addition, the structure change of remaining on mould unconfirmed releasing agent.Specify that the bad reason of the demoulding is coming off of releasing agent by this result.Therefore, by grasping the amount of the releasing agent of die surface, making to predict that the demoulding is bad in advance becomes possibility.
But, for TOF-SIMS, XPS, due to device form on problem, so a certain size above mould cannot be measured, carry out measuring more difficult in article manufacture, there is the problem that cannot monitor online.In addition, even if the ATR method of surface sensitivity excellence also cannot non-contactingly measure in infrared measure, can die surface be damaged, thus cannot measure in article manufacture.In addition, for these methods, because die surface has minute concave-convex structure, thus differentiate that it is also more difficult for which part measuring.Therefore, by carrying out the mensuration adopting reflective infrared optical spectroscopy, can solve the problem, the size of mould can be scrupled, and grasping the amount of releasing agent non-contactly.
At this, reflective infrared optical spectroscopy is described.When irradiating infrared ray to mould, infrared ray through the releasing agent be made up of the fluorine compounds with hydrolyzable silyl group, the most of anodised aluminium that are present in surface, and is reflected by the metal covering of aluminium base.By carrying out light splitting to this reverberation, obtain the infrared spectroscopy spectrum of releasing agent.Now, the information of inside and outside all releasing agents of the minute concave-convex structure of mould can be obtained.In addition, adopt the method, owing to can measure non-contactly with mould, thus can carry out measuring and not damaging mould in article manufacture.In addition, not by the size of large-scale roll mould etc., the restriction of shape.Due to these features, so also can online mensuration be carried out.In addition, as infrared ray, according to object, near-infrared ~ far infrared can be adopted.
Embodiment
Below, by embodiment, more specific description is carried out to the present invention, but the present invention is not limited to these embodiments.
(pore of anodised aluminium)
To prune the part of anodised aluminium, in cross section evaporation platinum 1 minute, use Flied emission shape SEM (company of NEC manufactures, JSM-7400F), under the condition of accelerating potential 3.00kV, observe cross section, measure the interval of pore and the degree of depth of pore.Each mensuration is carried out 50 places respectively, obtains mean value.
(transfer printing test)
Surface to the formation minute concave-convex structure side of mould flows into actinic energy ray curable resion composition, covers acrylic acid (ester) class film, then, utilizes UV irradiating machine (high-pressure sodium lamp: accumulated light 400mJ/cm
2) be cured.Afterwards, by by curing resin layer together with acrylic acid (ester) class film from mold releasability, thus minute concave-convex structure is transferred to the surface of acrylic acid (ester) class film.Repeatedly carry out this operation, by until occur by visual clearly can confirm that the bad number of times of the demoulding is set to can transfer printing number of times.The demoulding is now bad to be referred to and causes the micro concavo-convex face of mould that resin residue, mould and curing resin layer occur to become the state being difficult to the demoulding because cured resin is attached to the first-class reason of mould.
(actinic energy ray curable resion composition)
Following substances is mixed, preparation actinic energy ray curable resion composition:
Condensation reaction mixture 45 mass parts of butanedioic acid/trimethylolethane/acrylic acid mol ratio 1:2:4;
1,6-hexanediyl ester (manufacture of Osaka organic chemistry company) 45 mass parts;
Free-radical polymerised silicone oil (manufacture of chemical industrial company of SHIN-ETSU HANTOTAI, X-22-1602) 10 mass parts; And,
1-hydroxycyclohexylphenylketone (Ciba Specialty Chemicals Inc. manufactures, Irgacure 184) 3 mass parts.
(preparation method of mould)
Prepare to carry out electrolytic polishing to the aluminium sheet (purity 99.99%) of 50mm × 50mm × thickness 0.3mm in perchloric acid/alcohol mixed solution (1/4 volume ratio) and the aluminium sheet obtained.
Operation (a):
To aforementioned aluminium sheet, in 0.3M oxalic acid aqueous solution, under the condition of direct current 40V, temperature 16 DEG C, carry out anodic oxidation in 6 hours.
Operation (b):
The aluminium sheet defining oxidation overlay film to be immersed in 6 quality % phosphoric acid/1.8 quality % chromic acid mixed aqueous solutions 3 hours, to remove oxidation overlay film.
Operation (c):
To aforementioned aluminium sheet, in 0.3M oxalic acid aqueous solution, under the condition of direct current 40V, temperature 16 DEG C, carry out anodic oxidation in 30 seconds.
Operation (d):
The aluminium sheet defining oxidation overlay film to be immersed in the 5 quality % phosphate aqueous solutions of 32 DEG C 8 minutes, to carry out pore diameter and expand process.
Operation (e):
To aforementioned aluminium sheet, in 0.3M oxalic acid aqueous solution, under the condition of direct current 40V, temperature 16 DEG C, carry out anodic oxidation in 30 seconds.
Operation (f):
Repeat to amount to 4 foregoing sequence (d) and operation (e), finally carry out operation (d), obtain surface and be formed there is equispaced: the mould of the anodised aluminium of the pore of the roughly conical shape of 100nm, the degree of depth: 240nm.
Operation (g):
Use after shower washes away the phosphate aqueous solution on the surface of mould lightly, mould to be immersed in flowing water 10 minutes.
Operation (h):
From air gun to mould blow air, remove the water droplet of the surface attachment of mould.
Operation is (i):
At room temperature mould is immersed in and manufactures with diluent HD-ZV(Co., Ltd. HARVES) by OPTOOL(registration mark) DSX(Daikin ChemicalsSales, Ltd. manufacture) be diluted to 0.1 quality % and in the solution that obtains 10 minutes.
Operation (j):
Mould is mentioned lentamente from dilute solution second with 3mm/.
Operation (l):
Make mould air-dry 15 minutes, obtain by the mould of releasing agent process.
(embodiment 1)
Fourier-transform infrared light-dividing device (ThermoFisher Scientific society system, Nicolet380/Continum) is used to measure the infrared spectroscopy spectrum of die surface.Result is shown in Fig. 4.At 1080 ~ 1290cm
-1the peak A observed comes from releasing agent, at 730 ~ 1080cm
-1the peak B observed comes from anodised aluminium.The absorbance area (A) of peak A is 0.43, and the area ratio ((A)/(B)) of the absorbance at peak is 0.18, and use foregoing mould to carry out 1 transfer printing test, release property is good.
(embodiment 2)
Then embodiment 1, carries out 100 transfer printings test, measures the infrared spectroscopy spectrum of die surface.Its result, the absorbance area (A) of peak A is 0.21, and the area ratio ((A)/(B)) of the absorbance at peak is 0.089, and use foregoing mould to carry out 1 transfer printing test, release property is good.
(embodiment 3)
The infrared spectroscopy spectrum having made the different die surface made is measured according to method similarly to Example 1.Its result, the absorbance area (A) of peak A is 0.35, and the area ratio ((A)/(B)) of the absorbance at peak is 0.14.This external application foregoing mould carries out 1 transfer printing test, and release property is good.
(embodiment 4)
Measure the infrared spectroscopy spectrum repeatedly carrying out 19 transfer printing (, release property is good) rear mold surfaces from embodiment 3 around here.Its result, the absorbance area (A) of peak A is 0.29, and the area ratio ((A)/(B)) of the absorbance at peak is 0.12.This external application foregoing mould carries out 1 transfer printing test further, and release property is good.
(embodiment 5)
Measure the infrared spectroscopy spectrum repeatedly carrying out 19 transfer printing (, release property is good) rear mold surfaces from embodiment 4 around here.Its result, the area (A) of the absorbance of peak A is 0.22, and the area ratio ((A)/(B)) of the absorbance at peak is 0.085.This external application foregoing mould carries out 1 transfer printing test further, and release property is good.
(embodiment 6)
Measure the infrared spectroscopy spectrum repeatedly carrying out 19 transfer printing (, release property is good) rear mold surfaces from embodiment 5 around here.Its result, the area (A) of the absorbance of peak A is 0.18, and the area ratio ((A)/(B)) of the absorbance at peak is 0.074.This external application foregoing mould carries out 1 transfer printing test further, and release property is good.
(embodiment 7)
Measure the infrared spectroscopy spectrum repeatedly carrying out 19 transfer printing (, release property is good) rear mold surfaces from embodiment 6 around here.Its result, the area (A) of the absorbance of peak A is 0.13, and the area ratio ((A)/(B)) of the absorbance at peak is 0.056.This external application foregoing mould carries out 1 transfer printing test further, and taking a little power a little could the demoulding.
(comparative example 1)
9 transfer printings are repeatedly carried out from embodiment 7.Around here, power required for stripping increases, and from embodiment 7 during transfer printing the 10th time, the film with minute concave-convex structure of making cracks (release property is bad).The result measuring the infrared spectroscopy spectrum of now die surface is: the absorbance area (A) of peak A is 0.12, and the area ratio ((A)/(B)) of the absorbance at peak is 0.045.
(embodiment 8)
Again with the mould used in releasing agent process comparative example 1 in the same manner as aforementioned preparation method.Measure the infrared spectroscopy spectrum of this die surface.Its result, the absorbance area (A) of peak A is 0.26, and the area ratio ((A)/(B)) of the absorbance at peak is 0.11.This external application foregoing mould carries out 1 transfer printing test, and release property is good.
(embodiment 9)
Measure the infrared spectroscopy spectrum repeatedly carrying out 19 transfer printing (, release property is good) rear mold surfaces from embodiment 8 around here.Its result, the absorbance area (A) of peak A is 0.22, and the area ratio ((A)/(B)) of the absorbance at peak is 0.090.This external application foregoing mould carries out 1 transfer printing test further, and release property is good.
(embodiment 10)
Measure the infrared spectroscopy spectrum repeatedly carrying out 19 transfer printing (, release property is good) rear mold surfaces from embodiment 9 around here.Its result, the absorbance area (A) of peak A is 0.18, and the area ratio ((A)/(B)) of the absorbance at peak is 0.078.This external application foregoing mould carries out 1 transfer printing test further, and release property is good.
(embodiment 11)
Measure the infrared spectroscopy spectrum repeatedly carrying out 19 transfer printing (, release property is good) rear mold surfaces from embodiment 10 around here.Its result, the absorbance area (A) of peak A is 0.14, and the area ratio ((A)/(B)) of the absorbance at peak is 0.062.This external application foregoing mould carries out 1 transfer printing test further, needs the demoulding of expense a little power ability.
(embodiment 12)
Measure the infrared spectroscopy spectrum repeatedly carrying out 9 transfer printing (, release property is good) rear mold surfaces from embodiment 11 around here.Its result, the absorbance area (A) of peak A is 0.13, and the area ratio ((A)/(B)) of the absorbance at peak is 0.055.This external application foregoing mould carries out 1 transfer printing test further, needs the demoulding of expense a little power ability.
(comparative example 2)
8 transfer printings are repeatedly carried out from embodiment 12.Around here, power required for stripping increases, and from embodiment 12 during transfer printing the 9th time, the film with minute concave-convex structure of making cracks (release property is bad).The result measuring the infrared spectroscopy spectrum of now die surface is: the absorbance area (A) of peak A is 0.11, and the area ratio ((A)/(B)) of the absorbance at peak is 0.041.
utilizability in industry
Surface of the present invention there is the manufacture method of the article of minute concave-convex structure and manufacturing installation very useful in effective volume production reflection preventing article, anti-fog properties article, soil resistance article and hydrophobicity article.
description of reference numerals
12 pores (minute concave-convex structure)
18 moulds
20 roll moulds
40 article
42 films (main body of articles)
46 protuberances (minute concave-convex structure)
50 reflection-type infrared spectroscopy devices
60 identifying units
Claims (6)
1. surface has a manufacture method for the article of minute concave-convex structure, and the minute concave-convex structure of die surface is transferred to the surface of main body of articles by it, thus manufactures described article, and described die surface is by releasing agent process, and this manufacture method comprises:
Minute concave-convex structure is transferred to the surface of main body of articles;
After being peeled off from mould by described main body of articles, measure the infrared spectroscopy spectrum of die surface; And,
According to the state quality of the releasing agent of die surface, determine whether to continue to manufacture,
The absorbance area A at the peak near the wave number deriving from the chemical constitution of releasing agent in infrared spectroscopy spectrum or derive from releasing agent chemical constitution wave number near peak absorbance area A and derive from the chemical constitution that die surface exists wave number near the area ratio A/B of absorbance area B at peak when being more than the threshold value preset, judge the state of the releasing agent of die surface as well.
2. surface according to claim 1 has the manufacture method of the article of minute concave-convex structure, it also comprises: when the state of the releasing agent of die surface is judged as bad, stop the surface minute concave-convex structure of die surface being transferred to main body of articles, and/or, again with releasing agent process die surface.
3. surface according to claim 1 and 2 has the manufacture method of the article of minute concave-convex structure, and wherein, the infrared spectroscopy spectrum of described mensuration die surface comprises continuously or measures the infrared spectroscopy spectrum of described die surface discontinuously.
4. surface according to claim 1 and 2 has the manufacture method of the article of minute concave-convex structure, wherein,
Described mould is formed by aluminium oxide;
Described releasing agent is fluorine compounds;
The threshold value of described absorbance area A is 0.13, or the threshold value of described area ratio A/B is 0.047.
5. surface according to claim 4 has the manufacture method of the article of minute concave-convex structure, and wherein, described absorbance area A is more than 0.13 and less than 1, or described area ratio A/B is more than 0.047 and less than 10.
6. a surface has the manufacturing installation of the article of minute concave-convex structure, the minute concave-convex structure of die surface is transferred to the surface of main body of articles by it, thus manufacture the article that surface has minute concave-convex structure, described die surface is by releasing agent process, and this manufacturing installation has:
Surface there is minute concave-convex structure and described surface by the mould of releasing agent process;
Measure the reflection-type infrared spectroscopy device of infrared spectroscopy spectrum of die surface, determined die surface be minute concave-convex structure is transferred to main body of articles surface and peel off the die surface after described main body of articles from mould;
The identifying unit of the state quality of the releasing agent of die surface is judged based on described infrared spectroscopy spectrum.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-090456 | 2010-04-09 | ||
| JP2010090456 | 2010-04-09 | ||
| PCT/JP2011/058698 WO2011126044A1 (en) | 2010-04-09 | 2011-04-06 | Production method and production device for article having microrelief structure on surface thereof |
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| CN102933363A CN102933363A (en) | 2013-02-13 |
| CN102933363B true CN102933363B (en) | 2015-05-27 |
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| JP (1) | JP4856785B2 (en) |
| CN (1) | CN102933363B (en) |
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| 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 |
| JP6415590B2 (en) * | 2014-11-06 | 2018-10-31 | シャープ株式会社 | Mold manufacturing method and antireflection film manufacturing method |
| US10408812B2 (en) * | 2016-10-12 | 2019-09-10 | General Electric Company | Characterization and control system and method for a resin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1447740A (en) * | 2000-08-18 | 2003-10-08 | 瑞弗莱克塞特公司 | Differentaially cured materials and process for forming same |
| CN101378900A (en) * | 2006-02-07 | 2009-03-04 | 大日本印刷株式会社 | 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 em |
| CN101484614A (en) * | 2006-06-30 | 2009-07-15 | 三菱丽阳株式会社 | Mold, process for manufacturing mold, and process for producing sheet |
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| 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 |
| JP4853706B2 (en) * | 2006-03-22 | 2012-01-11 | 凸版印刷株式会社 | Imprint mold and manufacturing method thereof |
| JP2010005841A (en) * | 2008-06-25 | 2010-01-14 | Mitsubishi Rayon Co Ltd | Mold manufacturing method |
| 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 WO PCT/JP2011/058698 patent/WO2011126044A1/en active Application Filing
- 2011-04-06 JP JP2011518097A patent/JP4856785B2/en not_active Expired - Fee Related
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1447740A (en) * | 2000-08-18 | 2003-10-08 | 瑞弗莱克塞特公司 | Differentaially cured materials and process for forming same |
| CN101378900A (en) * | 2006-02-07 | 2009-03-04 | 大日本印刷株式会社 | 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 em |
| CN101484614A (en) * | 2006-06-30 | 2009-07-15 | 三菱丽阳株式会社 | Mold, process for manufacturing mold, and process for producing sheet |
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| WO2011126044A1 (en) | 2011-10-13 |
| JP4856785B2 (en) | 2012-01-18 |
| TWI418454B (en) | 2013-12-11 |
| TW201200328A (en) | 2012-01-01 |
| JPWO2011126044A1 (en) | 2013-07-11 |
| CN102933363A (en) | 2013-02-13 |
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