WO1997017181A1 - Procede de fabrication d'un article optique dans un moule scelle sous vide - Google Patents
Procede de fabrication d'un article optique dans un moule scelle sous vide Download PDFInfo
- Publication number
- WO1997017181A1 WO1997017181A1 PCT/BE1996/000118 BE9600118W WO9717181A1 WO 1997017181 A1 WO1997017181 A1 WO 1997017181A1 BE 9600118 W BE9600118 W BE 9600118W WO 9717181 A1 WO9717181 A1 WO 9717181A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mold
- lens
- curing
- optical article
- composition
- Prior art date
Links
- 230000003287 optical effect Effects 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 229920003023 plastic Polymers 0.000 claims abstract description 5
- 239000004033 plastic Substances 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 24
- -1 polybutylene Polymers 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 7
- 230000005855 radiation Effects 0.000 claims description 7
- 238000000137 annealing Methods 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 5
- 239000004800 polyvinyl chloride Substances 0.000 claims description 5
- 230000005670 electromagnetic radiation Effects 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 229920001748 polybutylene Polymers 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 229920001903 high density polyethylene Polymers 0.000 claims description 2
- 239000004700 high-density polyethylene Substances 0.000 claims description 2
- 229920001684 low density polyethylene Polymers 0.000 claims description 2
- 239000004702 low-density polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims 1
- 229920001155 polypropylene Polymers 0.000 claims 1
- 238000001723 curing Methods 0.000 description 25
- 230000008569 process Effects 0.000 description 11
- 239000000178 monomer Substances 0.000 description 10
- 229910052736 halogen Inorganic materials 0.000 description 9
- 150000002367 halogens Chemical class 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 6
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 6
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 238000001029 thermal curing Methods 0.000 description 4
- 239000012963 UV stabilizer Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000009863 impact test Methods 0.000 description 3
- OGBWMWKMTUSNKE-UHFFFAOYSA-N 1-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CCCCCC(OC(=O)C(C)=C)OC(=O)C(C)=C OGBWMWKMTUSNKE-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- PODOEQVNFJSWIK-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethoxyphenyl)methanone Chemical compound COC1=CC(OC)=CC(OC)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 PODOEQVNFJSWIK-UHFFFAOYSA-N 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- OZFIGURLAJSLIR-UHFFFAOYSA-N 1-ethenyl-2h-pyridine Chemical compound C=CN1CC=CC=C1 OZFIGURLAJSLIR-UHFFFAOYSA-N 0.000 description 1
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-M 3-mercaptopropionate Chemical compound [O-]C(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-M 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- LFOXEOLGJPJZAA-UHFFFAOYSA-N [(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphoryl]-(2,6-dimethoxyphenyl)methanone Chemical compound COC1=CC=CC(OC)=C1C(=O)P(=O)(CC(C)CC(C)(C)C)C(=O)C1=C(OC)C=CC=C1OC LFOXEOLGJPJZAA-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Polymers 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical class C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000013036 cure process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- MHCLJIVVJQQNKQ-UHFFFAOYSA-N ethyl carbamate;2-methylprop-2-enoic acid Chemical compound CCOC(N)=O.CC(=C)C(O)=O MHCLJIVVJQQNKQ-UHFFFAOYSA-N 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
-
- 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
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
-
- 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
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0888—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using transparant moulds
-
- 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
- B29C43/32—Component parts, details or accessories; Auxiliary operations
- B29C43/56—Compression moulding under special conditions, e.g. vacuum
-
- 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
- B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
- B29C71/02—Thermal after-treatment
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
- G02B1/043—Contact lenses
-
- 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
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
- B29C2035/0827—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using UV radiation
-
- 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
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
- B29C2035/0833—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using actinic light
-
- 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
- B29C2791/00—Shaping characteristics in general
- B29C2791/004—Shaping under special conditions
- B29C2791/006—Using vacuum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2011/00—Optical elements, e.g. lenses, prisms
- B29L2011/0016—Lenses
Definitions
- the present invention relates generally to methods for curing optical articles and more particularly to methods for producing ophthalmic lenses It is conventional in the art to produce optical lenses by thermal curing techniques from either allyl, methacrylate, acrylate or vinyl functional monomers and/or oligomers The thermal curing techniques for polymerizing these materials to produce optical lenses have several disadvantages The most significant drawback is that it may take between 6 and 20 hours to produce a lens.
- a lens forming mold is capable of producing two lenses per day
- UV ultraviolet light
- Tg glass transition temperatures
- UV cured lenses are actually cured using two different initiators. One is UV activated and the other is thermally activated. The lenses are partially cured under high intensity UV light and are then placed into an oven and thermally cured to completion.
- a final difficulty with UV cured lenses is keeping air from entering the mold during the cure cycle Because the cure and the shrinkage associated with the cure process occurs so rapidly, it is difficult to keep the molds sealed and eliminate air from entering the mold cavity during the cure cycle
- a metal clamp is placed on the mold in order to keep the mold sealed during cure, but UV cured lenses must use a transparent clamping mechanism, if they can use one at all
- disadvantages of methods of curing optical articles involving the use of ultra-violet light are the need for specific equipment, namely expensive light sources, dangerous working conditions for the personal handling such apparatus, as well as the overall length of such methods. Therefore it is an objective of the present invention to solve the various defects of the hitherto known methods of curing optical articles.
- the present invention provides a process for curing optical articles, in particular ophthalmic lenses, which involves the use of a specific wavelength range of visible light. This light causes no degradation of the polymer material during the cure cycle. Since UV light is not employed, the environment is much safer for the workers involved in the process.
- the articles, particularly lenses may also be heated during the cure cycle. However, no thermal initiator is used and the visible light exposure, optionally in conjunction with heat, is critical to developing the appropriate
- optical article is defined as an object that is designed to transmit, focus, defocus, block or otherwise act to interact or prevent interaction with electromagnetic radiation that ranges from a wavelength of about 250 nm to about 1200 nm, preferably from 300 nm to 900 nm, and more preferably from 380 nm to 750 nm.
- Cure and “curing” Applicant means to cause the chemical reaction of lower molecular weight species such that after they react their molecular weight has significantly increased.
- To "actively heat” means to cause an increase in temperature by either electromagnetic radiation, specifically infrared radiation or microwave radiation, radiant energy or convective energy
- the method is applicable to the manufacture of optical articles, in particular ophthalmic lenses, from a wide variety of materials, including virtually any double-bond containing materials which are radiation polymerisable.
- suitable materials include various acrylates, methacrylates, vinyl ethers, oxethanes and allyls, although allyls tend to react more slowly More specifically, they generally consist of a mixture of the following reactive components - at least one radiation polymerizable oligomer or reactive prepolymer, with a molecular weight of generally less than about 10,000 and having unsaturated groups such as acrylic, methacrylic, vinyl or allyl chain terminating or side groups.
- Such oligomers or prepolymers are well known, available commercially and can provide a great variety of structures such as polyesters, polyacrylics, polyepoxides, polyurethanes, etc..
- Examples include epoxy acrylates or methacrylates, of the type described in U.S. Patent Nos. 3,676,398, 3,770,602 and 4,511,732, urethane acrylates or methacrylates, such as those described in U.S. Patent Nos. 3,700,643, 4,133,723 and 4,188,455, polyester acrylates or methacrylates, such as those described in U.S. Patent Nos. 4,206,025 and 5,002,976, and acrylic acrylates or methacrylates, etc.
- polyethylemcally unsaturated reactive monomer preferably a di(meth)acrylate or a poly(meth)acrylate of a low molecular weight polyol, such as a diacrylate of 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, di-, tri- and/or tetraethylene glycol, tripropylene glycol, the
- Such monomers include monoacrylates and monomethacrylates of monohydroxylated and polyhydroxylated aliphatic alcohols, styrene, vinyl toluene, vinyl acetate, N-vinyl-2-pyrrolidone, N-vinylpyridine,
- This monomer may be added to the composition as a reactive diluent and the amount and nature thereof can be varied to allow the viscosity of the composition to be adjusted at will.
- Oligomer formulations which can be mentioned as examples oligomer are as follows: U. S. Patent No. 5,442,022 discloses a composition based on ethoxylated bis-phenol A dimethacrylate; U. S. Patent No. 5,502,139 disclose a composition based on fluorene di(meth)acrylate monomer; U. S. Patent No. 5,147,959 discloses the reaction product of a polyisocyanate with a halobisphenol A epichlorhydrin polycondensate-(meth)acrylic acid adduct, U. S. Patent No. 5,132,384 discloses resins based on
- U.S. Patent No. 5,133,370 discloses mixtures of (a) polybutylene glycol diacrylate, (b) a urethane polymethacrylate and (c) an aromatic or alicyclic mono (meth) acrylate;
- U. S. Patent No. 4,912,185 discloses a composition of (a) a polyoxyalkylene glycol di(meth)acrylate, (b) a t ⁇ functional (meth) acrylic monomer and (c) a polyacrylic urethane monomer.
- International Patent Publication No. WO96/26184 discloses polymeric compositions for the preparation of optical grade materials specifically formulated from
- urethane (meth)acrylate which comprises the components (a), (b), and (c):
- R 1 is a hydrogen atom or a methyl group
- R 2 is independently a hydrogen or an alkyl group having a carbon number ranging from 1 to 10
- R 3 , R 4 and R 5 are independently a hydrogen, an alkyl group having a carbon number ranging from 1 to 10, a phenyl group or bromine
- nl is an integer ranging from 1 to 7
- n2 is an integer ranging from 0 to 20
- R a and R b are independently a hydrogen or a methyl group
- n3 is independently an integer ranging from 0 to 10
- n4 is 0 or 1
- n5 is an integer ranging from 0 to 5 .
- compositions employed in this aspect of the invention may also contain UV stabilizer materials since the curing is carried out by employing visible light. Th s constitutes an additional advantage of the present invention since the UV stabilizer can be
- the wavelength of the visible light used in the method of the invention can vary between approximately 385 and 475 nm, with a preferred range of approximately 400 to 450 nm and a particularly preferred wavelength of approximately 420 nm.
- the advantage of using such actinic light is that at a wavelength of 420 nm they cause virtually no degradation of the optical article during the process of curing.
- Fluorescent Super Actinic light from Philips or its equivalent from another manufacturer
- 420 nm Metal Halide lamps from Electrolite Corporation. This should be used in conjunction with Uvilex 3902 UV Barrier Filter Glass from Schott Corporation. This filter glass will eliminate wavelengths below about 385 nm.
- the process of the invention is carried out using a photoinitiator suitable for use with the particular optical article material which is intended
- the photoinitiator must be one which possesses an absorption peak at or about the same wavelength as that of the visible light which is employed in the curing process.
- Preferred photoinitiators are Lucirin ® TPO (2,4,6-trimethyl-benzoyldiphenylphosphine oxide) from BASF, Irgacure 184 (1-hydroxycyclohexyl phenyl ketone), Darocur 1173 (2-hydroxy-2-methyl-1-phenyl-propan-1-one), bis(2,6-dimethoxybenzoyl)-2,4,4- trimethylpentylphosphine oxide from Ciba-Geigy and mixtures thereof
- the molds which are employed in carrying out the curing method of the invention are well known in the art For example, there can be mentioned a glass mold held together by a polyvinyl chloride (PVC) gasket Other molds will be apparent to the art-skilled. The mold must, of course, be such that it is penetrable by the visible light which is employed in curing.
- PVC polyvinyl chloride
- Fig. 1 is a schematic diagram of a lens curing apparatus.
- Fig. 1A is a front view showing lens molds (1) sitting in vertical position on the lens support (2) of the lens curing apparatus.
- Fig. 1B is an end view of the lens support mechanism (2) along with the actinic light assembly and halogen lights for providing heat to the lens mold (1).
- (3) denotes a halogen track lighting which is holded by a movable bracket (4)
- (5) denotes a fluorescent light fixture with actinic lights mounted on a L bracket (6).
- Fig. 2 is a schematic of an alternative apparatus for carrying out the inventive method employing convection heating.
- the upper chamber thereof comprises a cooling fan (7) and an exhaust port (8) and is provided with a series of fluorescent light fixtures (5) with actinic lamps and with a reflector (9) for actinic lights.
- the upper chamber is separated from the lower chamber by a heat resistant glass plate (10).
- the lower chamber is provided with a heating element (11), with a heat resistant glass plate (12) on which the lens molds (1) are set, and with a reflector (9') for actinic lights.
- Fig. 3 is a schematic of another alternative apparatus for carrying out the inventive method employing infrared heating.
- This alternative apparatus comprises elements similar to those of the apparatus of figure 2, except that the lower chamber is not provided with a heating element but instead comprises a series of quartz infrared lamps (13) near the separating heat resistant glass plate (10).
- halogen lamps are held approximately 20 cm from the lens molds
- the halogen lamps are on a track
- the halogen lamps are moved up and out of the way (as shown) during Phase I of the cure cycle.
- Phase I the fluorescent lamps are turned on and curing begins.
- Phase II the halogen lamps are moved vertically down so that the centerline of the halogen lights corresponds with the center of the lens. The lamps are turned on and heating begins while the visible light curing also continues.
- the visible light curing is begun by turning on the fluorescent lights. After a desired period of time, the heating element is turned on and visible light continues with heating until the desired cure is obtained.
- a method of curing in which an optical article mold, preferably an ophthalmic lens mold, containing the composition to be cured is sealed in a clear plastic container, preferably a bag, under vacuum, prior to curing and curing takes place with the mold thus sealed.
- an optical article mold preferably an ophthalmic lens mold
- a clear plastic container preferably a bag
- Vacuum as used herein means a vacuum greater than about 400 mm Hg (i.e. a pressure below 360 mm Hg) as measured by standard vacuum gauge, more preferably greater than 600 mm Hg.
- Sealing of the mold in this manner has the beneficial effect of exerting pressure on the mold to hold it together while, at the same time, preventing air from entering the mold cavity during the cure cycle.
- the mold containing the composition to be cured is first placed into a bag made of a suitable clear plastic material.
- a tube is inserted in the bag and the open end of the bag is sealed, for example, with a commercially available heat sealer, up to the inserted tube.
- a vacuum is then pulled on the bag, causing it to collapse around the mold.
- the heat sealer is then used to seal the bag in front of the inserted tube.
- This technique can be automated using equipment specifically designed to vacuum bag or seal materials on an industrial/commercial scale
- the plastic film that the mold is sealed into is not necessarily provided as a bag. Frequently these materials are sold on rolls in what is termed a "C Fold" configuration.
- a length of film is unrolled and the edge coming off the roll is sealed using a heat sealer.
- the mold is then placed between the two layers of film, i.e., in the C Fold.
- the film is then typically sealed and cut simultaneously on the other side of the mold.
- the mold is now "in a bag” with one end open. That end is then sealed and a vacuum is pulled as described above
- the particular mechanics of the operation are not critical but rather that the end result is the mold encased in a clear film under vacuum. Any method to achieve this end is acceptable.
- Adhesive sealing is acceptable so long as the vacuum conditions are achieved and maintained. Heat sealing is, however, preferred.
- composition to be cured will comprise the photoinitiator and optionally photosensitizer or, respectively, the thermal activator which are suitable for such curing technology.
- Non-limiting examples of suitable materials for the bag are low and high density polyethylene, polybutylene, polyvinyl chloride, polypropylene copolymers of ethylene and higher ⁇ -olefins such as propylene or 1-butene, copolymers of ethylene and alkyl acrylates or methacrylates and optionally maleic anhydride, etc.
- the films may also be coextruded films such that the inner film is designed to be easily sealed while the outer film provides the majority of the mechanical properties. Such coextruded films are well known in the packaging art.
- the bag or film must be flexible, clear, and - if it is to be used in the process of curing with visible light - transparent to light in the range of approximately 385 co 475 nm, preferably approximately 420 nm. It is also preferably heat sealable.
- the bag or film may also, if desired, be chosen to provide additional protection against UV light if it is made of polymer or contains additives that absorb UV light.
- a casting composition was prepared from a mixture of
- the oligomer composition comprises a urethane acrylate which is the reaction product of diphenylmethane dusocyanate and hydroxypropylacrylate in a 1.1 molar ratio, a photoinitiator (Lucirin TPO from BASF), a UV stabilizer and an antioxidant.
- the modified thiol is a functional product that can be prepared by thermal initiation from 4 equivalents of
- the above components were mixed together in a brown polyethylene bottle The material was allowed to degas overnight The formula was poured into a glass mold held together by a polyvinyl chloride (PVC) gasket The mold was set oetween two sets of fluorescent actinic lights (420 nm) (Phillips Corporation) approximately 60 cm apart. The lights were turned on. After twenty minutes, a pair of 75 watt halogen lamps directed at the mold were turned on. The lens was cured for an additional 30 minutes. At the end of this cycle, the lens temperature was approximately 95°C.
- PVC polyvinyl chloride
- the lens was clear and almost colorless at this point.
- the mold was then disassembled and the lens removed.
- the lens was cleaned and then placed in a 100°C oven for 15 minutes. This annealing cycle is performed only to allow the stress induced in the demolding process to be relieved.
- the lens was then removed from the oven and allowed to cool to room
- the lens exhibited very low color and very high clarity.
- the polymerized material was found to have a refractive index of 1.574 at 20°C and an Abbe number of approximately 33.
- the glass transition temperature was approximately 90°C.
- the power of the lens was measured to be
- This lens passed the dress lens impact test.
- Example 1 The material and mold were prepared as in Example 1.
- the initial actinic cure cycle was 20 minutes but the secondary cure with the halogen lamps was modified so that the temperature of the lens at the end of the second cure cycle was only about 75°C. This time the lens was very yellow when it came out of the cure cycle.
- Thermal post annealing did decrease the color of the lens to a similar color as the lens from Example 1.
- the polymerized material was found to have a refractive index of 1.574 at 20°C and an Abbe number of approximately 33.
- the glass transition temperature was approximately 85°C.
- Example 1 The material and mold were prepared as in Example 1. However, this time the lens mold was placed in a flexible, clear, transparent to 420 nm light and heat sealable polyethylene bag. A tube is inserted in the bag and the open end of the bag is sealed with a commercially available heat sealer up to the inserted tube. A vacuum is then pulled on the bag, causing it to collapse around the mold The heat sealer is then used to seal the bag in front of the inserted tube. The lens was then cured as in Example 1. The lens had no bubbles as a result of air entering the mold cavity during the cure cycle
- Example 4 A casting composition was prepared from
- the above components were mixed together in a brown polyethylene bottle.
- the material was allowed to degas overnight.
- the formula was poured into a lens mold consisting of a front curve of 200 mm and a back curve of 400 mm.
- the two halves of the glass mold were held together by a PVC gasket that provided a distance between the edges of the glass molds of 3.5 mm. This resulted in a lens with a center thickness of approximately 1.2 mm.
- the mold was then vacuum sealed in a polyethylene bag as described in Example 3. It was then set between two sets of fluorescent actinic lights (420 nm) (Phillips Corporation) approximately 60 cm apart. The lights were turned on. After ten minutes, a pair of 75 watt halogen lamps directed at the mold were turned on. The lens was cured for an additional 30 minutes.
- the lens temperature was approximately 95°C.
- the lens was clear and almost colorless at this point.
- the mold was then disassembled and the lens removed.
- the lens was cleaned and then placed in a 100°C oven for 20 minutes. This annealing cycle is performed only to allow the stress induced in the demolding process to be relieved.
- the lens was then removed from the oven and allowed to cool to room
- the lens exhibited very low color and very high clarity.
- the polymerized material was found to have a refractive index of 1.50 at 20°C and an Abbe number of approximately 52.
- the glass transition temperature was approximately 67°C.
- the power of the lens was measured to be
- This lens passed the dress lens impact test.
- a casting composition was prepared from
- This composition was then processed as in example 4.
- the lens exhibited very low color and very high clarity.
- the polymerized material was found to have a refractive index of 1.50 at 20°C and an Abbe number of approximately 52.
- the glass transition temperature was approximately 80°C.
- the power of the lens was measured to be
- the following formulations were made and cured into lenses.
- the lenses were cured for approximately 15 minutes using actinic light only.
- the intensity of the actinic lamps was approximately 3200 micro watts per square centimeter and the exposure occurred from both sides of the molds.
- a thermocouple was inserted in each lens and the cure response was noted.
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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Thermal Sciences (AREA)
- Toxicology (AREA)
- Oral & Maxillofacial Surgery (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
Abstract
Cette invention concerne un procédé de fabrication d'un article optique, de préférence un verre ophtalmique, qui consiste à sceller sous vide un moule contenant la composition à durcir, ledit moule se présentant à l'intérieur d'un sac en plastique, et à effectuer le durcissement tout en maintenant le moule dans des conditions de scellement sous vide.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU75575/96A AU7557596A (en) | 1995-11-09 | 1996-11-07 | Method for producing an optical article in a mold sealed under vacuum |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US670195P | 1995-11-09 | 1995-11-09 | |
US60/006,701 | 1995-11-09 | ||
US73690896A | 1996-10-25 | 1996-10-25 | |
US08/736,908 | 1996-10-25 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1997017181A1 true WO1997017181A1 (fr) | 1997-05-15 |
Family
ID=26675947
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/BE1996/000118 WO1997017181A1 (fr) | 1995-11-09 | 1996-11-07 | Procede de fabrication d'un article optique dans un moule scelle sous vide |
PCT/BE1996/000119 WO1997017182A1 (fr) | 1995-11-09 | 1996-11-07 | Procede de fabrication d'un article optique utilisant le rayonnement de lumiere visible |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/BE1996/000119 WO1997017182A1 (fr) | 1995-11-09 | 1996-11-07 | Procede de fabrication d'un article optique utilisant le rayonnement de lumiere visible |
Country Status (2)
Country | Link |
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AU (2) | AU7557696A (fr) |
WO (2) | WO1997017181A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999026087A1 (fr) * | 1997-11-14 | 1999-05-27 | Novartis Ag | Procedes et compositions pour la fabrication de lentilles ophtalmiques teintees |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3413015A1 (de) * | 1983-04-29 | 1984-10-31 | Dreve-Dentamid, 4750 Unna | Verfahren und vorrichtung zur polymerisation lichthaertender kunststoffe |
US5002476A (en) * | 1989-11-24 | 1991-03-26 | Lockheed Corporation | Tooling for composite parts |
WO1992004171A1 (fr) * | 1990-09-11 | 1992-03-19 | Gn Danavox A/S | Procede et appareil de durcissement de materiaux fusibles et utilisation de ceux-ci |
EP0484015A2 (fr) * | 1990-10-30 | 1992-05-06 | Minnesota Mining And Manufacturing Company | Procédé pour la polymèrisation des objets oculaires |
JPH05287315A (ja) * | 1992-04-07 | 1993-11-02 | Nippon Steel Corp | 金型を用いた静水圧成形による粉末成形方法 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59193915A (ja) * | 1983-04-20 | 1984-11-02 | Tokuyama Soda Co Ltd | 高屈折率透明樹脂の製造方法 |
US4719248A (en) * | 1985-08-08 | 1988-01-12 | Bausch & Lomb Incorporated | Ultraviolet blocking agents for contact lenses |
JPH01163027A (ja) * | 1987-12-21 | 1989-06-27 | Matsushita Electric Ind Co Ltd | 光学素子の成形方法およびその装置 |
JPH0390319A (ja) * | 1989-09-01 | 1991-04-16 | Sogo Shika Iryo Kenkyusho:Kk | 可視光重合型レジンの連続硬化方法及び装置 |
JP3027205B2 (ja) * | 1991-02-21 | 2000-03-27 | 三菱化学株式会社 | プラスチックレンズないしレンズ材料の製造法 |
ES2130384T3 (es) * | 1993-07-19 | 1999-07-01 | Novartis Ag | Procedimiento y dispositivo para la obtencion de cuerpos moldeados, asi como cuerpos moldeados obtenidos segun el procedimiento. |
-
1996
- 1996-11-07 WO PCT/BE1996/000118 patent/WO1997017181A1/fr active Application Filing
- 1996-11-07 AU AU75576/96A patent/AU7557696A/en not_active Abandoned
- 1996-11-07 AU AU75575/96A patent/AU7557596A/en not_active Abandoned
- 1996-11-07 WO PCT/BE1996/000119 patent/WO1997017182A1/fr active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3413015A1 (de) * | 1983-04-29 | 1984-10-31 | Dreve-Dentamid, 4750 Unna | Verfahren und vorrichtung zur polymerisation lichthaertender kunststoffe |
US5002476A (en) * | 1989-11-24 | 1991-03-26 | Lockheed Corporation | Tooling for composite parts |
WO1992004171A1 (fr) * | 1990-09-11 | 1992-03-19 | Gn Danavox A/S | Procede et appareil de durcissement de materiaux fusibles et utilisation de ceux-ci |
EP0484015A2 (fr) * | 1990-10-30 | 1992-05-06 | Minnesota Mining And Manufacturing Company | Procédé pour la polymèrisation des objets oculaires |
JPH05287315A (ja) * | 1992-04-07 | 1993-11-02 | Nippon Steel Corp | 金型を用いた静水圧成形による粉末成形方法 |
Non-Patent Citations (1)
Title |
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PATENT ABSTRACTS OF JAPAN vol. 018, no. 072 (M - 1555) 7 February 1994 (1994-02-07) * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999026087A1 (fr) * | 1997-11-14 | 1999-05-27 | Novartis Ag | Procedes et compositions pour la fabrication de lentilles ophtalmiques teintees |
Also Published As
Publication number | Publication date |
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AU7557596A (en) | 1997-05-29 |
WO1997017182A1 (fr) | 1997-05-15 |
AU7557696A (en) | 1997-05-29 |
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