AU8446098A - Polymerizable monomer compositions, transparent polymer substrates, and optical and ophthalmic articles obtained - Google Patents
Polymerizable monomer compositions, transparent polymer substrates, and optical and ophthalmic articles obtained Download PDFInfo
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- AU8446098A AU8446098A AU84460/98A AU8446098A AU8446098A AU 8446098 A AU8446098 A AU 8446098A AU 84460/98 A AU84460/98 A AU 84460/98A AU 8446098 A AU8446098 A AU 8446098A AU 8446098 A AU8446098 A AU 8446098A
- Authority
- AU
- Australia
- Prior art keywords
- monomers
- sic
- group
- meth
- acrylate
- 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.)
- Granted
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- 239000000178 monomer Substances 0.000 title claims description 108
- 239000000203 mixture Substances 0.000 title claims description 90
- 230000003287 optical effect Effects 0.000 title claims description 18
- 229920000307 polymer substrate Polymers 0.000 title claims description 10
- -1 alkylene radical Chemical class 0.000 claims description 39
- 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 claims description 31
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 25
- 239000000758 substrate Substances 0.000 claims description 23
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 13
- 230000000977 initiatory effect Effects 0.000 claims description 13
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical compound C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 239000011521 glass Substances 0.000 claims description 11
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 10
- 229920001451 polypropylene glycol Polymers 0.000 claims description 10
- 239000005977 Ethylene Substances 0.000 claims description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 8
- CKFGINPQOCXMAZ-UHFFFAOYSA-N methanediol Chemical compound OCO CKFGINPQOCXMAZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 6
- 230000009477 glass transition Effects 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 235000019256 formaldehyde Nutrition 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 150000003254 radicals Chemical class 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- LVOICKNPHXSSQM-UHFFFAOYSA-N prop-2-en-1-one Chemical compound C=C[C]=O LVOICKNPHXSSQM-UHFFFAOYSA-N 0.000 claims description 3
- RSROEZYGRKHVMN-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;oxirane Chemical compound C1CO1.CCC(CO)(CO)CO RSROEZYGRKHVMN-UHFFFAOYSA-N 0.000 claims description 2
- MQUMNTKHZXNYGW-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;propane-1,3-diol Chemical compound OCCCO.CCC(CO)(CO)CO MQUMNTKHZXNYGW-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 2
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000006833 (C1-C5) alkylene group Chemical group 0.000 claims 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims 1
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000004383 yellowing Methods 0.000 description 6
- 238000012719 thermal polymerization Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229920002574 CR-39 Polymers 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 3
- 229940035437 1,3-propanediol Drugs 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 3
- KHZBQMMGVPWWAU-UHFFFAOYSA-N 2-methylprop-2-en-1-one Chemical compound CC(=C)[C]=O KHZBQMMGVPWWAU-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- WPWHSFAFEBZWBB-UHFFFAOYSA-N 1-butyl radical Chemical compound [CH2]CCC WPWHSFAFEBZWBB-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- JLZIIHMTTRXXIN-UHFFFAOYSA-N 2-(2-hydroxy-4-methoxybenzoyl)benzoic acid Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1C(O)=O JLZIIHMTTRXXIN-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- FEJPWLNPOFOBSP-UHFFFAOYSA-N 2-[4-[(2-chloro-4-nitrophenyl)diazenyl]-n-ethylanilino]ethanol Chemical compound C1=CC(N(CCO)CC)=CC=C1N=NC1=CC=C([N+]([O-])=O)C=C1Cl FEJPWLNPOFOBSP-UHFFFAOYSA-N 0.000 description 1
- HNVRRHSXBLFLIG-UHFFFAOYSA-N 3-hydroxy-3-methylbut-1-ene Chemical compound CC(C)(O)C=C HNVRRHSXBLFLIG-UHFFFAOYSA-N 0.000 description 1
- NNWNNQTUZYVQRK-UHFFFAOYSA-N 5-bromo-1h-pyrrolo[2,3-c]pyridine-2-carboxylic acid Chemical compound BrC1=NC=C2NC(C(=O)O)=CC2=C1 NNWNNQTUZYVQRK-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 241001484259 Lacuna Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical class C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- PGOVCMQQKSNPOT-UHFFFAOYSA-N carboxyoxy cyclohexyl carbonate Chemical compound OC(=O)OOC(=O)OC1CCCCC1 PGOVCMQQKSNPOT-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000008371 chromenes Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000007688 edging Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- VBPSVYDSYVJIPX-UHFFFAOYSA-N methylbutenol Natural products CCC=C(C)O VBPSVYDSYVJIPX-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 229920005651 polypropylene glycol dimethacrylate Polymers 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
Landscapes
- Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Eyeglasses (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
- 1 POLYMERIZABLE MONOMER COMPOSITIONS, TRANSPARENT POLYMER SUBSTRATES, AND OPTICAL AND OPHTHALMIC ARTICLES OBTAINED 5 The present invention generally relates to polymerizable monomer compositions which, after polymerization, provide transparent polymerized substrates which are particularly suitable for the 10 manufacture of optical and ophthalmic articles, such as lenses or glasses for spectacles. More particularly, the present invention relates to such polymerizable monomer compositions which, after polymerization, result in transparent 15 substrates with a refractive index with a value generally of less than 1.54, preferably of less than 1.52 and preferably close to 1.5, and with a low density. The present invention also relates to the 20 substrates obtained by polymerization of the polymerizable monomer compositions according to the invention and to the optical and ophthalmic articles obtained from these substrates. The optical and ophthalmic articles must 25 possess the combination of following characteristics: e a high transparency (transmission generally of greater than 85% and preferably of greater than or equal to 90%), with an absence [lacuna] or optionally a very low light scattering; 30 * a high Abbe number of greater than or equal to 30 and preferably of greater than or equal to 35, in order to avoid chromatic aberrations; e a low yellowing index and an absence of yellowing over time; 35 e a good impact strength and resistance to abrasion; e good suitability for various treatments (shock-proof primer, anti-glare or hard coating cRAL/, - 2 deposition, and the like) and in particular a good suitability for colouring; e good suitability for surface working and edging treatments, without the overall geometry of the 5 glass being deformed during these operations. In addition, the polymerizable compositions for the manufacture of optical and ophthalmic articles must also be easy to process industrially. It is also desirable for the compositions to be 10 able to be easily and quickly polymerized, in particular for them to be able to be polymerized by photopolymerization techniques or mixed photopolymeri zation and thermal polymerization techniques, making it possible to reduce the cycle times for the manufacture 15 of the articles. It is also desirable for the polymerizable compositions to be able to be employed in overmoulding processes. Finally, it is also desirable for the 20 polymerizable compositions and the polymerized substrates obtained to be suitable for photo chromatization, in order to obtain optical and ophthalmic articles possessing photochromic properties. The object of the present invention is 25 therefore to provide a polymerizable monomer composition which, after polymerization, results in transparent substrates which meet the above requirements. Another subject-matter of the present invention 30 is the transparent substrates, in particular substrates having photochromic properties, obtained by polymerization, by a thermal or photochemical route or by a combination of these two routes, of the compositions according to the invention. 35 Finally, another subject-matter of the present invention is optical and ophthalmic articles, in particular substrates having photochromic properties, such as lenses and glasses for spectacles, obtained from the above substrates. R AL r'RA4 - 3 According to the invention, the polymerizable monomer composition comprises, with respect to the total weight of the polymerizable monomers present in the composition: 5 e 30 to 100% of one or more monomers (I) of formula:
CH
2 =C -+0-CH 2
CH-)--CH
2
-C-CH
2
G-(-HCH
2 0 ~--C=CH 2 (I) 0 Rb0 in which R 1 , R 2 , R' and R" represent, independently of one another, a hydrogen atom or a 10 methyl radical, Ra and Rb, which are identical or different, each represent an alkyl group having 1 to 10 carbon atoms, provided that Ra and Rb do not simultaneously represent a methyl group, and m and n are integers satisfying the relationship 2 m + n 15 20; e 0 to 70% of at least one other monomer (II) polymerizable by a radical route, other than the monomer (I), such that a transparent substrate resulting from the polymerization of the composition 20 has a glass transition temperature satisfying the relationship 70 0 C Tg 110 0 C; and e at least one system for initiating the polymerization. The first important constituent of the 25 polymerizable compositions according to the invention is the monomer or monomers (I) corresponding to the above formula. Preferably, in the above formula of the monomers (I), R 1 and R 2 represent a methyl group and Ra 30 and Rb represent an alkyl group having 2 to 10 carbon atoms. Preferably, Ra and Rb represent an ethyl, propyl or butyl radical. More preferably, Ra and Rb are different from one another and in particular Ra and Rb respectively represent an ethyl group and a butyl group 35 (preferably n-butyl).
AL
- 4 Preferably, m and n are integers such that 2 m + n 10 and better still 2 m + n 5. Mention may be made, among the monomers (I) particularly recommended in the compositions according 5 to the invention, of 2 ,2-di(C2-Clo)alkyl-1,3-propanediol 2x-propoxylate di (meth) acrylate and 2, 2-di (C 2 -Cio) alkyl 1,3 -propanediol 2x-ethoxylate di (meth) acrylate. As indicated above, the particularly recommended monomers (I) are dimethacrylates and very 10 particularly the compound 2-ethyl-2-n-butyl 1,3-propanediol 2x-propoxylate dimethacrylate (EBP 2PO DMA). (Meth)acrylic monomers (I) corresponding to the above formula and their process of preparation are 15 disclosed in the document WO-95/11219. The monomers (I) of the compositions of the present invention can be prepared by the process disclosed in the cited document. Briefly, these (meth)acrylic monomer [sic] (I) 20 are prepared by at least two stages of alkoxylation and of acrylation. Initially, the 2,2-dialkyl 1,3-propanediol is alkoxylated by reaction with the corresponding alkylene oxide. The product resulting from the alkoxylation is finally esterified with 25 acrylic and/or methacrylic acid, in order to obtain the desired (meth)acrylic monomer. It is also possible, instead of the direct esterification by (meth)acrylic acids, to use a transesterification reaction by using the corresponding (meth)acrylates. For further details 30 as regards the process of preparation of the (meth)acrylic monomers (I), reference may be made to the document WO-95/11219. The monomer or monomers (I) represent 30 to 100% by weight of the polymerizable monomers present in 35 the compositions, preferably 30 to 70% by weight and better still from 40 to 70% by weight. The second important constituent of the polymerizable compositions according to the invention, which can optionally be present in these compositions,
L/
- 5 is a monomer or a mixture of monomers (II), other than the monomers (I), polymerizable by a radical route. These polymerizable monomers (II) must be such that the transparent substrates resulting from the 5 polymerization of the polymerizable compositions have a glass transition temperature which satisfies the relationship 70 0 c [sic] 5 Tg 110 0 C, preferably 80 0 C Tg 100 0 C. The polymerizable monomers (II) generally 10 comprise one or more (meth)acrylate functional groups and/or one or more allyl groups. Preferably, these monomers (II) comprise one, two or three (meth)acrylate functional groups, better still one or two (meth)acrylate functional groups or 15 one or two allyl groups or alternatively one allyl group and one (meth)acrylate functional group. More preferably, the polymerizable monomers (II) comprise methacrylate functional groups, better still two methacrylate functional groups, two allyl groups or one 20 allyl group and one (meth)acrylate functional group. A first preferred class of the polymerizable monomers (II) comprises the monomers corresponding to the formula:
R
3 -O(RSOy, -OW )pR 4 (Ila) 25 in which R 3 is an acryloyl or methacryloyl radical, R4 is a hydrogen atom, an acryloyl radical, a methacryloyl radical or a hydrocarbon-comprising group having 1 to 40 carbon atoms, R 5 is an alkylene group having 1 to 5 carbon atoms and p is an integer from 2 30 to 50. Preferably, R 3 and R 4 represent methacryloyl groups and R 5 is an ethylene, propylene or butylene group, better still an ethylene or propylene group. Mention may be made, among the monomers of 35 formula (IIa), of poly(methylene glycol) mono- and di(meth)acrylates, poly(ethylene glycol) mono- and di(meth)acrylates, poly(propylene glycol) mono- and di (meth) acrylates, alkoxypoly (methylene glycol) mono and di (meth) acrylates [sic], alkoxypoly(ethylene S ~ uj' - 6 glycol) mono- and di(meth)acrylates [sic] and poly(ethylene glycol) -poly (propylene glycol) mono- and di(meth)acrylates. These monomers are disclosed, inter alia, in the document US-A-5,583,191. 5 A second class of monomers (II) suitable for the compositions of the present invention comprises the monomers corresponding to the formula: R 6-Y-R7 (IIb) where R 6 and R represent a hydrogen atom, an 10 acryloyl group or a methacryloyl group, at least one of R6 or R being a (meth)acryloyl group, and Y is an alkylene radical having at least 10 carbon atoms. Preferably, R 6 and R 7 are methacryloyl groups and Y is an alkylene group having 2 to 50 carbon atoms. 15 A third class of monomers (II) suitable for the compositions according to the invention comprises the monomers corresponding to the formula: Rd ReO(R'0O (OR 1V)rOR 9 in which R 8 and R 9 represent a hydrogen atom, an 20 acryloyl group or a methacryloyl group, provided that at least one of R 8 or R 9 is a (meth)acryloyl group, Rd and Re represent H or CH 3 , Ri 0 and R" represent a C 1
-C
5 alkylene group, and q and r are such that the mean value q+r 2. 25 Preferably, R 8 and R 9 are methacryloyl groups, Rd and Re are methyl groups, Ri 0 and Ril are ethylene or propylene groups and 4 < q+r 50. A fourth class of monomers (II) of use in the present invention comprises allyl monomers, preferably 30 difunctional monomers, such as poly(alkylene glycol) di(allyl carbonate) [sic], and monomers comprising a (meth)acrylate functional group and an allyl group, in particular a methacrylate functional group and an allyl group. 35 Mention may be made, among the poly(alkylene glycol) di(allyl carbonate) [sic] suitable for the - 7 present invention, of ethylene glycol di (2-chloroallyl carbonate), di(ethylene glycol) di(allyl carbonate), tri(ethylene glycol) di(allyl carbonate), propylene glycol di(2-ethylallyl carbonate), di(propylene glycol) 5 di(allyl carbonate), tri(methylene glycol) di(2-ethylallyl carbonate) and penta(methylene glycol) di(allyl carbonate). The preferred di(allyl carbonate) is di(ethylene glycol) di(allyl carbonate), sold under the 10 trade name CR-39 Allyl Diglycol Carbonate by the company PPG Industries Inc. The preferred monomer comprising an allyl group and a methacrylic functional group is allyl methacrylate. 15 Mention may be made, among the particularly recommended monomers (II), of tri(propylene glycol) di(meth)acrylate, poly(ethylene glycol) dimethacrylate [sic] (for example, poly(ethylene glycol-600) dimethacrylate, poly(propylene glycol) dimethacrylate 20 [sic] (for example, poly(propylene glycol-400) dimethacrylate), bisphenol A alkoxylate dimethacrylate [sic], in particular bisphenol A ethoxylate and propoxylate dimethacrylate [sic] (for example, bisphenol A 5-ethoxylate dimethacrylate, bisphenol A 25 4,8-ethoxylate dimethacrylate and bisphenol A 30-ethoxylate dimethacrylate). Mention may also be made, among the monofunctional mononiers (II), of aromatic mono(meth)acrylate oligomers, and, among the 30 trifunctional monomers, of tri(2-hydroxyethyl)iso cyanurate triacrylate, trimethylolpropane ethoxylate acrylate [sic] and trimethylolpropane propoxylate acrylate [sic]. An important condition of the polymerizable 35 compositions according to the invention is that they result in transparent polymer substrates having a glass transition temperature such that 70 0 C Tg 110 0 C, preferably 80 0 C Tg 1000C.
LU
- 8 When it is present, the monomer or the monomers (II) must be such that the final polymerizable composition results in substrates having a glass transition temperature which satisfies the above 5 relationship. The monomer or monomers (II), when they are present in the composition according to the invention, generally represent from 20 to 60% by weight of the polymerizable monomers of the composition. Preferably, when the mean value of m+n for the 10 monomers of formula (I) present in the composition according to the invention is less than approximately 4 to 5, the proportion of monomers (II) is generally between 35 and 60% by weight with respect to the total weight of the polymerizable monomers present in the 15 composition and use will be made of monomers (II) having relatively longer chains, while, when the mean value of m+n of the monomers (I) is greater than approximately 4 or [sic] 5, the monomer or monomers (II) preferably represent from 20 to 50% by weight of 20 the polymerizable monomers present in the composition and use will be made of monomers having relatively shorter chain lengths. For monomers of formula (I) for which the mean value is of the order of 4 to 5, use will be made of 0 25 to 50% by weight of monomers (II). In addition, when it is desired to obtain a polymerizable composition for the manufacture of optical or ophthalmic articles having photochromic properties, it is desirable for the composition to 30 comprise one or more monomers (II) chosen from the group (A) of long-chain monomers, this group being composed of the following monomers: - monomers of formula (IIa) in which p can take the values from 10 to 50; 35 - monomers of formula (IIb) in which Y is an alkylene group comprising 10 to 50 carbon atoms; and - monomers of formula (IIc) for which q+r > 15.
AL
- 9 This or these monomers of the group (A) preferably represent 5 to 15% by weight of the copolymerizable monomers of the composition. It is preferable for these long-chain monomers 5 not to be present at an excessively high concentration because they would lower to an excessively significant degree the value of Tg. Preferably, in order to obtain photochromic articles, use will be made of a mixture of monomers 10 (II) , at least one of which will be chosen from the monomers of the group (A) and at least one other of which will be chosen from the monomers (II) with a chain length lower than those of the monomers of the group (A). 15 It is remarkable to observe that the polymers obtained from the polymerizable compositions according to the invention are rendered photochromatizable without the addition of specific monomers, such as non polymerizable plasticizers of the poly(ethylene glycol) 20 dibenzoate type, as disclosed in the document WO-95/10790. This is a particularly attractive advantage of the invention, because such non polymerizable plasticizers present problems during subsequent treatments of optical glasses (vacuum 25 treatment, and the like), which are thus avoided in the case of the invention. The compositions according to the invention also comprise a system for initiating the polymerization. The polymerization initiating system 30 can comprise one or more thermal or photochemical polymerization initiating agents or alternatively, preferably, a mixture of thermal and photochemical polymerization initiating agents. These initiating agents are well known in the art and use may be made of 35 any conventional initiating agent. Mention may be made, among the thermal polymerization initiating agents which can be used in the present invention, of peroxides, such as benzoyl peroxide, cyclohexyl peroxydicarbonate and isopropyl peroxydicarbonate.
LU
- 10 Mention may be made, among the photoinitiators, of in particular 2,4,6-trimethylbenzoyldiphenyl phosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2, 2-dimethoxy-1, 2-diphenylethane-1-one [sic] and alkyl 5 benzoyl ethers. Generally, the initiating agents are used in a proportion of 0.01 to 5% by weight with respect to the total weight of the polymerizable monomers present in the composition. As indicated above, the composition 10 more preferably simultaneously comprises a thermal polymerization initiating agent and a photoinitiator. The polymerizable compositions according to the invention can also comprise additives conventionally used in polymerizable compositions for the moulding of 15 optical or ophthalmic articles, in particular glasses for spectacles and lenses, in conventional proportions, namely inhibitors, colorants, UV absorbers, fragrances, deodorants, antioxidants, anti-yellowing agents and photochromic compounds. 20 In order to obtain optical or ophthalmic articles having photochromic properties, one or more photochromic compounds can be incorporated by any known means. The photochromic compound or compounds can either be directly incorporated in the pigment form in 25 the polymerizable composition or the photochromic material or materials can be incorporated in the polymer substrate obtained from the polymerizable compositions by a well known process of impregnation and of heat transfer. 30 Any conventional photochromic compound, such as spirooxazines and chromenes, can be used. In the following examples, except when otherwise indicated, all the parts and percentages are expressed by weight and the proportions of the 35 additives, other than the polymerizable monomers, are expressed with respect to the total weight of the polymerizable monomers of the composition.
AL
- 11 Comparative Example A and Example 1 The polymerizable compositions in Table I below were prepared and these compositions were cast between two flat moulds exhibiting a separation of 2 mm and 5 were then prepolymerized for 3 seconds in an IST batch photopolymerization furnace. The mould was placed vertically between two lamps, the illumination of which was adjusted to 70 milliwatts/cm 2 . These compositions were subsequently polymerized for 10 minutes in a 10 continuous furnace for UV polymerization thermally assisted at 120 0 C. The moulds were taken apart and the biplanar polymer substrate obtained was annealed for two hours at 60-120 0 C. The physical properties of the polymer substrates are also shown in Table I below. 15 TABLE I COMPARATIVE EXAMPLE EXAMPLE A 1 Polymerizable monomers Neopentyl glycol dimethacrylate 100 EBP2PODMA - 100 Additives Photoinitiator CGI 1850 (CIBA) 0.1% 0.1% UV absorber Cyasorb* UV 5411 (Cyanamid) 0.07% 0.07% Index, nd [sic], 25 0 C 1.4983 1.4930 Abbe number 54 55 Density, g/cm 3 1.18 1.07 Shrinkage, % 11.3 8.9 Colour Pale yellow Colour less Tg, OC 145 109 Water uptake, % 1.7 0.6
L,
- 12 The polymerized material obtained from the composition according to the invention exhibits a lower density than the material of Comparative Example A. The composition of Example 1 exhibits superior 5 photochromic properties to those of Comparative Example A. Comparative Examples B and C and Examples 2 to 5 The polymer substrates were prepared from 10 polymerizable compositions according to the invention as above. The compositions and the properties of the substrates obtained are shown in Table II below. ~A I,,
CCLI
in oc 0 LnL M n c o E0n r q -0 ML q ' r *00 ONO V4 r- M - nC ) 0o )0 C*C r4C 0 0 I~ n l N v- L L r-4 rf 0-I 0 r H M *o r-I C w L r-I N 0 - v-I E-4I ~~CN ~~C a%0 r 0 0 iO n .) 4-)d C)) oCI- - 0 w 0b *H t4 C'o >4 4. . 0 f l- o o H> q u)mOn 0IH4-- 0Q 0 U)5~ X 0 a)~N L) 4 - 14 EBP2PODMA: 2-ethyl-2-butyl-1, 3-propanediol 2x-propoxylate dimethacrylate PPG400DMA: poly(propylene glycol-400) dimethacrylate 5 BPA5EODMA: Bisphenol A 5-ethoxylate dimethacrylate TPP: Triphenylphosphine (antioxidant) Analogous results were obtained with a mixed UV and thermal initiating system. The polymerization 10 process then comprises a prepolymerization by UV radiation (or gelling) of 3 seconds and then a thermal polymerization in an air oven (lh, 1200C) and the catalyst used is TBPEH (tert-butyl per(2-ethylethanoate)) provided by the company SPQ. 15 The compositions 2 to 4 provide an excellent compromise between the various properties. In all cases, the densities of the polymerized substrates obtained are much lower than those of the low index reference material CR390 (1.32) sold by the company PPG 20 Industries. The polymerized materials obtained from the compositions B and C are deformed during a surface working operation. Examples 6 to 12 25 The compositions shown in Table III below were prepared and polymerized as above. The properties of the materials are also given in Table III. TABLE III 6 7 8 9 10 11 12 EBP2PODMA 80 60 60 60 60 60 60 D101 30 PPG400DMA 30 20 20 SR344 30 DCPMA 30 CN131 20 10 5 SR368 10 10 5 CD501 20 CD502 20 - 15 Additives % CGI1850 0.15 0.15 0.15 0.15 0.15 0.15 0.15 % UV5411 0.07 0.07 0.07 0.07 0.07 0.07 0.07 % TPP 0.2 0.2 0.2 0.2 0.2 0.2 0.2 5 Properties Index, nD, 25 0 C 1.504 1.49 1.52 1.49 1.49 1.49 1.49 Abbe 57 58 55 58 57 57 58 Density, g/cm 3 1.09 1.1 1.1 1.09 1.09 1.09 1.08 Colourability, Tv red, PS 20/10 41.3 44 39 35 40 35 32 Tg, OC 92 80 88 82 91 92.5 101 Monofunctional monomers: - Aromatic monoacrylate oligomer, CN131, Cray 10 Valley Difunctional monomers: - Bisphenol A diethoxylate dimethacrylate, D101, Akzo - Poly(ethylene glycol-400) diacrylate, SR344, 15 Sartomer - Dicyclopentadiene [sic] dimethacrylate, DCPMA, Shin Nakamura Trifunctional monomers: - Tris (2-hydroxyethyl) isocyanurate triacrylate, 20 SR368, Sartomer - Trimethylolpropane ethoxylate acrylate [sic], CD502, Sartomer - Trimethylolpropane propoxylate acrylate [sic], CD501, Sartomer 25 Comparative Example D and Examples 13 to 16 The compositions shown in Table IV below were prepared and polymerized as above. Photochromic compounds (T4-Gray formulation from the company Transitions Optical) were incorporated
R//
- 16 in the polymerized substrates obtained by impregnation with two impregnation conditions, namely: (a) 3 hours at 1350C, and (b) 6 hours at 1400C. 5 By way of comparison, a commercially available substrate, CR-407 (aromatic acrylic polymer, nD = 1.55, Tg = 88 0 C), was also impregnated under the conditions (a). The photochromic kinetics of the impregnated 10 polymerized substrates were determined at a temperature of 300C. The substrates were irradiated for 15 minutes, in a thermostatically-controlled cell exposed to the air, with UV radiation of 365 nm, 10 W/m 2 and 53.4 klux. 15 The decoloration was carried out in the dark. The results are given in Table V. TABLE IV Comparative Example Example Example Example D 13 14 15 NPG2PODMA 100 - - EBP2PODMA - 100 50 50 PPG400DMA - - 10 10 BPA4, 8EODMA - - 30 30 BPA30EODMA - - 9 PEG600DMA - - 9 MBOL - - 1 1 Initiator, CGI 1850 0.15 0.15 0.15 0.15 UV absorber, UV5411 0.07 0.07 0.07 0.07 Refractive index, nD - - 1.5 1.5 Abbe - - 57 58 Tg, OC 119 108 90 86 20 NPG2PODMA: Neopentyl glycol 2x-propoxylate dimethacrylate PPG400DMA: Poly(propylene glycol-400) dimethacrylate
AL/
- 17 BPA4,8EODMA: Bisphenol A 4,8-ethoxylate dimethacrylate BPA30EODMA: Bisphenol A 30-ethoxylate dimethacrylate 5 PEG600DMA: Poly(ethylene glycol-600) dimethacrylate MBOL: Methylbutenol (anti-yellowing agent) 10 TABLE V Transmission, % Decoloration time o [sic] 15 t 1/2 t 3/4 minutes minutes [sic] (s) [sic] (s) Comparative D, (a) 91.2 41.9 122 662 Comparative D, (b) 90.4 35.9 151 874 Example 13, (a) 90.7 30.9 66 324 Example 13, (b) 90 30.8 65 310 Example 14, (a) 88.3 23.4 34 116 Example 14, (b) 87.6 25.7 35 135 Example 15, (a) 89.2 25.5 56 219 Example 15, (b) 88 24.7 59 300 CR 407 (a) 84 26 34 121 The composition of Example 14 exhibits photochromic properties superior to or comparable with 15 those of the substrate CR407 Another important aspect of the polymerizable compositions according to the invention is that they lend themselves well to the manufacture of optical and ophthalmic articles, such as lenses, by the 20 overmoulding technique. A technique for manufacturing lenses by overmoulding on the front surface of a preform is disclosed, inter alia, in the documents US-A-5,531,940, US-5,372,755 and US-5,288,221. The preparation of photochromic articles by 25 overmoulding is set out more particularly in the document US-5, 531,940.
\-?AL/
- 18 Briefly, this overmoulding technique consists in casting a polymerizable composition into an organic glass of optical quality in the space provided between a mould and the front surface of a lens preform made of 5 organic glass of optical quality and in polymerizing the cast composition in order to form a polymerized coating adhere [sic] to the surface of the lens. The lens preform can be finished or semi-finished and the coated surface of the preform can optionally be 10 depolished. It is also possible to carry out the overmoulding on the rear surface of the lens of a preform. In order to demonstrate the suitability for overmoulding of the compositions according to the 15 invention, photopolymerizable compositions according to the invention and according to the prior art were cast between the rear surface of a lens preform with a thickness of 2 mm made of various organic glasses (including made of an organic glass obtained from a 20 composition according to the invention) and a mould made of an inorganic material. These cast compositions were polymerized by UV irradiation (between two 70 mw/cm2 [sic] mercury lamps) for 60 seconds. The products obtained are subsequently removed from the 25 mould and fractured with a hammer. The polymerized layer is regarded as adhering to the preform if the pieces do not exhibit adhesive failure at the interface between the layer and the preform. The compositions are given below and the results summed up in Table VI. 30 COMPOSITION 1 (according to the invention) EBP2PODMA 50 PPG 400 DMA 19 BPA 4,8 EODMA 30 35 MBOL 1 CGI 1850 0.1 UV 5411 0.07 Lu 0 - 19 COMPOSITION 2 (conventional) Tri(propylene glycol) dimethacrylate (TPGDMA) 37.4 PPG 400 DMA 48.5 5 D 121 14.1 TPP 0.2 CGI 1850 0.10 The lens preforms were obtained by casting the 10 chosen composition in a mould and by carrying out a prepolymerization by the photochemical route for 3 seconds under 70 mW/cm 2 UV, followed by a thermal polymerization at 120 0 C for 10 minutes. After removing from the mould, annealing is carried out for 2 hours at 15 120 0 C. TABLE VI Lens preform overmoulding composition Adhesion Composition Depolished rear face 2 no 2 no 2 yes 2 no 2 yes CR39 (di(ethylene glycol) no bis(allyl carbonate) 2 yes BPA polyethoxylate DMA no 1 no 2 yes 1 no 1 yes 1 no BPA polyethoxylate DMA yes TPGDMA: Tri(propylene glycol) dimethacrylate 20 EBP2PODMA: 2-ethyl-2-butyl-1, 3-propanediol 2x-propxylate dimethacrylate BPA polyethoxylate DMA: Bisphenol A polyethoxylate dimethacrylate (Polymerizable compositions based on these monomers are disclosed in 25 FR-A-2,699,541) CR39@: Composition based on di(ethylene glycol) bis(allyl carbonate) sold by PPG Industries.
- 20 The physical properties of the polymer substrates were determined as indicated below. The yellowing index was measured according to ASTM Standard D 1925-63. 5 The Bayer resistance to abrasion was determined according to ASTM Standard F 735-81. The impact strength was determined according to the United States FDA test (ball drop test) in which a 16 g ball is allowed to fall onto a lens from a height 10 of 1.27 m, corresponding to an energy of 200 mJ. OK means that the glass is intact after the impact. The test of exposure to sunlight consists in subjecting the lenses for 200 hours to exposure to 15 sunlight under the same conditions with a Suntest Hanau device emitting radiation of 24.4 w/m 2 [sic] in the 300 400 nm spectral range and in measuring the yellowing index (YI) before and after irradiation. The test is regarded as positive (OK) if the difference in YI is 20 less than or equal to 1. Measurement of the colourability The measurement given is the value of the transmission, measured in the visible, of a glass with a centre thickness of 2 mm coloured by steeping in an 25 aqueous bath at 94 0 C, in which bath is dispersed a red pigment "Disperse Red 13" from the company Eastman Kodak. The Tg is measured by DMA (Dynamic mechanical analysis) on a flat test specimen of 5.2 cm x 1 cm x 30 2 mm (thickness). The test is carried out in 3-point bending. Tg corresponds to the maximum of the ratio E" (lossmodulus) E' (storage modulus) 35 The water uptake test consists in placing a piece of lens in an oven for 12 hours at 50 0 C. The sample is subsequently weighed (measurement of the - 21 starting mass) and then it is immersed in distilled water at 50 0 C at atmospheric pressure for 12 hours. After 12 hours, the sample is removed, wiped dry and weighed (mass after immersion). 5 The value for the water uptake is given by: mass after immersion - starting mass Water uptake = x 100 starting mass The hardness values were measured by means of a Fischer micro hardness tester equipped with a Bergovitch tip on a flat lens with a thickness of 10 1.6 mm. Generally, except when otherwise indicated, all the tests were carried out on samples with a thickness of 2 mm.
Claims (9)
1. Polymerizable monomer composition, charac terized in that it comprises, with respect to the total weight of the polymerizable monomers present in the 5 composition: e 30 to 100% of one or more monomers (I) of formula: R R'@R R" R CH 2 =C -tC--(- H 2 CH.O-CH 2 -C-CH 2 G-CHCH 2 0 ,-CCHz ( o Rb 0 in which R 1 , R 2 , R' and R" represent, 10 independently of one another, a hydrogen atom or a methyl radical, Ra and Rb, which are identical or different, each represent an alkyl group having 1 to 10 carbon atoms, provided that Ra and Rb do not simultaneously represent a methyl group, and m and n 15 are integers satisfying the relationship 2 m + n 20; e 0 to 70% of at least one other monomer polymerizable (II) [sic] by a radical route, other than the monomer (I), such that a transparent substrate 20 resulting from the polymerization of the composition has a glass transition temperature satisfying the relationship 70 0 C Tg 110 0 C; and * at least one system for initiating the polymerization. 25 2. Composition according to Claim 1, characterized in that the monomer or monomers (II) comprise one or more (meth)acrylate functional groups and/or one or more allyl groups, preferably two methacrylate functional groups, two allyl groups or one methacrylate 30 functional group and one allyl group.
3. Composition according to Claim 1 or 2, characterized in that Ra and Rb represent a C 2 to C 6 alkyl group, preferably an ethyl, propyl or butyl group. 35 4. Composition according to any one of Claims 1 to 3, characterized in that R 1 and R 2 are CH 3 groups. - 23 5. Composition according to Claim 1, characterized in that the monomer (I) is 2-ethyl-2-n-butyl 1,3-propanediol 2x-propoxylate dimethacrylate.
6. Composition according to any one of Claims 1 to 5 5, characterized in that the monomer(s) (II) is (are) chosen from: a) monomers of formula R 3 -O(R 5 O-p R 4 (Ha) in which R 3 is a (meth)acryloyl radical, R 4 is 10 H, a (meth)acryloyl radical or a hydrocarbon-comprising radical having 1 to 40 carbon atoms, R 5 is a C 1 -C 5 alkylene group and p is an integer from 2 to 50; b) monomers of formula: R 6 -Y-R 7 (IIb) 15 where R 6 and R 7 represent H, an acryloyl group or a (meth)acryloyl group [sic], at least one of R 6 or R 7 being a (meth)acryloyl group, and Y is an alkylene radical having from 2 to 50 carbon atoms; c) monomers of formula: RIO(R'O ( (OR")rOR' 1O _ r 010c 20 in which R 8 and R 9 represent a hydrogen atom, an acryloyl group or a methacryloyl group, provided that at least one of R 8 or R 9 is a (meth)acryloyl group, Rd and Re represent H or CH 3 , R 10 and R 11 represent a Ci-C 5 25 alkylene group, and q and r are such that q+r > 2; and d) poly(alkylene glycol) di(allyl carbonate) [sic] and monomers comprising a methacrylate functional group and an allyl group.
7. Composition according to Claim 6, characterized 30 in that the monomers (IIa) are chosen from poly(methylene glycol) mono- and di(meth)acrylate [sic], poly(ethylene glycol) mono- and di(meth)acrylate [sic], poly(propylene glycol) mono- and di (meth) acrylate [sic], alkoxypoly(methylene glycol) 35 mono- and di(meth)acrylate [sic], alkoxypoly(ethylene ,A L /glycol) mono- and di(meth)acrylate [sic], alkoxy uJI - 24 poly(propylene glycol) mono- and di(meth)acrylate [sic] and poly(ethylene glycol)-poly(propylene glycol) mono and di(meth)acrylate [sic].
8. Composition according to Claim 6, characterized 5 in that, in the formula (IIc), Rd and Re represent CH 3 and R 10 and R" are ethylene or propylene groups.
9. Composition according to Claim 6, characterized in that it comprises one or more monomers (II) chosen from the group (A) of long-chain monomers, this group 10 (A) being composed: - of monomers of formula (IIa) in which p can take the values from 10 to 50; - of monomers of formula (IIb) in which Y is an alkylene group comprising 10 to 50 carbon atoms; and 15 - of monomers of formula (IIc) for which q+r > 15.
10. Composition according to Claim 9, characterized in that the monomer or monomers of the group (A) represent 5 to 15% by weight of the copolymerizable 20 monomers of the composition.
11. Composition according to any one of Claims 1 to 10, characterized in that the monomer or monomer [sic] (II) are chosen from poly(propylene glycol-400) dimethacrylate, poly(ethylene glycol-600) dimeth 25 acrylate, bisphenol A diethoxy [sic] dimethacrylate, bisphenol A 5-ethoxylate dimethacrylate, bisphenol A 4,8-ethoxylate dimethacrylate, bisphenol A
30-ethoxylate dimethacrylate, the aromatic monoacrylate oligomer, dicyclopentadiene [sic] dimethacrylate, 30 tri (2-hydroxyethyl) isocyanurate triacrylate, trimethylolpropane ethoxylate acrylate [sic], trimethylolpropane propoxylate acrylate [sic], di(ethylene glycol) di(allyl carbonate) and allyl methacrylate. 35 12. Composition according to any one of Claims 1 to 11, characterized in that the polymerization initiating system comprises one or more thermal initiators, one or more photoinitiators or a mixture of one or more AL thermal initiators and of one or more photoinitiators. - 25 13. Transparent polymer substrate obtained by polymerization of a composition according to any one of Claims 1 to 12. 14. Optical or ophthalmic article comprising a 5 polymer substrate according to Claim 13. 15. Optical or ophthalmic article according to Claim 13, characterized in that the polymer substrate is overmoulded on a surface of a preform made of transparent organic glass. 10 16. Optical or ophthalmic article according to either one of Claims 14 and 15, characterized in that a photochromic pigment is incorporated in the substrate which constitutes it in all or part. LU
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9708614A FR2765583A1 (en) | 1997-07-07 | 1997-07-07 | Polymerisable acrylic compositions for ophthalmic articles |
| FR97/08614 | 1997-07-30 | ||
| FR97/09733 | 1997-07-30 | ||
| FR9709733A FR2765584B1 (en) | 1997-07-07 | 1997-07-30 | POLYMERIZABLE MONOMER COMPOSITIONS, TRANSPARENT POLYMERIC SUBSTRATES, AND OPTICAL AND OPHTHALMIC ARTICLES OBTAINED |
| PCT/FR1998/001421 WO1999002574A1 (en) | 1997-07-07 | 1998-07-03 | Polymerisable monomer compositions, transparent polymer substrates, and resulting optical and ophthalmologic articles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU8446098A true AU8446098A (en) | 1999-02-08 |
| AU731071B2 AU731071B2 (en) | 2001-03-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU84460/98A Ceased AU731071B2 (en) | 1997-07-07 | 1998-07-03 | Polymerizable monomer compositions, transparent polymer substrates, and optical and ophthalmic articles obtained |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0925315B1 (en) |
| JP (1) | JP3868005B2 (en) |
| AU (1) | AU731071B2 (en) |
| CA (1) | CA2264906A1 (en) |
| DE (1) | DE69809698T2 (en) |
| FR (1) | FR2765584B1 (en) |
| WO (1) | WO1999002574A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2307634C (en) * | 1997-11-14 | 2008-02-05 | Novartis Ag | Methods and compositions for manufacturing tinted ophthalmic lenses |
| US6149842A (en) * | 1998-11-12 | 2000-11-21 | Novartis Ag | Methods and compositions for manufacturing tinted ophthalmic lenses |
| US6774178B2 (en) | 2001-01-05 | 2004-08-10 | Novartis Ag | Tinted, high Dk ophthalmic molding and a method for making same |
| FR2832717B1 (en) * | 2001-11-26 | 2004-07-09 | Essilor Int | RADICAL-POLYMERIZABLE COMPOSITION CONDUCTING ORGANIC SHOCK-RESISTANT GLASSES |
| JP4398427B2 (en) * | 2003-01-27 | 2010-01-13 | 株式会社メニコン | Photochromic contact lens with excellent color erasability |
| JP4870374B2 (en) * | 2005-03-25 | 2012-02-08 | 株式会社日本触媒 | Curable composition for optical parts |
| JP2007084782A (en) * | 2005-08-26 | 2007-04-05 | Nippon Shokubai Co Ltd | (meth)acrylic resin composition and (meth)acrylic cured product |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR0173110B1 (en) * | 1988-12-27 | 1999-05-01 | 나가이 야타로 | Lens sheet |
| CA2007295C (en) * | 1989-01-10 | 2001-02-20 | Max Hunziker | Photocurable compositions |
| FR2699541B1 (en) * | 1992-12-22 | 1995-04-28 | Essilor Int | Polymeric compositions with a low yellow index, polymerizable compositions and lenses using them. |
| SE9303503D0 (en) * | 1993-10-22 | 1993-10-22 | Perstorp Ab | Acrylic Monomer |
| US5663264A (en) * | 1993-12-27 | 1997-09-02 | Hitachi Chemical Company, Ltd. | Transparent resin and plastic lens |
| JP3085570B2 (en) * | 1994-07-08 | 2000-09-11 | 株式会社トクヤマ | Polymerizable composition |
-
1997
- 1997-07-30 FR FR9709733A patent/FR2765584B1/en not_active Expired - Fee Related
-
1998
- 1998-07-03 EP EP98935088A patent/EP0925315B1/en not_active Expired - Lifetime
- 1998-07-03 WO PCT/FR1998/001421 patent/WO1999002574A1/en active IP Right Grant
- 1998-07-03 JP JP50823299A patent/JP3868005B2/en not_active Expired - Fee Related
- 1998-07-03 AU AU84460/98A patent/AU731071B2/en not_active Ceased
- 1998-07-03 DE DE69809698T patent/DE69809698T2/en not_active Expired - Fee Related
- 1998-07-03 CA CA002264906A patent/CA2264906A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| DE69809698T2 (en) | 2003-08-21 |
| EP0925315A1 (en) | 1999-06-30 |
| AU731071B2 (en) | 2001-03-22 |
| JP3868005B2 (en) | 2007-01-17 |
| DE69809698D1 (en) | 2003-01-09 |
| CA2264906A1 (en) | 1999-01-21 |
| FR2765584B1 (en) | 1999-10-22 |
| FR2765584A1 (en) | 1999-01-08 |
| EP0925315B1 (en) | 2002-11-27 |
| WO1999002574A1 (en) | 1999-01-21 |
| JP2001500566A (en) | 2001-01-16 |
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| Date | Code | Title | Description |
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| FGA | Letters patent sealed or granted (standard patent) |