EP3174947A1 - Anti-abrasion varnish composition for a substrate made from thermoplastic polyacrylate - Google Patents
Anti-abrasion varnish composition for a substrate made from thermoplastic polyacrylateInfo
- Publication number
- EP3174947A1 EP3174947A1 EP15756201.8A EP15756201A EP3174947A1 EP 3174947 A1 EP3174947 A1 EP 3174947A1 EP 15756201 A EP15756201 A EP 15756201A EP 3174947 A1 EP3174947 A1 EP 3174947A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- alkyl
- monomer
- independently selected
- composition
- 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.)
- Withdrawn
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 74
- 239000002966 varnish Substances 0.000 title claims abstract description 33
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 21
- 239000000758 substrate Substances 0.000 title claims description 23
- 229920001169 thermoplastic Polymers 0.000 title claims description 8
- 239000004416 thermosoftening plastic Substances 0.000 title claims description 8
- 238000005299 abrasion Methods 0.000 title description 18
- 239000000178 monomer Substances 0.000 claims abstract description 66
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 238000009833 condensation Methods 0.000 claims abstract description 16
- 230000005494 condensation Effects 0.000 claims abstract description 16
- 150000003961 organosilicon compounds Chemical class 0.000 claims abstract description 10
- 239000004593 Epoxy Substances 0.000 claims abstract description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000012815 thermoplastic material Substances 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims description 46
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 39
- 238000006460 hydrolysis reaction Methods 0.000 claims description 32
- 230000007062 hydrolysis Effects 0.000 claims description 28
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 16
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 14
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 14
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 12
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 10
- 239000012736 aqueous medium Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 150000001735 carboxylic acids Chemical class 0.000 claims description 6
- 235000019260 propionic acid Nutrition 0.000 claims description 6
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 6
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000001409 amidines Chemical class 0.000 claims description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 3
- -1 bicyclic imidazoles Chemical class 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 1
- 238000012719 thermal polymerization Methods 0.000 claims 1
- JABYJIQOLGWMQW-UHFFFAOYSA-N undec-4-ene Chemical compound CCCCCCC=CCCC JABYJIQOLGWMQW-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 125000003545 alkoxy group Chemical group 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical compound C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical group C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- UTPYTEWRMXITIN-YDWXAUTNSA-N 1-methyl-3-[(e)-[(3e)-3-(methylcarbamothioylhydrazinylidene)butan-2-ylidene]amino]thiourea Chemical compound CNC(=S)N\N=C(/C)\C(\C)=N\NC(=S)NC UTPYTEWRMXITIN-YDWXAUTNSA-N 0.000 description 1
- QDFXRVAOBHEBGJ-UHFFFAOYSA-N 3-(cyclononen-1-yl)-4,5,6,7,8,9-hexahydro-1h-diazonine Chemical compound C1CCCCCCC=C1C1=NNCCCCCC1 QDFXRVAOBHEBGJ-UHFFFAOYSA-N 0.000 description 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002578 polythiourethane polymer Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying 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
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/00865—Applying coatings; tinting; colouring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
- G02B27/0006—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 with means to keep optical surfaces clean, e.g. by preventing or removing dirt, stains, contamination, condensation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
Definitions
- the present invention relates to a polymerizable composition for producing an anti-abrasion varnish for an ophthalmic lens made of a thermoplastic material of the polyacrylate family, such as polymethyl methacrylate (PMMA). It also relates to a process for preparing this composition and a varnish obtained from this composition, an ophthalmic lens comprising said varnish and a method of manufacturing this ophthalmic lens.
- PMMA polymethyl methacrylate
- Polyacrylates are thermoplastic materials used in ophthalmic applications such as the manufacture of spectacle lenses. Because of their thermoplastic properties, they can be shaped by inexpensive processes. In addition, waste or scrap can be reused, which has economic and environmental benefits.
- organic substrates especially polyacrylates, generally have a very low abrasion resistance to glass substrates. It is therefore customary to apply a coating on the surface of organic substrates to improve their resistance to abrasion.
- the anti-abrasion varnishes conventionally used for substrates made of polycarbonate or of polyurethane copolymer do not adhere sufficiently to polyacrylate substrates.
- the adhesion of these varnishes to the polyacrylate substrates could be improved by the use of adhesion primers.
- adhesion primers the formation of a primary bilayer / anti-abrasion varnish is an expensive process. There remains therefore a need for abrasion-resistant varnish having good adhesion to polyacrylate substrates without the need for adhesion primer.
- the Applicant has developed a polymerizable composition comprising a curable organosilicic compound which makes it possible to obtain an abrasion-resistant varnish having good adhesion properties on the polyacrylate substrates even in the absence of an adhesion primer, and that a good behavior over time and which, moreover, has good anti-abrasion properties similar or even superior to those of commonly used varnishes.
- the present invention relates to a polymerizable composition for producing lacquer on at least one face of an ophthalmic lens made of thermoplastic material of the family of polyacrylates, comprising at least one curable organosilicon compound and a condensation catalyst, said composition being devoid of any monomer comprising a vinyl or epoxy function and any compound derived from such monomers, to improve the adhesion of said varnish on said lens.
- Vinyl or epoxy monomers such as ⁇ -glycidoxypropyltrimethoxysilane, are often used in ophthalmics to promote the adhesion of varnish to lens substrates, said substrates being, for example polycarbonate, or based on polythiourethanes or polysuflides.
- the inventors have identified that, surprisingly, the vinyl or epoxy monomers decreased the adhesion of the lacquers to the substrates made of polyacrylate material, in particular polymethyl methacrylate.
- the curable organosilicon compound according to the present invention is a compound resulting from a hydrolysis reaction, in the presence of a first acid, of at least two monomers of formula (1)
- the first acid used for the hydrolysis reaction is a weak acid in an aqueous medium.
- a weak acid in an aqueous medium is an acid that does not dissociate completely in water.
- the inventors have identified that the use of a weak acid instead of a strong acid, in a composition without vinyl or epoxy monomers, made it possible to improve the adhesion to substrates made of polyacrylate material, in particular polymethyl methacrylate, and allowed in particular to improve the life of the composition.
- the life of the composition is the time during which the composition can be preserved after being manufactured without creating defects in the varnish when used to form a varnish on a lens.
- the polymerizable composition is intended for producing a varnish on at least one face of an ophthalmic lens whose substrate is a thermoplastic of the polyacrylate family.
- (C1-C6) alkyl in the sense of the present invention denotes any monovalent linear or branched group of 1 to 6 carbon atoms.
- the (C1-C6) alkyls include especially (C1-C4) alkyls such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
- aryl in the sense of the present invention denotes any monovalent aromatic group of 6 to 18 carbon atoms, optionally substituted with 1 to 4 groups, identical or different independently of one another, chosen from halogens ( C1-C6) alkyl, (C1-C6) alkyloxy.
- aryls are especially the phenyl radical, tolyl or naphthyl.
- aryl (C1-C6) alkyl within the meaning of the present invention denotes any (Cl-C6) alkyl group as defined above substituted by an aryl group as defined above.
- the aryl (C1-C6) alkyls include in particular aryl (C1-C4) alkyls such as benzyl and phenylethyl.
- each R ' is preferably independently selected from (C1-C4) alkyl, phenyl and phenyl (C1-C4) alkyl, more preferably independently selected from (C1-C4) alkyl, still more preferably independently selected from methyl and ethyl; and each R is preferably independently selected from (C1-C4) alkyl, more preferably independently selected from methyl and ethyl.
- the organosilicon compound is obtained by hydrolysis of at least two monomers of formula (1) as defined above.
- said at least two monomers comprise a monomer (A) of formula (1) in which n is an integer 1 to 3, each R 'is independently selected from (C 1 -C 6) alkyl, aryl, aryl (Cl- C6) alkyl, and each R is independently selected from (C1-C6) alkyl; and a monomer (B) of formula (1) wherein n is 0 and each R is independently selected from (C1-C6) alkyl.
- the monomer (A) is preferably a monomer of formula (1) in which n is 1 or 2, and each R is independently selected from (C 1 -C 4) alkyl, and each R 'is independently selected from (C 1 -C 4) alkyl.
- the monomer (A) may be chosen from methyltrimethoxysilane, methyltriethoxysilane and dimethyldiethoxysilane.
- the monomer (B) is preferably a monomer of formula (1) wherein n is 0 and each R is independently selected from (C1-C4) alkyl.
- the monomer (B) may be chosen from tetramethoxysilane and tetraethoxysilane.
- the organosilicon compound is obtained by hydrolysis of a monomer (A) chosen from methyltriethoxysilane and methyltriethoxysilane, and tetraethoxysilane as monomer (B).
- A a monomer chosen from methyltriethoxysilane and methyltriethoxysilane
- B tetraethoxysilane
- the composition according to the invention typically comprises from 80 to 98% by weight, preferably from 85 to 95% by weight, of organosilicic compound relative to the total dry weight of the composition.
- the proportion of monomer (A) is typically 50 to 90% by weight, preferably 60 to 85% by weight. % by weight, more preferably 70 to 80% by weight relative to the total dry weight of the composition, and the monomer (B) is typically 5 to 40% by weight, preferably 8 to 30% by weight, more preferably from 10 to 20% by weight relative to the total dry weight of the composition.
- the molar ratio of the monomer (B) relative to the monomer (A) is preferably between 0.01 to 0.5, more preferably between 0.1 to 0.3.
- the hydrolysis is carried out in the presence of a first acid which is a weak acid in an aqueous medium.
- the first acid may be a carboxylic acid selected for example from acetic acid, propionic acid, butyric acid, acrylic acid and mixtures thereof.
- the weak acid is acetic acid.
- the hydrolysis is preferably carried out at a pH of between 4.0 and 4.5.
- the composition according to the invention comprises a condensation catalyst chosen in particular from imidazoles, amidines and cyclic or bicyclic amidines.
- the condensation catalyst include N-methylimidazole, diazabicycloundecene and diazabicyclononene.
- the condensation catalyst is 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU).
- composition according to the invention typically comprises from 0.1 to 2% by weight, preferably from 0.3 to 1% by weight of condensation catalyst relative to the dry weight of the composition.
- the composition according to the invention optionally comprises a second acid, said acid being preferably a weak acid in an aqueous medium, and more preferably a carboxylic acid, more preferably chosen from acetic acid, propionic acid or butyric acid. acrylic acid and mixtures thereof, with acetic acid being preferred.
- This second acid is added during the steps of preparing the composition after the first hydrolysis step, and it may be the same or different from the first acid used during the first hydrolysis step.
- This second acid has a role in adjusting the pH of the polymerizable composition and can make it possible to stabilize the composition and thus extend the life of said composition.
- the composition according to the invention typically has a pH of between 3.5 and 5, preferably between 4.0 and 4.7.
- composition according to the invention may also comprise additional additives such as organic solvents or surfactants, such as those conventionally used by those skilled in the art of anti-abrasion varnishes for the ophthalmic field.
- additional additives such as organic solvents or surfactants, such as those conventionally used by those skilled in the art of anti-abrasion varnishes for the ophthalmic field.
- composition according to the invention may also comprise colloids in order to increase the hardness and the resistance to abrasion of the varnish.
- colloids are, for example, colloids of silica, hollow silica, zirconia or titanium dioxide.
- the composition according to the invention may comprise at most 60% by weight of colloids relative to the dry weight of the composition.
- composition is free of monomer comprising an epoxy or vinyl function.
- the composition does not comprise any silane monomer comprising a polymerizable function other than an alkyloxy. More preferably, the composition does not comprise any monomer comprising a polymerizable function other than an alkyloxy.
- the composition according to the invention comprises as monomers only monomers of formula (1) or their hydrolysates.
- the present invention also relates to a method for preparing a polymerizable composition for producing a varnish on at least one face of an ophthalmic lens of thermoplastic material of the family of polyacrylates, preferably polymethyl methacrylate (PMMA), as defined above.
- PMMA polymethyl methacrylate
- This process comprises:
- the hydrolysis is carried out from a mixture to be hydrolysed comprising at least two monomers of formula (1) in the presence of the first acid and water. It leads to a hydrolyzate comprising a curable organosilicon compound.
- the first acid is a weak acid in an aqueous medium.
- the hydrolysis is carried out in the presence of a first acid.
- the first acid may be a carboxylic acid selected for example from acetic acid, propionic acid, butyric acid, acrylic acid and mixtures thereof.
- the first acid is acetic acid.
- the monomers of formula (1) are preferably as defined above for the composition according to the invention.
- the molar ratio of the monomer (B) relative to the monomer (A) is preferably between 0.01 to 0.5, more preferably between 0.1 to 0.3.
- the mixture to be hydrolysed typically comprises 40 to 80% by weight, preferably 50 to 70% by weight, more preferably 55 to 65% by weight of monomer (A); 2 to 20% by weight, preferably 5 to 15% by weight, more preferably 7 to 13% by weight of monomer (B); 1 to 9% by weight, preferably 3 to 7% by weight of the first weak acid; and 15 to 35% by weight, preferably 20 to 30% by weight of water.
- the hydrolysis is carried out at a pH of between 3.5 and 5.0, preferably 4.0 to 4.7.
- the hydrolysis is typically carried out for 10 to 50 hours, preferably for 20 to 30 hours.
- the hydrolysis is generally carried out at room temperature. However, the hydrolysis reaction may increase the temperature of the reaction medium during hydrolysis. The temperature is preferably maintained below 50 ° C.
- the hydrolysis does not involve any monomer comprising an epoxy or vinyl function.
- the hydrolysis does not involve any silane monomer comprising a polymerizable function different from an alkyloxy.
- the hydrolysis does not involve any monomer comprising a polymerizable function different from an alkyloxy.
- the hydrolysis involves only monomers of formula (1).
- the condensation catalyst and optionally the second weak acid are added to the hydrolyzate obtained.
- the addition of the condensation catalyst and the second acid if present weak can be carried out simultaneously or separately.
- the second weak acid is added after the condensation catalyst.
- the condensation catalyst is preferably as defined above for the composition according to the invention.
- the condensation catalyst may be added in a proportion of 0.1 to 2% by weight, preferably 0.3 to 1% by weight relative to the total dry weight of the polymerizable composition.
- the second acid is preferably a weak acid in an aqueous medium. It may be the same or different from the first acid.
- the first acid and the second acid are identical.
- the second acid may be a carboxylic acid selected for example from acetic acid, propionic acid, butyric acid, acrylic acid and mixtures thereof.
- the second acid is acetic acid.
- the second acid is added in an amount sufficient for the polymerizable composition to have a pH of between 4.0 and 4.7.
- Other components such as a solvent, surfactants or colloids as defined above for the composition according to the invention may be added.
- the composition according to the invention comprises only monomers of formula (1).
- the composition according to the invention makes it possible to obtain varnishes having a very good resistance, in particular an abrasion resistance greater than or equal to 1.8, preferably greater than or equal to 2. Moreover, these varnishes have good adhesion.
- Abrasion resistance is measured using the BAYER test performed in accordance with ASTM F735.81. A high value in the BAYER test corresponds to a high degree of resistance to abrasion.
- the present invention also relates to a varnish obtained from the polymerizable composition as defined above. More specifically, the varnish is obtained by application, by methods well known to those skilled in the art such as for example by "spin coating” (that is to say spin coating), or “spray” (either spraying), or jet printing of material ("ink-jet” in English) or “dip-coating” (that is to say, dip coating) of a layer of the composition according to the invention on a substrate and polymerizing said composition layer thermally, preferably at a temperature below the glass transition temperature of the substrate.
- the present invention also relates to an ophthalmic lens comprising a substrate made of thermoplastic polyacrylate material, preferably made of PMMA, coated with the varnish according to the invention as defined above.
- Such an ophthalmic lens may be manufactured by a process comprising applying the polymerizable composition according to the invention to at least one face of a substrate made of thermoplastic polyacrylate material, preferably PMMA, and the polymerization by a thermal route, preferably at a temperature less than the glass transition temperature of said substrate of the polymerizable composition layer thus obtained.
- Example 1 267.8 g of methyltriethoxysilane and 38.8 g of tretraethoxysilane in the presence of 20 g of acetic acid and 94.6 g of water are hydrolyzed for 24 hours.
- the hydrolysis is carried out for 487.4 g of methyltrimethoxysilane and 142 g of tetraethoxysilane in the presence of 50 g of acetic acid and 248 g of water.
- 80 g of glycidyloxypropyltrimethoxysilane and 20 g of water are added to the hydrolyzate.
- a second hydrolysis is carried out for 3 to 4 days. At the end of the second hydrolysis, between 0.8% and 1.3% of DBU to obtain a ready-to-use varnish.
- a composition layer according to Example 1 or Comparative Example 1 is applied by immersion to a PMMA lens without adhesion primer. This coating is polymerized for 3 hours at a temperature of 100 ° C.
- the adhesion of the coating is measured according to the crosshatch adhesion test according to the ISTM 02-010 standard. This test defines a membership score of 0 to 5. A score of 0 or 1 is acceptable for ophthalmic lenses while scores of 3 to 5 are not acceptable.
- the abrasion resistance is measured according to the Bayer test according to ATSM F735.81. The higher the value, the better the resistance to abrasion. The results are shown in Table 1 below.
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Abstract
The invention relates to a polymerisable composition for the formation of a varnish on at least one face of an ophthalmic lens made from thermoplastic material from the polyacrylate family. According to the invention, the composition includes a curable organosilicon compound and a condensation catalyst, but does not contain any monomer having an epoxy or vinyl function or any compound originating from such monomers, so as to improve the adhesion of the varnish to the lens.
Description
Composition de vernis anti-abrasion pour substrat en polyacrylate thermoplastique Anti-abrasion varnish composition for a thermoplastic polyacrylate substrate
La présente invention concerne une composition polymérisable pour la réalisation d'un vernis anti-abrasion pour lentille ophtalmique en matériau thermoplastique de la famille des polyacrylates tels que le polyméthylméthacrylate (PMMA). Elle concerne également un procédé de préparation de cette composition ainsi qu'un vernis obtenu à partir de cette composition, une lentille ophtalmique comprenant ledit vernis et un procédé de fabrication de cette lentille ophtalmique. The present invention relates to a polymerizable composition for producing an anti-abrasion varnish for an ophthalmic lens made of a thermoplastic material of the polyacrylate family, such as polymethyl methacrylate (PMMA). It also relates to a process for preparing this composition and a varnish obtained from this composition, an ophthalmic lens comprising said varnish and a method of manufacturing this ophthalmic lens.
Les polyacrylates sont des matériaux thermoplastiques utilisés dans des applications ophtalmiques telles que la fabrication de verres de lunettes. De par leurs propriétés thermoplastiques, ils peuvent être mis en forme par des procédés peu coûteux. De plus les chutes ou rebuts peuvent être réutilisés, ce qui présence des avantages du point de vue économique et environnemental. Polyacrylates are thermoplastic materials used in ophthalmic applications such as the manufacture of spectacle lenses. Because of their thermoplastic properties, they can be shaped by inexpensive processes. In addition, waste or scrap can be reused, which has economic and environmental benefits.
Toutefois, les substrats organiques, notamment en polyacrylates, ont généralement une résistance à l'abrasion très inférieure aux substrats en verre. Il est donc d'usage d'appliquer un revêtement sur la surface des substrats organiques pour améliorer leurs résistances à l'abrasion. However, organic substrates, especially polyacrylates, generally have a very low abrasion resistance to glass substrates. It is therefore customary to apply a coating on the surface of organic substrates to improve their resistance to abrasion.
Les vernis anti-abrasion utilisés classiquement pour les substrats en polycarbonate, ou en copolymère de polyuréthane n'adhèrent pas suffisamment aux substrats en polyacrylate. L'adhérence de ces vernis sur les substrats en polyacrylate a pu être améliorée par l'utilisation de primaires d'adhérence. Cependant, la formation d'une bicouche primaire/vernis antiabrasion est un procédé coûteux. Il subsiste donc un besoin de disposer de vernis antiabrasion présentant une bonne adhérence sur les substrats en polyacrylate sans nécessiter de primaire d'adhérence. The anti-abrasion varnishes conventionally used for substrates made of polycarbonate or of polyurethane copolymer do not adhere sufficiently to polyacrylate substrates. The adhesion of these varnishes to the polyacrylate substrates could be improved by the use of adhesion primers. However, the formation of a primary bilayer / anti-abrasion varnish is an expensive process. There remains therefore a need for abrasion-resistant varnish having good adhesion to polyacrylate substrates without the need for adhesion primer.
Partant de ce constat, la Demanderesse a développé une composition polymérisable comprenant un composé organosilicique durcissable permettant l'obtention d'un vernis antiabrasion présentant de bonne propriétés d'adhérence sur les substrats en polyacrylate même en l'absence de primaire d'adhérence, ainsi qu'une bonne tenue dans le temps et qui, par ailleurs, présente de bonnes propriétés anti-abrasion semblables voire supérieures à celles des vernis couramment utilisés.
Ainsi, la présente invention porte sur une composition polymérisable pour la réalisation de vernis sur au moins une face d'une lentille ophtalmique en matériau thermoplastique de la famille des polyacrylates, comprenant au moins un composé organosilicique durcissable et un catalyseur de condensation, la dite composition étant dépourvue de tout monomère comprenant une fonction vinyle ou époxy et de tout composé issu de tels monomères, afin d'améliorer l'adhésion dudit vernis sur ladite lentille. On the basis of this observation, the Applicant has developed a polymerizable composition comprising a curable organosilicic compound which makes it possible to obtain an abrasion-resistant varnish having good adhesion properties on the polyacrylate substrates even in the absence of an adhesion primer, and that a good behavior over time and which, moreover, has good anti-abrasion properties similar or even superior to those of commonly used varnishes. Thus, the present invention relates to a polymerizable composition for producing lacquer on at least one face of an ophthalmic lens made of thermoplastic material of the family of polyacrylates, comprising at least one curable organosilicon compound and a condensation catalyst, said composition being devoid of any monomer comprising a vinyl or epoxy function and any compound derived from such monomers, to improve the adhesion of said varnish on said lens.
Les monomères vinyliques ou époxy, tel que le γ-Glycidoxypropyltriméthoxysilane, sont souvent utilisés en ophtalmique pour promouvoir l'adhésion de vernis sur les substrats de lentilles, lesdits substrats étant, par exemple en polycarbonate, ou à base de polythiouréthanes ou de polysuflides. Vinyl or epoxy monomers, such as γ-glycidoxypropyltrimethoxysilane, are often used in ophthalmics to promote the adhesion of varnish to lens substrates, said substrates being, for example polycarbonate, or based on polythiourethanes or polysuflides.
Les inventeurs ont cependant identifié que de façon surprenante, les monomères vinyliques ou époxy diminuaient l'adhésion des vernis sur les substrats en matériau polyacrylate, en particulier en polyméthylméthacrylate. The inventors, however, have identified that, surprisingly, the vinyl or epoxy monomers decreased the adhesion of the lacquers to the substrates made of polyacrylate material, in particular polymethyl methacrylate.
Le composé organosilicique durcissable selon la présente invention est un composé résultant d'une réaction d'hydrolyse, en présence d'un premier acide, d'au moins deux monomères de formule (1) The curable organosilicon compound according to the present invention is a compound resulting from a hydrolysis reaction, in the presence of a first acid, of at least two monomers of formula (1)
R'„Si(OR)4-„ (1) dans laquelle n est un entier compris entre 0 et 3, chaque R' est indépendamment choisi parmi (Cl-Cô)alkyle, aryle et aryl(Cl-C6)alkyle, et chaque R est indépendamment choisi parmi (Cl-C6)alkyle. R '"Si (OR) 4 -" (1) wherein n is an integer from 0 to 3, each R' is independently selected from (C1-C6) alkyl, aryl and aryl (C1-C6) alkyl, and each R is independently selected from (C1-C6) alkyl.
De plus, le premier acide, utilisé pour la réaction d'hydrolyse, est un acide faible en milieu aqueux. In addition, the first acid used for the hydrolysis reaction is a weak acid in an aqueous medium.
Pour rappel, un acide faible en milieu aqueux est un acide qui ne se dissocie pas totalement dans l'eau. Les inventeurs ont identifié que l'usage d'un acide faible au lieu d'un acide fort, dans une composition sans monomères vinyliques ou époxy, permettait d'améliorer l'adhérence sur des substrats en matériau polyacrylate, en particulier le polyméthylméthacrylate et permettait notamment d'améliorer la durée de vie de la composition. La durée de vie de la composition
est la durée pendant laquelle la composition peut être conservée après avoir été fabriquée sans créer de défauts dans le vernis lors de son utilisation pour former un vernis sur une lentille. As a reminder, a weak acid in an aqueous medium is an acid that does not dissociate completely in water. The inventors have identified that the use of a weak acid instead of a strong acid, in a composition without vinyl or epoxy monomers, made it possible to improve the adhesion to substrates made of polyacrylate material, in particular polymethyl methacrylate, and allowed in particular to improve the life of the composition. The life of the composition is the time during which the composition can be preserved after being manufactured without creating defects in the varnish when used to form a varnish on a lens.
Selon un mode de réalisation préféré de l'invention, la composition polymérisable est destinée à la réalisation d'un vernis sur au moins une face d'une lentille ophtalmique dont le substrat est un thermoplastique de la famille des polyacrylates. According to a preferred embodiment of the invention, the polymerizable composition is intended for producing a varnish on at least one face of an ophthalmic lens whose substrate is a thermoplastic of the polyacrylate family.
Le terme « (Cl-Cô)alkyle » au sens de la présente invention désigne tout groupement linéaire ou ramifié monovalent de 1 à 6 atomes de carbone. Les (Cl-Cô)alkyles comprennent notamment les (Cl-C4)alkyles tels que méthyle, éthyle, propyle, isopropyle, butyle, isobutyle et tert-butyle. Le terme « aryle » au sens de la présente invention désigne tout groupement aromatique monovalent de 6 à 18 atomes de carbone, éventuellement substitué par 1 à 4 groupements, identiques ou différents indépendamment l'un de l'autre, choisis parmi les halogènes, (Cl- C6) alkyles, (C1-C6) alkyloxy. Les aryles sont notamment le radical phényle, le tolyle ou le naphtyle. Le terme « aryl(Cl-C6)alkyle » au sens de la présente invention désigne tout groupement (Cl-Cô)alkyle tel que défini ci-dessus substitué par un groupement aryle tel que défini ci-dessus. Les aryl(Cl-C6)alkyles comprennent notamment les aryl(Cl-C4)alkyles tels que le benzyle et le phényléthyle. The term "(C1-C6) alkyl" in the sense of the present invention denotes any monovalent linear or branched group of 1 to 6 carbon atoms. The (C1-C6) alkyls include especially (C1-C4) alkyls such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl. The term "aryl" in the sense of the present invention denotes any monovalent aromatic group of 6 to 18 carbon atoms, optionally substituted with 1 to 4 groups, identical or different independently of one another, chosen from halogens ( C1-C6) alkyl, (C1-C6) alkyloxy. The aryls are especially the phenyl radical, tolyl or naphthyl. The term "aryl (C1-C6) alkyl" within the meaning of the present invention denotes any (Cl-C6) alkyl group as defined above substituted by an aryl group as defined above. The aryl (C1-C6) alkyls include in particular aryl (C1-C4) alkyls such as benzyl and phenylethyl.
Dans la formule (1), chaque R' est de préférence indépendamment choisi parmi (Cl- C4)alkyle, phényle et phényl(Cl-C4)alkyle, plus préférentiellement indépendamment choisi parmi (Cl-C4)alkyle, encore plus préférentiellement indépendamment choisi parmi méthyle et éthyle ; et chaque R est de préférence indépendamment choisi parmi (Cl-C4)alkyle, plus préférentiellement indépendamment choisi parmi méthyle et éthyle. In the formula (1), each R 'is preferably independently selected from (C1-C4) alkyl, phenyl and phenyl (C1-C4) alkyl, more preferably independently selected from (C1-C4) alkyl, still more preferably independently selected from methyl and ethyl; and each R is preferably independently selected from (C1-C4) alkyl, more preferably independently selected from methyl and ethyl.
Le composé organosilicique est obtenu par hydrolyse d'au moins deux monomères de formule (1) telle que définie ci-dessus. De préférence, lesdits au moins deux monomères comprennent un monomère (A) de formule (1) dans laquelle n est un entier compris 1 à 3, chaque R' est indépendamment choisi parmi (Cl-Cô)alkyle, aryle, aryl(Cl-C6)alkyle, et chaque R est indépendamment choisi parmi (Cl-Cô)alkyle ; et un monomère (B) de formule (1) dans laquelle n est 0 et chaque R est indépendamment choisi parmi (Cl-Cô)alkyle.
Le monomère (A) est de préférence un monomère de formule (1) dans laquelle n est 1 ou 2, et chaque R est indépendamment choisi parmi (Ci-C4)alkyl, et chaque R' est indépendamment choisi parmi (Cl-C4)alkyle. En particulier, le monomère (A) peut être choisi parmi le méthyltriméthoxysilane, le méthyltriéthoxysilane et le diméthyldiéthoxysilane. Le monomère (B) est de préférence un monomère de formule (1) dans laquelle n est 0 et chaque R est indépendamment choisi parmi (Cl-C4)alkyle. En particulier, le monomère (B) peut être choisi parmi le tétraméthoxysilane et tétraéthoxysilane. The organosilicon compound is obtained by hydrolysis of at least two monomers of formula (1) as defined above. Preferably, said at least two monomers comprise a monomer (A) of formula (1) in which n is an integer 1 to 3, each R 'is independently selected from (C 1 -C 6) alkyl, aryl, aryl (Cl- C6) alkyl, and each R is independently selected from (C1-C6) alkyl; and a monomer (B) of formula (1) wherein n is 0 and each R is independently selected from (C1-C6) alkyl. The monomer (A) is preferably a monomer of formula (1) in which n is 1 or 2, and each R is independently selected from (C 1 -C 4) alkyl, and each R 'is independently selected from (C 1 -C 4) alkyl. In particular, the monomer (A) may be chosen from methyltrimethoxysilane, methyltriethoxysilane and dimethyldiethoxysilane. The monomer (B) is preferably a monomer of formula (1) wherein n is 0 and each R is independently selected from (C1-C4) alkyl. In particular, the monomer (B) may be chosen from tetramethoxysilane and tetraethoxysilane.
Dans un mode de réalisation particulier, le composé organosilicique est obtenu par hydrolyse d'un monomère (A) choisi parmi le méthyltriéthoxysilane et le méthyltriéthoxysilane, et du tétraéthoxysilane en tant que monomère (B). In a particular embodiment, the organosilicon compound is obtained by hydrolysis of a monomer (A) chosen from methyltriethoxysilane and methyltriethoxysilane, and tetraethoxysilane as monomer (B).
La composition selon l'invention comprend typiquement de 80 à 98% en poids, de préférence de 85 à 95% en poids, de composé organosilicique par rapport au poids sec total de la composition. Dans le cas où lesdits au moins deux monomères de formule (1) comprennent un monomère (A) et un monomère (B), la proportion de monomère (A) représente typiquement de 50 à 90% en poids, de préférence de 60 à 85% en poids, plus préférentiellement de 70 à 80% en poids par rapport au total poids sec de la composition, et le monomère (B) représente typiquement de 5 à 40% en poids, de préférence de 8 à 30% en poids, plus préférentiellement de 10 à 20% en poids par rapport au total poids sec de la composition. Le ratio molaire du monomère (B) par rapport au monomère (A) est de préférence compris entre 0,01 à 0,5, plus préférentiellement compris entre 0,1 à 0,3. The composition according to the invention typically comprises from 80 to 98% by weight, preferably from 85 to 95% by weight, of organosilicic compound relative to the total dry weight of the composition. In the case where said at least two monomers of formula (1) comprise a monomer (A) and a monomer (B), the proportion of monomer (A) is typically 50 to 90% by weight, preferably 60 to 85% by weight. % by weight, more preferably 70 to 80% by weight relative to the total dry weight of the composition, and the monomer (B) is typically 5 to 40% by weight, preferably 8 to 30% by weight, more preferably from 10 to 20% by weight relative to the total dry weight of the composition. The molar ratio of the monomer (B) relative to the monomer (A) is preferably between 0.01 to 0.5, more preferably between 0.1 to 0.3.
L'hydrolyse est réalisée en présence d'un premier acide qui est un acide faible en milieu aqueux. Le premier acide peut être un acide carboxylique choisi par exemple parmi l'acide acétique, l'acide propionique, l'acide butyrique, l'acide acrylique et leurs mélanges. De préférence, l'acide faible est l'acide acétique. L'hydrolyse est de préférence réalisée à un pH compris entre 4,0 et 4,5. The hydrolysis is carried out in the presence of a first acid which is a weak acid in an aqueous medium. The first acid may be a carboxylic acid selected for example from acetic acid, propionic acid, butyric acid, acrylic acid and mixtures thereof. Preferably, the weak acid is acetic acid. The hydrolysis is preferably carried out at a pH of between 4.0 and 4.5.
La composition selon l'invention comprend un catalyseur de condensation choisi notamment parmi les imidazoles, les amidines et les amidines cycliques ou bicycliques. Des exemples de catalyseur de condensation comprennent le N-méthylimidazole, le
diazabicycloundecène et le diazabicyclononène. De préférence, le catalyseur de condensation est le l,8-diazabicyclo[5.4.0]undéc-7-ène (DBU). The composition according to the invention comprises a condensation catalyst chosen in particular from imidazoles, amidines and cyclic or bicyclic amidines. Examples of the condensation catalyst include N-methylimidazole, diazabicycloundecene and diazabicyclononene. Preferably, the condensation catalyst is 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU).
La composition selon l'invention comprend typiquement de 0,1 à 2% en poids, de préférence de 0,3 à 1% en poids de catalyseur de condensation par rapport au poids sec de la composition. The composition according to the invention typically comprises from 0.1 to 2% by weight, preferably from 0.3 to 1% by weight of condensation catalyst relative to the dry weight of the composition.
La composition selon l'invention comprend optionnellement un second acide, ledit acide étant de préférence un acide faible en milieu aqueux, et plus préférentiellement un acide carboxylique, encore plus préférentiellement choisi parmi l'acide acétique, l'acide propionique, l'acide butyrique, l'acide acrylique et leurs mélanges, l'acide acétique étant préféré. Ce second acide est ajouté durant les étapes de préparation de la composition postérieurement à la première étape d'hydrolyse, et il peut être identique ou différent du premier acide utilisé durant la première étape d'hydrolyse. Ce second acide a un rôle d'ajustement du pH de la composition polymérisable et peut permettre de stabiliser la composition et donc allonger la durée de vie de la dite composition. La composition selon l'invention présente typiquement un pH compris entre 3,5 et 5, de préférence compris entre 4,0 et 4,7. The composition according to the invention optionally comprises a second acid, said acid being preferably a weak acid in an aqueous medium, and more preferably a carboxylic acid, more preferably chosen from acetic acid, propionic acid or butyric acid. acrylic acid and mixtures thereof, with acetic acid being preferred. This second acid is added during the steps of preparing the composition after the first hydrolysis step, and it may be the same or different from the first acid used during the first hydrolysis step. This second acid has a role in adjusting the pH of the polymerizable composition and can make it possible to stabilize the composition and thus extend the life of said composition. The composition according to the invention typically has a pH of between 3.5 and 5, preferably between 4.0 and 4.7.
La composition selon l'invention peut également comprendre des additifs complémentaires tels que des solvants organiques ou des tensio-actifs, tels que ceux usuellement utilisés par l'homme de l'art des vernis anti-abrasion pour le domaine ophtalmique. The composition according to the invention may also comprise additional additives such as organic solvents or surfactants, such as those conventionally used by those skilled in the art of anti-abrasion varnishes for the ophthalmic field.
La composition selon l'invention peut également comprendre des colloïdes afin d'accroître la dureté et la résistance à l'abrasion du vernis. Ces colloïdes sont par exemple des colloïdes de silice, de silice creuse, de zircone ou de dioxyde de titane. Typiquement, la composition selon l'invention peut comprendre au plus 60% en poids de colloïdes par rapport au poids sec de la composition. The composition according to the invention may also comprise colloids in order to increase the hardness and the resistance to abrasion of the varnish. These colloids are, for example, colloids of silica, hollow silica, zirconia or titanium dioxide. Typically, the composition according to the invention may comprise at most 60% by weight of colloids relative to the dry weight of the composition.
La composition est dépourvue de monomère comprenant une fonction époxy ou vinyle. De préférence, la composition ne comprend aucun monomère silane comprenant une fonction polymérisable différente d'un alkyloxy. Plus préférentiellement, la composition ne comprend aucun monomère comprenant une fonction polymérisable différente d'un alkyloxy. Dans un
mode de réalisation particulier, la composition selon l'invention ne comprend comme monomères que des monomères de formule (1) ou leurs hydrolysats. The composition is free of monomer comprising an epoxy or vinyl function. Preferably, the composition does not comprise any silane monomer comprising a polymerizable function other than an alkyloxy. More preferably, the composition does not comprise any monomer comprising a polymerizable function other than an alkyloxy. In one particular embodiment, the composition according to the invention comprises as monomers only monomers of formula (1) or their hydrolysates.
La présente invention porte également sur un procédé de préparation d'une composition polymérisable pour la réalisation de vernis sur au moins une face d'une lentille ophtalmique en matériau thermoplastique de la famille des polyacrylates, de préférence du polyméthylméthacrylate (PMMA), telle que définie ci-dessus. The present invention also relates to a method for preparing a polymerizable composition for producing a varnish on at least one face of an ophthalmic lens of thermoplastic material of the family of polyacrylates, preferably polymethyl methacrylate (PMMA), as defined above.
Ce procédé comprend : This process comprises:
- l'hydrolyse, en présence d'un premier acide, d'au moins deux monomères de formule de formule (1) the hydrolysis, in the presence of a first acid, of at least two monomers of formula of formula (1)
R'nSi(OR)4-„ (1) dans laquelle n est un entier compris entre 0 et 3, chaque R' est indépendamment choisi parmi (Cl-Cô)alkyle, aryle, aryl(Cl-C6)alkyle, et chaque R est indépendamment choisi parmi (Cl- C6)alkyle; R ' n Si (OR) 4 - "(1) wherein n is an integer from 0 to 3, each R' is independently selected from (C1-C6) alkyl, aryl, aryl (C1-C6) alkyl, and each R is independently selected from (C1-C6) alkyl;
pour obtenir un hydrolysat comprenant un composé organosilicique durcissable ; to obtain a hydrolyzate comprising a curable organosilicon compound;
- l'ajout d'un catalyseur de condensation et optionnellement d'un second acide à l'hydrolysat obtenu à l'étape d'hydrolyse. the addition of a condensation catalyst and optionally a second acid to the hydrolyzate obtained in the hydrolysis step.
L'hydrolyse est réalisée à partir d'un mélange à hydrolyser comprenant au moins deux monomères de formule (1) en présence du premier acide et d'eau. Elle conduit à un hydrolysat comprenant un composé organosilicique durcissable. The hydrolysis is carried out from a mixture to be hydrolysed comprising at least two monomers of formula (1) in the presence of the first acid and water. It leads to a hydrolyzate comprising a curable organosilicon compound.
Le premier acide est un acide faible en milieu aqueux. The first acid is a weak acid in an aqueous medium.
L'hydrolyse est réalisée en présence d'un premier acide. Le premier acide peut être un acide carboxylique choisi par exemple parmi l'acide acétique, l'acide propionique, l'acide butyrique, l'acide acrylique et leurs mélanges. De préférence, le premier acide est l'acide acétique. The hydrolysis is carried out in the presence of a first acid. The first acid may be a carboxylic acid selected for example from acetic acid, propionic acid, butyric acid, acrylic acid and mixtures thereof. Preferably, the first acid is acetic acid.
Les monomères de formule (1) sont de préférence tels que définis plus haut pour la composition selon l'invention. Dans le cas où lesdits moins deux monomères de formule (1) comprennent un monomère (A) et un monomère (B), le ratio molaire du monomère (B) par rapport au monomère (A) est de préférence compris entre 0,01 à 0,5, plus préférentiellement
compris entre 0,1 à 0,3. Le mélange à hydrolyser comprend typiquement 40 à 80% en poids, de préférence 50 à 70% en poids, plus préférentiellement 55 à 65% en poids de monomère (A) ; 2 à 20% en poids, de préférence 5 à 15% en poids, plus préférentiellement 7 à 13% en poids de monomère (B) ; 1 à 9% en poids, de préférence 3 à 7% en poids du premier acide faible ; et 15 à 35% en poids, de préférence 20 à 30% en poids d'eau. The monomers of formula (1) are preferably as defined above for the composition according to the invention. In the case where said at least two monomers of formula (1) comprise a monomer (A) and a monomer (B), the molar ratio of the monomer (B) relative to the monomer (A) is preferably between 0.01 to 0.5, more preferably between 0.1 to 0.3. The mixture to be hydrolysed typically comprises 40 to 80% by weight, preferably 50 to 70% by weight, more preferably 55 to 65% by weight of monomer (A); 2 to 20% by weight, preferably 5 to 15% by weight, more preferably 7 to 13% by weight of monomer (B); 1 to 9% by weight, preferably 3 to 7% by weight of the first weak acid; and 15 to 35% by weight, preferably 20 to 30% by weight of water.
Dans un mode de réalisation préféré, l'hydrolyse est réalisée à un pH compris entre 3,5 et 5,0, préférentiellement 4,0 à 4,7. L'hydrolyse est typiquement réalisée pendant 10 à 50h, de préférence pendant 20 à 30h. L'hydrolyse est généralement réalisée à température ambiante. Cependant, la réaction d'hydrolyse peut faire augmenter la température du milieu de réaction au cours de l'hydrolyse. La température est de préférence maintenue en deçà de 50°C. In a preferred embodiment, the hydrolysis is carried out at a pH of between 3.5 and 5.0, preferably 4.0 to 4.7. The hydrolysis is typically carried out for 10 to 50 hours, preferably for 20 to 30 hours. The hydrolysis is generally carried out at room temperature. However, the hydrolysis reaction may increase the temperature of the reaction medium during hydrolysis. The temperature is preferably maintained below 50 ° C.
L'hydrolyse ne fait intervenir aucun monomère comprenant une fonction époxy ou vinyle. De préférence, l'hydrolyse ne fait intervenir aucun monomère silane comprenant une fonction polymérisable différente d'un alkyloxy. De préférence, l'hydrolyse ne fait intervenir aucun monomère comprenant une fonction polymérisable différente d'un alkyloxy. Dans un mode de réalisation particulier, l'hydrolyse ne fait intervenir que des monomères de formule (1). The hydrolysis does not involve any monomer comprising an epoxy or vinyl function. Preferably, the hydrolysis does not involve any silane monomer comprising a polymerizable function different from an alkyloxy. Preferably, the hydrolysis does not involve any monomer comprising a polymerizable function different from an alkyloxy. In a particular embodiment, the hydrolysis involves only monomers of formula (1).
A l'issue de l'étape d'hydrolyse, le catalyseur de condensation et optionnellement le second acide faible sont ajoutés à l'hydrolysat obtenu. L'ajout du catalyseur de condensation et du second acide si présent faible peut être réalisé simultanément ou séparément. Par exemple, le second acide faible est ajouté postérieurement au catalyseur de condensation. At the end of the hydrolysis step, the condensation catalyst and optionally the second weak acid are added to the hydrolyzate obtained. The addition of the condensation catalyst and the second acid if present weak can be carried out simultaneously or separately. For example, the second weak acid is added after the condensation catalyst.
Le catalyseur de condensation est de préférence tel que défini plus haut pour la composition selon l'invention. Le catalyseur de condensation peut être ajouté à raison de 0,1 à 2% en poids, de préférence de 0,3 à 1% en poids par rapport au poids sec total de la composition polymérisable. Le second acide est de préférence un acide faible en milieu aqueux. Il peut être identique ou différent du premier acide. De préférence, le premier acide et le second acide sont identiques. Le second acide peut être un acide carboxylique choisi par exemple parmi l'acide acétique, l'acide propionique, l'acide butyrique, l'acide acrylique et leurs mélanges. De préférence, le second acide est l'acide acétique. Le second acide est ajouté en quantité suffisante pour que la composition polymérisable présente un pH compris entre 4,0 et 4,7.
D'autres composants tels qu'un solvant, des tensio-actifs ou des colloïdes tels que définis plus haut pour la composition selon l'invention peuvent être ajoutés. The condensation catalyst is preferably as defined above for the composition according to the invention. The condensation catalyst may be added in a proportion of 0.1 to 2% by weight, preferably 0.3 to 1% by weight relative to the total dry weight of the polymerizable composition. The second acid is preferably a weak acid in an aqueous medium. It may be the same or different from the first acid. Preferably, the first acid and the second acid are identical. The second acid may be a carboxylic acid selected for example from acetic acid, propionic acid, butyric acid, acrylic acid and mixtures thereof. Preferably, the second acid is acetic acid. The second acid is added in an amount sufficient for the polymerizable composition to have a pH of between 4.0 and 4.7. Other components such as a solvent, surfactants or colloids as defined above for the composition according to the invention may be added.
Dans le procédé selon l'invention, aucun monomère comprenant une fonction époxy ou vinyle n'est ajouté à l'hydrolysat obtenu à l'issue de l'étape d'hydrolyse. De préférence, aucun monomère silane comprenant une fonction polymérisable différente d'un alkyloxy n'est ajouté à l'hydrolysat. De préférence, aucun monomère comprenant une fonction polymérisable différente d'un alkyloxy n'est ajouté à l'hydrolysat. Dans un mode de réalisation particulier, la composition selon l'invention ne comprend que des monomères de formule (1). La composition selon l'invention permet d'obtenir des vernis présentant une très bonne résistance, notamment une résistance à l'abrasion supérieure ou égale à 1,8, de préférence supérieur ou égale à 2. De plus, ces vernis présentent une bonne adhérence sur les supports en polyacrylates, notamment le PMMA, même en l'absence de primaire d'adhérence. La résistance à l'abrasion est mesurée en utilisant le test BAYER effectuée conformément à la norme ASTM F735.81. Une valeur élevée au test BAYER correspond à un degré élevé de résistance à l'abrasion. In the process according to the invention, no monomer comprising an epoxy or vinyl function is added to the hydrolyzate obtained at the end of the hydrolysis step. Preferably, no silane monomer comprising a polymerizable function different from an alkyloxy is added to the hydrolyzate. Preferably, no monomer comprising a polymerizable function other than an alkyloxy is added to the hydrolyzate. In a particular embodiment, the composition according to the invention comprises only monomers of formula (1). The composition according to the invention makes it possible to obtain varnishes having a very good resistance, in particular an abrasion resistance greater than or equal to 1.8, preferably greater than or equal to 2. Moreover, these varnishes have good adhesion. on polyacrylate supports, in particular PMMA, even in the absence of adhesion primer. Abrasion resistance is measured using the BAYER test performed in accordance with ASTM F735.81. A high value in the BAYER test corresponds to a high degree of resistance to abrasion.
Ainsi, la présente invention porte également sur un vernis obtenu à partir de la composition polymérisable telle que définie ci-dessus. Plus précisément, le vernis est obtenu par application, par des procédés bien connu de l'homme du métier tels que par exemple par « spin coating » (c'est-à-dire dépôt à la tournette), ou « spray » (soit pulvérisation), ou impression jet de matière (« ink-jet » en anglais) ou encore « dip-coating » (c'est-à-dire dépôt par immersion) d'une couche de la composition selon l'invention sur un substrat et à polymériser ladite couche de composition par voie thermique, de préférence à une température inférieure à la température de transition vitreuse du substrat. La présente invention porte également sur une lentille ophtalmique comprenant un substrat en matériau thermoplastique polyacrylate, de préférence en PMMA, revêtu du vernis selon l'invention tel que défini ci-dessus. Une telle lentille ophtalmique peut être fabriquée par un procédé comprenant l'application de la composition polymérisable selon l'invention sur au moins une face d'un substrat en matériau thermoplastique polyacrylate, de préférence en PMMA, et la polymérisation par voie thermique, de préférence à une température
inférieure à la température de transition vitreuse dudit substrat de la couche de composition polymérisable ainsi obtenue. Thus, the present invention also relates to a varnish obtained from the polymerizable composition as defined above. More specifically, the varnish is obtained by application, by methods well known to those skilled in the art such as for example by "spin coating" (that is to say spin coating), or "spray" (either spraying), or jet printing of material ("ink-jet" in English) or "dip-coating" (that is to say, dip coating) of a layer of the composition according to the invention on a substrate and polymerizing said composition layer thermally, preferably at a temperature below the glass transition temperature of the substrate. The present invention also relates to an ophthalmic lens comprising a substrate made of thermoplastic polyacrylate material, preferably made of PMMA, coated with the varnish according to the invention as defined above. Such an ophthalmic lens may be manufactured by a process comprising applying the polymerizable composition according to the invention to at least one face of a substrate made of thermoplastic polyacrylate material, preferably PMMA, and the polymerization by a thermal route, preferably at a temperature less than the glass transition temperature of said substrate of the polymerizable composition layer thus obtained.
Exemples Examples
Exemple 1 On effectue l'hydrolyse, pendant 24h, de 267,8 g de méthyltriéthoxysilane et 38,8 g de trétraéthoxysilane en présence de 20 g d'acide acétique et 94,6 g d'eau. Example 1 267.8 g of methyltriethoxysilane and 38.8 g of tretraethoxysilane in the presence of 20 g of acetic acid and 94.6 g of water are hydrolyzed for 24 hours.
A l'issue de l'hydrolyse, 2,2 g de DBU (diazabicycloundécène) sont ajoutés et mélangés à l'hydrolysat obtenu. Enfin, 15 g d'acide acétique et 0,6 g d'un tensio-actif (EFKA 3034 commercialisé par Aldrich) sont ajoutés à la composition pour obtenir un vernis prêt à l'emploi After the hydrolysis, 2.2 g of DBU (diazabicycloundecene) are added and mixed with the hydrolyzate obtained. Finally, 15 g of acetic acid and 0.6 g of a surfactant (EFKA 3034 marketed by Aldrich) are added to the composition to obtain a ready-to-use varnish.
Exemple comparatif 1 Comparative Example 1
On effectue l'hydrolyse, pendant 24h de 487,4 g de méthyltriméthoxysilane, et 142 g de tétraéthoxysilane en présence de 50 g d'acide acétique et 248 g d'eau. A l'issue de la première hydrolyse, 80 g de glycidyloxypropyltriméthoxysilane et 20 g d'eau sont ajoutés à l'hydrolysat. Une seconde hydrolyse est réalisée pendant 3 à 4 jours. A l'issue de la seconde hydrolyse, entre 0,8 % et 1,3 % de DBU pour obtenir un vernis prêt à l'emploi. The hydrolysis is carried out for 487.4 g of methyltrimethoxysilane and 142 g of tetraethoxysilane in the presence of 50 g of acetic acid and 248 g of water. At the end of the first hydrolysis, 80 g of glycidyloxypropyltrimethoxysilane and 20 g of water are added to the hydrolyzate. A second hydrolysis is carried out for 3 to 4 days. At the end of the second hydrolysis, between 0.8% and 1.3% of DBU to obtain a ready-to-use varnish.
Caractérisation des vernis Characterization of varnishes
Une couche de composition selon l'exemple 1 ou selon l'exemple comparatif 1 est appliquée par immersion sur une lentille en PMMA sans primaire d'adhésion. Ce revêtement est polymérisé pendant 3h à une température de 100°C. A composition layer according to Example 1 or Comparative Example 1 is applied by immersion to a PMMA lens without adhesion primer. This coating is polymerized for 3 hours at a temperature of 100 ° C.
L'adhésion du revêtement est mesuré selon le test d'adhésion par quadrillage (crosshatch adhésion test) en suivant la norme ISTM 02-010. Ce test défini une note d'adhésion de 0 à 5. Une note de 0 ou 1 est acceptable pour des verres ophtalmiques tandis que les notes de 3 à 5 ne sont pas acceptables. The adhesion of the coating is measured according to the crosshatch adhesion test according to the ISTM 02-010 standard. This test defines a membership score of 0 to 5. A score of 0 or 1 is acceptable for ophthalmic lenses while scores of 3 to 5 are not acceptable.
La résistance à l'abrasion est mesurée selon le test Bayer en suivant la ATSM F735.81. Plus la valeur est élevée, plus la résistance à l'abrasion est bonne.
Les résultats sont présentés dans le tableau 1 ci-des The abrasion resistance is measured according to the Bayer test according to ATSM F735.81. The higher the value, the better the resistance to abrasion. The results are shown in Table 1 below.
Tableau 1 Table 1
Exemple Example
Exemple 1 Example 1
comparatif 1 comparative 1
Adhésion 0 5Membership 0 5
Résistance à l'abrasion 2,0 1,6
Abrasion resistance 2.0 1.6
Claims
1. Composition polymérisable pour la réalisation de vernis sur au moins une face d'une lentille ophtalmique en matériau thermoplastique de la famille des polyacrylates, comprenant un composé organosilicique durcissable, et un catalyseur de condensation, la dite composition étant dépourvue de tout monomère comprenant une fonction vinyle ou époxy et de tout composé issu de tels monomères, afin d'améliorer l'adhésion dudit vernis sur ladite lentille, dans laquelle le composé organosilicique durcissable est un composé résultant d'une réaction d'hydrolyse, en présence d'un premier acide, d'au moins deux monomères de formule de formule (1) 1. Polymerizable composition for producing a varnish on at least one side of an ophthalmic lens made of thermoplastic material of the polyacrylate family, comprising a curable organosilicon compound and a condensation catalyst, said composition being free of any monomer comprising a vinyl or epoxy function and any compound derived from such monomers, in order to improve the adhesion of said varnish to said lens, wherein the curable organosilicon compound is a compound resulting from a hydrolysis reaction, in the presence of a first acid, of at least two monomers of formula of formula (1)
R'nSi(OR)4-„ (1) dans laquelle n est un entier compris entre 0 et 3, chaque R' est indépendamment choisi parmi (Cl-Cô)alkyle, aryle, aryl(Cl-C6)alkyle, et chaque R est indépendamment choisi parmi (Cl- C6)alkyle, et R ' n Si (OR) 4 - "(1) wherein n is an integer from 0 to 3, each R' is independently selected from (C1-C6) alkyl, aryl, aryl (C1-C6) alkyl, and each R is independently selected from (C 1 -C 6) alkyl, and
dans laquelle le premier acide est un acide faible en milieu aqueux. wherein the first acid is a weak acid in an aqueous medium.
2. Composition selon la revendication 1, dans laquelle lesdits au moins deux monomères comprennent : The composition of claim 1, wherein said at least two monomers comprise:
un monomère (A) de formule (1) dans laquelle n est un entier compris 1 à 3, chaque R' est indépendamment choisi parmi (Cl-Cô)alkyle, aryle, aryl(Cl-C6)alkyle, et chaque R est indépendamment choisi parmi (Cl-Cô)alkyle ; et a monomer (A) of formula (1) wherein n is an integer 1 to 3, each R 'is independently selected from (C1-C6) alkyl, aryl, aryl (C1-C6) alkyl, and each R is independently selected from (C1-C6) alkyl; and
un monomère (B) de formule (1) dans laquelle n est 0 et chaque R est indépendamment choisi parmi (Cl-Cô)alkyle. a monomer (B) of formula (1) wherein n is 0 and each R is independently selected from (C1-C6) alkyl.
3. Composition selon la revendication 2, dans laquelle le monomère (A) est un monomère de formule (1) dans laquelle n est 1 ou 2, et chaque R est indépendamment choisi parmi (Cl- C4)alkyl, et chaque R' est indépendamment choisi parmi (Cl-C4)alkyle ; et le monomère (B) est un monomère de formule (1) dans laquelle n est 0 et chaque R est indépendamment choisi parmi (Cl-C4)alkyle ; de préférence, le monomère (A) est choisi parmi le méthyltriméthoxysilane, le méthyltriéthoxysilane et le diméthyldiéthoxysilane, et le monomère (B) est le tétraéthoxysilane.
The composition of claim 2, wherein the monomer (A) is a monomer of formula (1) wherein n is 1 or 2, and each R is independently selected from (C 1 -C 4) alkyl, and each R 'is independently selected from (C1-C4) alkyl; and the monomer (B) is a monomer of formula (1) wherein n is 0 and each R is independently selected from (C1-C4) alkyl; preferably, the monomer (A) is chosen from methyltrimethoxysilane, methyltriethoxysilane and dimethyldiethoxysilane, and the monomer (B) is tetraethoxysilane.
4. Composition selon l'une quelconque des revendications 2 ou 3, dans laquelle le ratio molaire du monomère (B) par rapport au monomère (A) est de 0,01 à 0,5, de préférence de 0,1 à 0,3. 4. Composition according to any one of claims 2 or 3, wherein the molar ratio of the monomer (B) relative to the monomer (A) is from 0.01 to 0.5, preferably from 0.1 to 0, 3.
5. Composition selon l'une quelconque des revendications 1 à 4, dans laquelle le catalyseur de condensation est choisi parmi les imidazoles, les amidines et les amidines cycliques ou bicycliques, de préférence le catalyseur de condensation est le l,8-diazabicyclo[5.4.0]undéc- 7-ène (DBU). 5. Composition according to any one of claims 1 to 4, wherein the condensation catalyst is chosen from cyclic or bicyclic imidazoles, amidines and amidines, preferably the condensation catalyst is 1,8-diazabicyclo [5.4]. .0] undec-7-ene (DBU).
6. Composition selon l'une quelconque des revendications 1 à 5, dans laquelle le premier acide faible utilisé pour l'hydrolyse desdits au moins deux monomères de formule (1) est un acide carboxylique, de préférence choisi parmi l'acide acétique, l'acide propionique, l'acide butyrique, l'acide acrylique et leurs mélanges. 6. Composition according to any one of claims 1 to 5, wherein the first weak acid used for the hydrolysis of said at least two monomers of formula (1) is a carboxylic acid, preferably selected from acetic acid, propionic acid, butyric acid, acrylic acid and mixtures thereof.
7. Composition selon l'une quelconque des revendications 1 à 6 comprenant un second acide, de préférence un acide carboxylique, plus préférentiellement choisi parmi l'acide acétique, l'acide propionique, l'acide butyrique, l'acide acrylique et leurs mélanges. 7. Composition according to any one of claims 1 to 6 comprising a second acid, preferably a carboxylic acid, more preferably chosen from acetic acid, propionic acid, butyric acid, acrylic acid and mixtures thereof. .
8. Composition selon l'une quelconque des revendications 1 à 7, ayant un pH compris entre 3,5 et 5,0, de préférence entre 4,0 et 4,7 inclus. 8. Composition according to any one of claims 1 to 7, having a pH between 3.5 and 5.0, preferably between 4.0 and 4.7 inclusive.
9. Composition selon l'une des revendications 1 à 8, le substrat étant du polyméthylméthacrylate (PMMA). 9. Composition according to one of claims 1 to 8, the substrate being polymethylmethacrylate (PMMA).
10. Procédé de préparation d'une composition polymérisable telle que définie à l'une quelconque des revendications 1 à 9, comprenant : 10. Process for the preparation of a polymerizable composition as defined in any one of Claims 1 to 9, comprising:
- l'hydrolyse, en présence d'un premier acide, d'au moins deux monomères de formule de formule (1) the hydrolysis, in the presence of a first acid, of at least two monomers of formula of formula (1)
R'nSi(OR)4-„ (1) dans laquelle n est un entier compris entre 0 et 3, chaque R' est indépendamment choisi parmi (Cl-Cô)alkyle, aryle, aryl(Cl-C6)alkyle, et chaque R est indépendamment choisi parmi (Cl- C6)alkyle ; R ' n Si (OR) 4 - "(1) wherein n is an integer from 0 to 3, each R' is independently selected from (C1-C6) alkyl, aryl, aryl (C1-C6) alkyl, and each R is independently selected from (C1-C6) alkyl;
pour obtenir un hydrolysat comprenant un composé organosilicique durcissable et to obtain a hydrolyzate comprising a curable organosilicon compound and
ledit premier acide étant un acide faible en milieu aqueux ;
- l'ajout d'un catalyseur de condensation et optionnellement d'un second acide faible à l'hydrolysat obtenu à l'étape d'hydrolyse. said first acid being a weak acid in an aqueous medium; the addition of a condensation catalyst and optionally a second weak acid to the hydrolyzate obtained in the hydrolysis step.
11. Vernis obtenu à partir de la composition polymérisable telle que définie à l'une quelconque des revendications 1 à 9. 11. Varnish obtained from the polymerizable composition as defined in any one of claims 1 to 9.
12. Lentille ophtalmique comprenant un substrat en matériau thermoplastique polyacrylate, de préférence en PMMA, revêtu d'un vernis obtenu à partir de la composition polymérisable telle que définie à l'une quelconque des revendications 1 à 9. 12. Ophthalmic lens comprising a substrate made of thermoplastic polyacrylate material, preferably PMMA, coated with a varnish obtained from the polymerizable composition as defined in any one of claims 1 to 9.
13. Procédé de fabrication d'une lentille ophtalmique selon la revendication 12, comprenant : l'application de la composition polymérisable telle que définie selon l'une quelconque des revendications 1 à 9 sur au moins une face d'un substrat en matériau thermoplastique polyacrylate, de préférence en PMMA, et 13. A method of manufacturing an ophthalmic lens according to claim 12, comprising: applying the polymerizable composition as defined according to any one of claims 1 to 9 on at least one side of a substrate made of thermoplastic polyacrylate material preferably in PMMA, and
la polymérisation par voie thermique de la couche de composition polymérisable ainsi obtenue.
the thermal polymerization of the polymerizable composition layer thus obtained.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1457394A FR3024457B1 (en) | 2014-07-30 | 2014-07-30 | ANTI-ABRASION VARNISH COMPOSITION FOR THERMOPLASTIC POLYACRYLATE SUBSTRATE |
| PCT/FR2015/052066 WO2016016562A1 (en) | 2014-07-30 | 2015-07-27 | Anti-abrasion varnish composition for a substrate made from thermoplastic polyacrylate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP3174947A1 true EP3174947A1 (en) | 2017-06-07 |
Family
ID=51830508
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP15756201.8A Withdrawn EP3174947A1 (en) | 2014-07-30 | 2015-07-27 | Anti-abrasion varnish composition for a substrate made from thermoplastic polyacrylate |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20170210942A1 (en) |
| EP (1) | EP3174947A1 (en) |
| CN (1) | CN106661378A (en) |
| FR (1) | FR3024457B1 (en) |
| WO (1) | WO2016016562A1 (en) |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4006271A (en) * | 1976-01-28 | 1977-02-01 | Itek Corporation | Abrasion resistant coating for polycarbonate substrates |
| JPS6017380B2 (en) * | 1979-06-06 | 1985-05-02 | ダイセル化学工業株式会社 | Composition for surface coating |
| FR2523590B1 (en) * | 1982-03-16 | 1984-06-29 | Inst Nat Rech Chimique | BASIC LIQUID COMPOSITION SUITABLE FOR PRODUCING TRANSPARENT OR VARNISHED COATINGS ON SOLID SURFACES, PROCESS FOR OBTAINING VARNISHES AND VARNISHES THEREFROM |
| WO1995016731A1 (en) * | 1993-12-13 | 1995-06-22 | Ppg Industries, Inc. | Coating composition and articles having a cured coating |
| KR100879490B1 (en) * | 2001-12-19 | 2009-01-20 | 바셀 폴리올레핀 이탈리아 에스.알.엘 | Impact Resistant Polyolefin Composition |
| FR2874007B1 (en) * | 2004-08-03 | 2007-11-23 | Essilor Int | PROCESS FOR PRODUCING A SUBSTRATE COATED WITH A MESOPOROUS LAYER AND ITS OPTICAL APPLICATION |
| US7294405B2 (en) * | 2004-08-26 | 2007-11-13 | 3M Innovative Properties Company | Antiglare coating and articles |
| CN1752165A (en) * | 2004-09-23 | 2006-03-29 | 张崇照 | Organic silicon transparent wear-proof hardened coating and mfg. process thereof |
| US7709551B2 (en) * | 2005-06-02 | 2010-05-04 | Lg Chem, Ltd. | Coating composition for film with low refractive index and film prepared therefrom |
-
2014
- 2014-07-30 FR FR1457394A patent/FR3024457B1/en not_active Expired - Fee Related
-
2015
- 2015-07-27 US US15/329,481 patent/US20170210942A1/en not_active Abandoned
- 2015-07-27 CN CN201580036423.1A patent/CN106661378A/en active Pending
- 2015-07-27 WO PCT/FR2015/052066 patent/WO2016016562A1/en active Application Filing
- 2015-07-27 EP EP15756201.8A patent/EP3174947A1/en not_active Withdrawn
Non-Patent Citations (2)
| Title |
|---|
| None * |
| See also references of WO2016016562A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106661378A (en) | 2017-05-10 |
| WO2016016562A1 (en) | 2016-02-04 |
| FR3024457B1 (en) | 2018-01-12 |
| US20170210942A1 (en) | 2017-07-27 |
| FR3024457A1 (en) | 2016-02-05 |
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