WO2000050533A1 - Procede de preparation d'un latex a proprietes photochromiques et ses applications, en particulier dans le domaine ophtalmique - Google Patents

Procede de preparation d'un latex a proprietes photochromiques et ses applications, en particulier dans le domaine ophtalmique Download PDF

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Publication number
WO2000050533A1
WO2000050533A1 PCT/FR2000/000397 FR0000397W WO0050533A1 WO 2000050533 A1 WO2000050533 A1 WO 2000050533A1 FR 0000397 W FR0000397 W FR 0000397W WO 0050533 A1 WO0050533 A1 WO 0050533A1
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WO
WIPO (PCT)
Prior art keywords
latex
photochromic
organic
monomer
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.)
Ceased
Application number
PCT/FR2000/000397
Other languages
English (en)
French (fr)
Inventor
Sylvette Maisonnier
Pascale Tardieu
Jean-Paul Cano
Georges Wajs
Jean-Pierre Vairon
Bernadette Charleux
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EssilorLuxottica SA
Original Assignee
Essilor International Compagnie Generale dOptique SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Essilor International Compagnie Generale dOptique SA filed Critical Essilor International Compagnie Generale dOptique SA
Priority to JP2000601098A priority Critical patent/JP4641621B2/ja
Priority to BRPI0008529-4A priority patent/BR0008529B1/pt
Priority to AT00906415T priority patent/ATE258970T1/de
Priority to EP00906415A priority patent/EP1161512B1/fr
Priority to DE60008076T priority patent/DE60008076T2/de
Priority to AU28097/00A priority patent/AU762653B2/en
Publication of WO2000050533A1 publication Critical patent/WO2000050533A1/fr
Priority to US09/939,151 priority patent/US7186359B2/en
Anticipated expiration legal-status Critical
Priority to US11/625,087 priority patent/US20070115426A1/en
Ceased legal-status Critical Current

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Classifications

    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/23—Photochromic filters

Definitions

  • the subject of the invention is a process for the preparation of a photochromic latex, the photochromic thin films obtained from the latter and the articles coated with such thin films, in particular photochromic ophthalmic lenses.
  • Photochromism has been known for many years. We say that a compound is photochromic, for example when this compound, irradiated by a light beam, some wavelengths of which lie in the ultraviolet range, changes color and returns to its original color as soon as the irradiation stops.
  • the applications of this phenomenon are multiple, but one of the known applications which is more particularly interesting relates to the field of ophthalmic optics, in the manufacture of lenses or glasses for glasses, with a view to filtering light radiation as a function of their intensity.
  • Another technique known as "cast in place” consists in incorporating the organic photochromic compounds in a polymerizable mixture leading to a transparent organic material, in introducing it into a mold and in causing its polymerization.
  • a photochromic ophthalmic lens After demolding, a photochromic ophthalmic lens is obtained, the photochromic pigments of which are incorporated into the whole mass of this lens.
  • An advantageous and alternative technique to thermal transfer or "in situ molding” techniques consists in applying a photochromic coating on a preformed ophthalmic lens.
  • the subject of the invention is a method for preparing a latex having photochromic properties, the properties of which do not change or change little over time, leading, after drying, to transparent photochromic thin films, usable on ophthalmic lenses.
  • Aqueous emulsions containing a photochromic pigment have already been described in the prior art.
  • Russian patent RU-2095836 describes a process for obtaining photochromic microcapsules which find their essential application as agents for the identification of official documents.
  • a photochromic compound in this case 6-nitro -1,3,3 -trimethyl styrene (2H-1-benzopyran) -2,2-indoline
  • a photochromic compound in this case 6-nitro -1,3,3 -trimethyl styrene (2H-1-benzopyran) -2,2-indoline
  • polyfunctional oligoesters in this case a mixture of ethylene glycol di (meth) acrylate (DMEG) and triethylene glycol di (meth) acrylate
  • DMEG ethylene glycol di (meth) acrylate
  • benzoyl peroxide initiator in the presence of a benzoyl peroxide initiator.
  • the mixture is emulsified in an aqueous solution containing an ammonium salt of a copolymer of butyl acrylate and (meth) acrylic acid.
  • a mixture of a melamine-formaldehyde-polyvinyl alcohol resin is then introduced into the emulsion formed, then a crosslinked envelope is formed, while simultaneously polymerizing the core of the microcapsules.
  • microcapsules thus obtained have a diameter of 3 to 5 ⁇ m, which makes them unusable for deposits of thin layers from 3 to
  • the process for preparing a latex with properties photochromic according to the invention comprises the following steps:
  • At least one organic monomer Z with groups C C, polymerizable by the radical route, and
  • organic photochromic compound comprising a nucleus of formula:
  • the inventors have found that by polymerizing in aqueous emulsion, that is to say with a water-soluble initiator, the monomer (s) Z and the photochromic compound as defined above, surprisingly a photochromic latex having the desired properties.
  • latexes are stable dispersions of one or more polymers in an aqueous medium.
  • the presence of the initiator in aqueous solution implies a reduced contact between the radicals created in the aqueous phase and the photochromic compound present in the organic phase and that the possible degradation photochromic compound is particularly minimized.
  • the preferred Z monomers are chosen from (meth) alkyl acrylates in CJ-CJQ and preferably mixtures of C 2 -alkyl acrylate monomers - CJQ and C1-C3 alkyl methacrylate.
  • the final polymer resulting from the drying of the latex obtained according to the method of the invention to have a glass transition temperature Tg of less than or equal to 0 ° C.
  • At least one monomer Z is capable of leading, by homopolymerization to a homopolymer having a Tg of less than 0 ° C, and preferably less than -20 ° C and better still less than -30 ° C.
  • these monomers will be called hereinafter "low Tg monomers”.
  • Tg monomers which are particularly recommended, mention may be made of butyl acrylate (Tg homopolymer: -55 ° C.), of propyl or ethyl.
  • Tg monomers Z consisting of a low Tg monomer defined above and at least one second monomer Z capable of leading, by homopolymerization, to a homopolymer of higher Tg improving the mechanical properties.
  • the low monomer Tg represents at least 40%, preferably at least 50% by weight relative to the total weight of the monomers Z of composition A.
  • a preferred composition A contains a mixture of propyl, butyl acrylate, or methyl, ethyl or propyl hexyl and methacrylate.
  • Composition A can also comprise one or more crosslinking agents, such as, for example, poly (alkylene glycols) di (meth) crylate.
  • crosslinking agents such as, for example, poly (alkylene glycols) di (meth) crylate.
  • crosslinking agents such as, for example, poly (alkylene glycols) di (meth) crylate.
  • GMA glycidyl methacrylate
  • interparticle crosslinking in the presence of piperazine
  • di (ethylene glycol) methacrylate di (ethylene glycol) methacrylate
  • crosslinking agents can represent up to 10%, but generally represent up to 5% by weight of composition A.
  • composition A leads, as appropriate, to particles of homopolymers or random copolymers.
  • the invention also includes within its scope the case of latex with at least biphasic particles, in particular comprising a structure of the heart / bark type.
  • Such a structure is obtained by adding to the latex resulting from the at least partial polymerization of composition A a second aqueous emulsion (II) containing a composition B of at least one organic monomer which can be polymerized by the radical route and then by polymerizing said composition B.
  • composition B are preferably chosen from the same families of monomers as those used in composition A.
  • the monomers Z used in composition B can lead to a homopolymer of Tg greater than 0 ° C., in the measurement where the photochromic pigments are located in the core of the particles.
  • the more rigid bark makes it possible to increase the mechanical properties of the films obtained subsequently.
  • organic photochromic compounds which can be used in the context of the invention are photochromic compounds comprising a core of formula:
  • these photochromic compounds do not include an indoline ring.
  • the photochromic compounds are preferably naphthopyrans, in particular those described in documents US-A-5,066,818, WO 93/17071, F-A-2688782.
  • naphtopyrans having two phenyl groups substituted or not on the carbon in position adjacent to the oxygen of the pyrannic nucleus.
  • photochromic compounds exhibit excellent resistance to degradation by radicals in an aqueous medium.
  • the photochromic compound is introduced in an amount sufficient to obtain the photochromic effect sought in the final films.
  • concentrations of photochromic compound generally vary from 2 to 5% by weight relative to the weight of the polymerizable monomers present in the latex.
  • the water-soluble initiators used for the polymerization of the compositions of the invention are salts and compounds having at least one hydrophilic function.
  • these salts and compounds there may be mentioned the alkali metal and ammonium persulfates, in particular sodium or potassium persulfate, hydrogen peroxide, and 2,2'-azobis (2-amidino propane) dihydrochloride .
  • the preferred initiators are the alkali metal persulfates.
  • Sodium or potassium persulfate will preferably be used, rather than the ammonium salt, capable of causing pH variations which can create some colored degradation products of the photochromic compound.
  • the quantity of initiator is variable and can be adapted as appropriate. Generally, the amount of initiator varies from 0.1 to 1% by weight relative to the total weight of the polymerizable monomers present in the latex.
  • the latex is prepared by mixing the photochromic compound in the monomer (s) Z, generally in an aqueous medium, preferably in the presence of surfactants, then by causing the polymerization by means of the initiator which is added. preferably in the above mixture gradually, with vigorous stirring.
  • the surfactants can be ionic surfactants such as sodium dodecyl sulfate, dodecylbenzene sulfate, sodium sulfonate or sulfates of ethoxylated fatty alcohols, nonionic such as ethoxylated or amphoteric fatty alcohols. can also use a mixture of surfactants.
  • the preferred system is the combination of ionic and nonionic surfactants.
  • the aqueous emulsion of the composition may also comprise a conventional buffering agent, and therefore the pH of the emulsion remains constant (preferably 5 to 7) during the preparation of the latex.
  • the polymerization time generally varies from 30 minutes to a few hours.
  • the initiator and the aqueous emulsion are each gradually introduced into the reaction medium during the duration of the polymerization step.
  • the temperature of the reaction mixture is generally between 50 and 90 ° C., the temperature necessary for activating the initiator.
  • the mixture and the initiator are introduced concomitantly in an aqueous solution containing surfactants, a solution called "base stock".
  • the latexes obtained by the process of the invention have a particle diameter between 50 and 400 nm, preferably between 80 and 300 nm and better still between 150 and 250 nm.
  • the dry extract of the latexes generally represents from 30 to 50% by weight of the total mass of the latex and preferably from 40 to 50% by weight. A dilution is possible, by adding water if one wishes to reduce the dry extract in order to obtain varnishes of smaller thickness.
  • the pH of the latexes according to the invention can generally vary from 5 to 7.
  • the photochromic latexes according to the invention can be applied to any type of substrate by conventional techniques known to those skilled in the art, in particular: by immersion in the bath of photochromic latex (dip coating) or by application to the surface of the substrate followed centrifugation to ensure uniform application of latex on the surface.
  • the latex film is then dried under the following conditions:
  • Drying time 5 minutes to 1 hour.
  • the thicknesses of the films obtained are fixed according to the importance of the desired photochromic effect.
  • the thickness varies from 3 to 20 ⁇ m and better still from 5 to 15 ⁇ m.
  • the preferred substrates to which the latexes obtained by the process of the invention are applied are all organic glass substrates commonly used for organic ophthalmic lenses.
  • Polycarbonate (thermoplastic) substrates in particular ophthalmic lenses manufactured by the company Gentex Optics, are the particularly recommended substrates to which the latexes obtained by the process of the invention are applied.
  • substrates obtained by polymerization of alkyl methacrylates in particular C2-C4 alkyl methacrylates such as methyl (meth) acrylate and ethyl (meth) acrylate, the derivatives allylics such as the allyl carbonates of aliphatic or aromatic polyols, linear or branched, thio (meth) acrylics, thiourethanes, polyhethoxylated aromatic (meth) acrylates such as polyethoxylated dimethacrylate bisphenolates.
  • alkyl methacrylates in particular C2-C4 alkyl methacrylates such as methyl (meth) acrylate and ethyl (meth) acrylate
  • the derivatives allylics such as the allyl carbonates of aliphatic or aromatic polyols, linear or branched, thio (meth) acrylics, thiourethanes, polyhethoxylated aromatic (meth) acrylates such as polyethoxy
  • substrates obtained by polymerization of polyol allyl carbonates among which there may be mentioned ethylene glycol bis (allyl carbonate), diethylene glycol bis (2-methyl carbonate), diethylene glycol bis (allyl carbonate) , ethylene glycol bis (2-chloro allyl carbonate), triethylene glycol bis
  • the substrates which are particularly recommended are the substrates obtained by polymerization of the bis (allyl carbonate) of diethylene glycol, sold under the trade name CR 39® by the company PPG INDUSTRIES (lens ORMA® ESSILOR).
  • the substrates also recommended, mention may be made of the substrates obtained by polymerization of thio (meth) acrylic monomers, such as those described in French patent application FR-A-2 734 827. Obviously, the substrates can be obtained by polymerization mixtures of the above monomers.
  • abrasion resistant coatings can be applied to the photochromic film.
  • Hard abrasion resistant coatings can be all abrasion-resistant coatings known in the field of ophthalmic optics.
  • compositions based on silane hydrolyzate in particular epoxysilane hydrolyzate, such as those described in the French patent application. No. 93 026 49 and in US patent -A-4,211,823.
  • the ophthalmic lens according to the invention may also comprise an anti-reflection coating deposited on the anti-abrasion coating.
  • the anti-reflection coating may consist of a mono- or multilayer film, of dielectric materials such as SiO, Si ⁇ 2, Si3N ⁇ Ti ⁇ 2- ⁇ ⁇ ⁇ ⁇ 2 ' ⁇ 2 ⁇ 3 ' MgF2 or ⁇ 205 , or their mixtures.
  • This anti-reflection coating is generally applied by vacuum deposition according to one of the following techniques:
  • a mineral layer by the sol / gel route (for example from tetraethoxy silane hydrolyzate).
  • the film comprises a single layer, its optical thickness must be equal to ⁇ / 4 ( ⁇ is a wavelength between 450 and 650 nm).
  • the present invention also relates to latexes with photochromic properties comprising polymer particles as defined. above which contain an effective amount of at least one photochromic compound as defined above.
  • DISPONTL® A 3065 surfactant (mixture of fatty alcohols with 30 EO, 65% of active ingredients) and 0.55 g of DISPONIL® FES surfactant (C 12 _i4 (OCH 2 CH2) 1 2 OSO _ 3 Na + ) are dissolved in 148.9 g of water.
  • the mixture is stirred for 10 minutes and then it is introduced into a double-walled reactor, the cover of which has 5 inlets (for nitrogen, the thermometer, the stirrer, the casting of the initiator and the casting of the emulsion ).
  • the mixture is degassed for 1 hour at 70 ° C.
  • DISPONIL® A 3065 and 4.8 g of DISPONIL® FES are dissolved in 164.8 g of buffered water by adding 0.57 g of NaHH. The solution is stirred, then, while stirring is continued, a mixture of 185.7 g of butyl acrylate and 79.6 g of methyl methacrylate is added, a mixture into which 11.7 g of d has previously been incorporated.
  • the reaction temperature is 70 ° C.
  • the product obtained is a photochromic butyl acrylate / methyl methacrylate latex 70/30, statistical, according to the invention having the following characteristics:
  • the latex is prepared under the same conditions as above except that the amounts of monomers used are:
  • the amount of photochromic compound Pch introduced is 4.34% relative to the weight of the monomers ABu and MMA.
  • the product obtained is a photochromic butyl acrylate / methyl methacrylate latex 60/40, statistical, having the following characteristics:
  • the heart of the latex was firstly prepared by pouring emulsion I in 2 h 48 min, then, secondly, the bark by pouring emulsion II in lhl2.
  • the priming solution is poured in parallel into the reaction mixture, for a period of 4 hours from the addition of the first drop of emulsion I.
  • compositions of the base stock, the emulsions I and II and the priming solution are indicated in the table below:
  • the product obtained is a photochromic butyl acrylate / methyl methacrylate latex 70/30, core / core, according to the invention having the following characteristics:
  • the latex films were deposited on flat ORMA® glasses by centrifugation at thicknesses 6 ⁇ m.
  • UV light 10.2W / m2

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Physics & Mathematics (AREA)
  • Eyeglasses (AREA)
  • Graft Or Block Polymers (AREA)
  • Polymerisation Methods In General (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Optical Filters (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
PCT/FR2000/000397 1999-02-26 2000-02-17 Procede de preparation d'un latex a proprietes photochromiques et ses applications, en particulier dans le domaine ophtalmique Ceased WO2000050533A1 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
JP2000601098A JP4641621B2 (ja) 1999-02-26 2000-02-17 フォトクロミック特性を有するラテックスの調製方法、および得られたラテックスの利用、特に眼科学の分野での利用
BRPI0008529-4A BR0008529B1 (pt) 1999-02-26 2000-02-17 processo de preparação de um látex com propriedades fotocrÈmicas, látex com propriedades fotocrÈmicas, e, substrato revestido de uma pelìcula.
AT00906415T ATE258970T1 (de) 1999-02-26 2000-02-17 Verfahren zur herstellung von einem photochromen latex und dessen verwendung, insbesondere für ophthalmische anwendung
EP00906415A EP1161512B1 (fr) 1999-02-26 2000-02-17 Procede de preparation d'un latex a proprietes photochromiques et ses applications, en particulier dans le domaine ophtalmique
DE60008076T DE60008076T2 (de) 1999-02-26 2000-02-17 Verfahren zur Darstellung eines Latex mit photochromatischen Eigenschaften und dessen Anwendung insbesondere im ophthalmischen Bereich
AU28097/00A AU762653B2 (en) 1999-02-26 2000-02-17 Method for preparing a latex with photochromic properties and uses thereof, particularly in ophthalmology
US09/939,151 US7186359B2 (en) 1999-02-26 2001-08-24 Method for preparing a latex with photochromic properties and uses thereof, particularly in ophthalmology
US11/625,087 US20070115426A1 (en) 1999-02-26 2007-01-19 Method for preparing a latex with photochromic properties and uses thereof, particularly in ophthalmology

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9902437A FR2790264A1 (fr) 1999-02-26 1999-02-26 Procede de preparation d'un latex a proprietes photochromiques et ses applications, en particulier dans le domaine ophtalmique
FR99/02437 1999-02-26

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US09/939,151 Continuation US7186359B2 (en) 1999-02-26 2001-08-24 Method for preparing a latex with photochromic properties and uses thereof, particularly in ophthalmology

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WO2000050533A1 true WO2000050533A1 (fr) 2000-08-31

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PCT/FR2000/000397 Ceased WO2000050533A1 (fr) 1999-02-26 2000-02-17 Procede de preparation d'un latex a proprietes photochromiques et ses applications, en particulier dans le domaine ophtalmique

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US (2) US7186359B2 (https=)
EP (1) EP1161512B1 (https=)
JP (1) JP4641621B2 (https=)
AT (1) ATE258970T1 (https=)
AU (1) AU762653B2 (https=)
BR (1) BR0008529B1 (https=)
DE (1) DE60008076T2 (https=)
ES (1) ES2211508T3 (https=)
FR (1) FR2790264A1 (https=)
WO (1) WO2000050533A1 (https=)

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FR2816950B1 (fr) * 2000-11-17 2003-02-14 Essilor Int Procede d'obtention d'un latex photochromique
FR2819258B1 (fr) * 2001-01-11 2003-04-11 Essilor Int Procede d'obtention d'un latex photochromique stabilise, latex obtenu et application a l'optique ophtalmique
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US6562466B2 (en) 2001-07-02 2003-05-13 Essilor International Compagnie Generale D'optique Process for transferring a coating onto a surface of a lens blank
US8563212B2 (en) * 2004-07-16 2013-10-22 Transitions Optical, Inc. Methods for producing photosensitive microparticles, non-aqueous dispersions thereof and articles prepared therewith
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US20080006368A9 (en) 2005-02-01 2008-01-10 Peiqi Jiang Process for applying a coating onto a surface of a lens substrate
US20060219347A1 (en) 2005-04-04 2006-10-05 Essilor International Compagnie Generale D'optique Process for transferring coatings onto a surface of a lens substrate with most precise optical quality
KR100875364B1 (ko) * 2005-12-02 2008-12-22 주식회사 엘지화학 광변색성 나노입자의 제조방법 및 이로부터 제조되는광변색성 나노 입자
US7892387B2 (en) 2006-05-19 2011-02-22 International Compagnie Generale d'Optique Process and system for applying a coating onto a surface of a lens substrate
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US9132594B2 (en) 2008-11-04 2015-09-15 Essilor International (Compagnie Générale d'Optique) Bi-layer adhesive for lens lamination
US8287953B2 (en) 2009-02-09 2012-10-16 Essilor International (Compagnie Generale D'optique) Method for spin coating a surface of an optical article
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ES2771099T3 (es) 2012-05-22 2020-07-06 Dsm Ip Assets Bv Composición y proceso para producir un recubrimiento de óxido inorgánico poroso
FR2996930B1 (fr) 2012-10-11 2017-11-24 Essilor Int Lentille ophtalmique photochromique
CA2930509A1 (en) * 2013-11-22 2015-05-28 Dsm Ip Assets B.V. Process for making an anti-reflective coating composition and a porous coating made therefrom
ES2689126T3 (es) 2014-01-31 2018-11-08 Essilor International Estructura de polarización que comprende un sistema adhesivo de glioxal y lente polarizada que la comprende
EP3164892B1 (en) 2014-07-04 2018-08-29 DSM IP Assets B.V. Co-extruded backsheet for solar cell modules
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ES2929943T3 (es) * 2017-12-29 2022-12-05 Essilor Int Proceso de fabricación de una matriz polimérica absorbente de luz
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JP4641621B2 (ja) 2011-03-02
AU762653B2 (en) 2003-07-03
ES2211508T3 (es) 2004-07-16
ATE258970T1 (de) 2004-02-15
BR0008529A (pt) 2001-11-06
EP1161512A1 (fr) 2001-12-12
FR2790264A1 (fr) 2000-09-01
EP1161512B1 (fr) 2004-02-04
DE60008076T2 (de) 2004-11-11
DE60008076D1 (de) 2004-03-11
US20070115426A1 (en) 2007-05-24
US7186359B2 (en) 2007-03-06
AU2809700A (en) 2000-09-14
JP2002537473A (ja) 2002-11-05

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