Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
• • 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
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
  • G02B1/041—Lenses
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/106—Esters of polycondensation macromers
  • C08F222/1063—Esters of polycondensation macromers of alcohol terminated polyethers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
  • Y10S526/937—Optical clarity

Definitions

• the present invention relates to the field of polymerizable monomer compositions which, after polymerization, provide transparent polymer substrates and to their use for the manufacture of optical lenses, in particular ophthalmic.
• Optical lenses for ophthalmic use made of organic polymer material have been known and used for many years.
• compositions containing diallyl carbonate of diethylene glycol hereinafter designated by CAD.
• This base monomer is commercially available, for example, under the brand CR39®.
• O MA® lens An example of an ophthalmic lens sold in a material of this type is the O MA® lens. This material intrinsically has good mechanical properties, in particular impact resistance and abrasion resistance as well as good resistance to organic solvents.
• This material can also be easily colored at the request of the customer.
• One of the drawbacks associated with the use of CAD is the fact that the polymerization of this monomer is essentially carried out thermally, according to particularly long heating cycles (several hours, even several days).
• This methacrylic monomer can be used in an amount of 20 to 70% by weight of the polymerizable mixture.
• the mixture is photopolymerized, preferably at low temperature, then a heat treatment is carried out.
• compositions of monomers comprising from 0 to 100 parts by weight of a first component which is a poly (meth) acrylate urethane monomer, and from 100 to 0 parts by weight of a second component which is a composition comprising:
• compositions are preferably photopolymerized.
• the compositions described generally lead to highly crosslinked polymers due to the presence of monomers comprising numerous functional groups.
• compositions generally contain monomers comprising at least 4 (meth) acrylate groups.
• compositions of polymerizable monomers for the manufacture of ophthalmic lenses or video discs, comprising at least one monomer polyoxyalkylene glycol acrylate or methacrylate, at least one crosslinking agent comprising several unsaturated functions and at least one urethane monomer having from 2 to 6 methacrylic end groups.
• the crosslinking agent mentioned above comprises 3 to 4 functional vinyl, acrylic or methacrylic groups.
• compositions are preferably cured by mixed UV / thermal polymerization.
• Patent EP-A-453149 describes compositions containing a polyoxyaUcylene glycol di (meth) acrylate monomer; a monomer containing a bisphenol A unit and leading, by homopolymerization, to a polymer with a refractive index greater than 1.55 and a urethane monomer having from 2 to 6 (meth) acrylic end groups.
• the polymerization is preferably mixed
• compositions comprising from 10 to 60% by weight of a polybutylene glycoldi (meth) acrylate, from 20 to 80% by weight of a urethane ⁇ oly (meth) acrylate, from 5 to 60% by weight of a specific mono (meth) acrylate monomer and from 0 to 60% by weight of a compound having at least one polymerizable double bond.
• polybutylene glycol di (meth) acrylate is essential to achieve a good compromise between impact resistance properties and low water absorption.
• Comparative Example 7 describes a composition containing a polyethylene glycol di (meth) acrylate, a urethane dimethacrylate and a tricyclo methacrylate [5.2.1.0 2 6 ] decane-8-yl.
• the polymer obtained from this composition has a high water absorption rate of 3.6%.
• US-A-5880171 describes photopolymerizable compositions containing: from 20 to 90%, and preferably at least 50% by weight of a urethane, epoxy or polyester oligomer, the dyes of which are (meth) acrylates and 5 to 80% by weight of an optional diluent which is a hydrocarbon diol ester terminated by (meth) acrylate groups and / or a tri, tetra or ⁇ oly (meth) acrylate.
• This composition is used as a varnish applied to ophthalmic lenses.
• a first object of the present invention is therefore to provide new compositions of polymerizable monomers leading to transparent polymer substrates capable of being substituted for polymers based on CAD, that is to say having properties generally similar to those of CAD. , and preferably improved.
• optical substrates must have all of the following characteristics:
• the polymeric substrates according to the invention have a water absorption rate preferably less than 1.5% and better still less than 1%.
• a second object of the invention is to provide compositions which can be easily and quickly polymerized, in particular that they can be polymerized by photopolymerization techniques or mixed photopolymerization and thermal polymerization techniques making it possible to reduce cycle times. lens manufacturing.
• composition of polymerizable monomers according to the invention comprises:
• R j and R 2 represent H or CH 3
• A. represents a divalent radical of formula - CH 2 -CH 2 -CH 2 0% ll OR
• CH, m 1 and m 2 are each an integer varying from 2 to 6, and
• a monomer (II) comprising at least one urethane unit and at least two (meth) acrylate functions.
• composition of monomers according to the invention generally has a viscosity less than or equal to 0.3 Pa.s, preferably less than 0.2 Pa.s.
• the first important constituent of the compositions according to the invention is (or the) monomer (s) (I) corresponding to the above formula.
• these are (meth) acrylic esters of polypropylene glycol comprising a central radical A, linear or branched, as defined above.
• the first constituent is a monomer or a mixture of monomers (I) of relatively short chain lengths, that is to say that the number of polypropylene glycol units present in the radical A must be equal to or less than 6 and preferably for each of the monomers (I) between 2 and 6.
• Sm represents the area of the peak corresponding to the monomer (I) comprising m propylene glycol unit in the divalent radical A
• S total represents the total area of all the peaks corresponding to the monomers (I) for which m varies from 2 to 6.
• mixtures of several monomers (I) are preferably used for which the average value m as defined above is less than 5 and preferably varies from 2 to 4.
• the monomers (I) have a branched structure, that is to say that the divalent radical A represents:
• compositions according to the invention comprise from 50 to 95 parts by weight of monomer (I), the total weight of the monomers (I) and (LT) representing 100 parts by weight.
• a mixture of several monomers (I) is preferably used, the central unit A of which is:
• the first constituent brings rigidity to the polymer network constituting the final substrate.
• the second constituent of the compositions according to the invention is a monomer or mixture of monomers (IL) comprising at least one urethane unit and at least two (meth) acrylate functions.
• the first family is made up of di (meth) acrylate urethane oligomers, and preferably those which are aliphatic polyesters.
• Examples of such compounds are the urethane di (meth) acrylate oligomers from the company Cray Valley, in particular the product known under the trade name CN934®.
• the second family is composed of the monomers (H) having the formula
• Q is a radical of valence n, with a linear, branched or cyclic structure, containing at least two units of formula: - C - NR '-
• OW is a divalent alkyl radical, of linear or branched structure, from 1 to 5 carbon atoms, n varies from 2 to 4, R represents H or CH 3 -, and
• R ' represents H or a valential link.
• W represents the radical - CH 2 CH, -
• the radical Q is a divalent radical of formula: O o
• X represents a linear or branched divalent alkyl chain of 1 to 15 carbon atoms, preferably of 8 to 12 carbon atoms.
• R ' ⁇ and R' 2 denote independently of each other H or CH 3 .
• a monomer of this type is commercially available under the trade name PLEX® 6661-0 and has the formula:
• CH 2 C- C-0-CH 2 -CH 2 - C-NH-CHy- C CH,
• CH 2 C- C-0-CH 2 -CH 2 -0-C-NH-CH 2 --CH 2 - C-R ' 4
• R ' 3 and R' 4 denote, independently of one another H or CH 3 .
• R '' ⁇ R " 2 and R" 3 represent, independently of each other H or CH 3 .
• the monomer (H) is present in a proportion of 5 to 50 parts by weight, preferably 10 to 40 parts by weight relative to the total weight of the monomers (I) and (II).
• urethanes aliphatic methacrylates :
• the monomer compositions according to the invention can comprise other polymerizable monomers (TU) different from the monomers (I) and (II), which can be integrated into the final network obtained, in particular monomers which can be polymerized by the radical route.
• TU polymerizable monomers
• These monomers (lu) represent from 0 to 30%, preferably
• alkyl (meth) - acrylates such as methyl (meth) acrylate and rethyl (meth) acrylate
• cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate and dicyclopentyl (meth ) acrylate
• phenoxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylate and phenoxybutyl (meth) acrylate
• alkylene glycoldi (meth ) acrylates such as ethylene glycol di (meth) acrylate and propylene glycoldi (metha) acrylate
• poly (alkylene) glycoldi (meth) - acrylates different from the monomers (I) such as poly (ethylene)
• R 5 represents H or CH 3 and n j + n has an average value, from 0 to 40.
• the monomer (m) can be a monomer or a mixture of monomers corresponding to the chemical structure of the monomer (!) And for which m l or m 2 is an integer greater than 6, generally from 7 to 20.
• the amount of monomers (IH) is such that the average:
• the additional monomer (III) can be a monomer with a high Abbe number and comprising one or more (meth) acrylate functions.
• the monomer with a high Abbe number it is necessary to understand a monomer capable of generating, by homopolymerization, a transparent polymer with high Abbe number, that is to say at least 50, and preferably at least 55.
• the monomer with a high Abbe number comprises at least one cyclic or polycyclic non-aromatic hydrocarbon radical.
• the monomer (TU) with a high Abbe number is preferably chosen from at least one of the monomers of the following formula:
• Y is a divalent radical chosen from -O-, -CH 2 -, -C (CH 3 ) 2 -, -C (H) (CH 3 ) - Z is a divalent radical chosen from - (CH 9 ) -O- p being an integer from 1 to 4, and CH,
• R j ,, R d represent, independently of one another, a linear or branched alkyl radical of 1 to 6 carbon atoms
• R j , R represent, independently of one another, a linear or branched alkyl radical of 1 to 10 carbon atoms w is an integer from 1 to 3, x is an integer from 0 to 3, y is an integer from 0 to 3, provided that x + y> 1, k is an integer from 0 to 6, 1 is an integer from 0 to 6, r is an integer from 0 to 6, s is an integer from 0 to 6 , z is an integer from 0 to 3, and t is an integer from 0 to 3.
• the monomers (III) with a high Abbe number in particular preferred are chosen from the monomers of formula
• compositions according to the invention also comprise a system for initiating the polymerization.
• the polymerization initiation system may include one or more thermal or photochemical polymerization initiators or a mixture of thermal and photochemical polymerization initiators. These initiators are well known in the art and any conventional initiator can be used.
• thermal polymerization usable in the present invention there may be mentioned peroxides such as benzoyl peroxide, cyclohexyl peroxydicarbonate, and isopropyl peroxydicarbonate.
• photoinitiators mention may be made in particular of 2,4,6-trimethylbenzoyldiphenylphos ⁇ hine, 1-hydroxycyclohexylephenylketone, 2,2-dimethoxy 1,2-diphenylethane 1-one, and alkyl benzoyl ethers.
• the initiating agents are used in a proportion of 0.01 to 5% by weight relative to the total weight of the polymerizable monomers contained in the composition.
• the polymerizable compositions according to the invention may also comprise additives conventionally used in polymerizable compositions for molding optical or ophthalmic articles, in particular spectacle glasses and lenses, in conventional proportions, namely inhibitors, dyes, UV absorbers, perfumes, deodorants, antioxidants, anti-yellowing agents and photochromic compounds.
• additives conventionally used in polymerizable compositions for molding optical or ophthalmic articles in particular spectacle glasses and lenses, in conventional proportions, namely inhibitors, dyes, UV absorbers, perfumes, deodorants, antioxidants, anti-yellowing agents and photochromic compounds.
• the compositions according to the invention can be polymerized thermally, photochemically or by a combination of these two methods.
• compositions are weighed in a room with controlled lighting, in smoked glass bottles.
• the PPG200DMA, monomer (I), and the comonomers (II) as well as a photoinitiator and a UV absorber are mixed by sustained agitation for a few minutes.
• a thermal initiator stored at low temperature is added as a last step (for reasons of stability).
• compositions prepared as indicated above are poured into molds consisting of two parts of mineral glass mold previously cleaned with soda, assembled in parallel by Barnier adhesive tape and spaced 2 mm apart. The pouring takes place as follows: • Sampling of the composition using a sterile syringe (20ml)
• the filled molds are placed in a photocMrriique polymerization oven consisting of two U.V. PRJMA lamps.
• Infrared measurements make it possible to follow the conversion of the (meth) acrylic double bonds as a function of the UV irradiation time.
• the yellow index YI was measured according to standard ASTM D1925. Colorability measurement (% Tv red)
• the measurement given is the value of the transmission measured in the visible of a 2 mm thick glass center colored by soaking in an aqueous bath at 94 ° C in which is dispersed a red pigment "disperses Red 13" of the company Eastman Kodak.
• the measurement of the Tg is carried out by DMA (dynamic mechanical analysis) on a 5.2 cm ⁇ 1 cm ⁇ 2 mm (thickness) plane test tube.
• the test is carried out in 3-point bending.
• Tg corresponds to the maximum of the ratio
• the impact resistance was determined from 21 glasses of -2 diopters, with a center thickness of 1.07 mm obtained by polymerization of the composition of Example 12, as described above. In this test, balls are dropped with increasing energy in the center of the glass until the glass stars or breaks. The average energy of rupture is then calculated.
• the average energy of rupture is 1900 ⁇ 500 mJ.
• CGI1850 photoinitiator from the company CIB A GEIGY consisting of a mixture (in a mass ratio of 50/50)
• tBPEH tertiobutyl peroxy-2-ethylhexanoate
• UV5411 2- (2'-hydroxy-5'-t-octyl ⁇ henyl) benzotriazole from the company American Cyanamid
• the viscosities are determined on 250 ml samples at 25 ° C using a BROOKFIELD viscometer model DV2 at shear speeds varying from 6 to 60 revolutions / minute (mobile No. 61 or No. 62). Mobile No. 61 was used at a shear speed of 12 rpm.
• the DMA analyzes were carried out with a Rhéometrics Solid Analyzer RSA H device on 52 x 10 x 2 mm test tubes, at a frequency of 1 Hz and over a temperature range of -50 ° C to 170 ° C at 2 ° C / minute.
• the average energy at break is 1200 ⁇ 900 m d and two glasses out of 18 do not pass the test.
• the impact resistance of 20 lenses of power -2 diopters and of center thickness 1.09 mm obtained by polymerization of the composition of example 22 was also determined.
• the average energy at break is 1200 ⁇ 800 mJ and 1 glass in 20 does not pass the test.
• the impact resistance test consists in dropping beads of increasing energy in the center of the lenses until rupture (breakage or star formation of the lens). The average energy of rupture is then determined.
• a water absorption test was carried out on the glasses of Examples 6 and 12.
• the glasses, dried in an oven, are weighed and then immersed in water at 90 ° C. for 30 minutes.
• the glasses are collected and wiped, then weighed again.
• CD6440P is a mixture of several monomers corresponding to general formula (I), the motif of which is

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• Macromonomer-Based Addition Polymer (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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• 1999
  • 1999-08-02 FR FR9910032A patent/FR2797265B1/fr not_active Expired - Fee Related
• 2000
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  • 2000-08-01 WO PCT/FR2000/002213 patent/WO2001009206A1/fr active Application Filing
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