EP1453874A1 - Composition polymerisable par voie radicalaire conduisant a des verres organiques resistants au choc - Google Patents

Composition polymerisable par voie radicalaire conduisant a des verres organiques resistants au choc

Info

Publication number
EP1453874A1
EP1453874A1 EP02799758A EP02799758A EP1453874A1 EP 1453874 A1 EP1453874 A1 EP 1453874A1 EP 02799758 A EP02799758 A EP 02799758A EP 02799758 A EP02799758 A EP 02799758A EP 1453874 A1 EP1453874 A1 EP 1453874A1
Authority
EP
European Patent Office
Prior art keywords
composition according
meth
oligomer
composition
monomer
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Withdrawn
Application number
EP02799758A
Other languages
German (de)
English (en)
French (fr)
Inventor
Gilles Richard
Odile Primel
Leanirith Yean
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
Publication of EP1453874A1 publication Critical patent/EP1453874A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/061—Polyesters; Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers

Definitions

  • the invention relates generally to photopolymerizable and / or thermally polymerizable compositions, depending on the type of initiator used for the reaction, which lead to transparent glasses, in particular ophthalmic glasses, having good impact resistance .
  • One of the most well-known organic glasses used for its excellent impact resistance properties is bisphenol-A polycarbonate, commonly known as PC, - and its derivatives.
  • This' glass which is a thermoplastic material, is entirely satisfactory to the wearer and can be produced by injection of advantageous cost by using injection molding, well suited for mass production.
  • European patent application EP 1 035 142 describes the polymerization of an acrylic copolymer material for obtaining ophthalmic articles which comprises the polymerization of at least one ⁇ , ⁇ -ethylenically unsaturated carboxylic acid and at least one monomer of aryl (meth) acrylate in the presence of a crosslinking agent.
  • the crosslinking agent which can represent 0.5 to 15% by weight of the total weight of the monomers present in the composition, comprises in particular ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, allyl methacrylate, 1, 3- propanediol dimethacrylate, allyl methacrylate, 1, 6-hexanediol dimethacrylate, 1, 3-butanediol dimethacrylate, 1, 4-butanediol dimethacrylate as well as divinyl compounds including divinyl hydrocarbons and divinyl benzene.
  • compositional effects on network structure of highly cross-Iinked copolymers of PEG- containing multiacrylates with acrylic acid influence of the composition on the network structure of highly crosslinked copolymers of multiacrylates containing PEG with acrylic acid
  • concentrational effects on network structure of highly crosslinked copolymers of multiacrylates containing PEG with acrylic acid "describes a photopolymerizable composition containing PEG 400 diacrylate and 23.6% by weight of acrylic acid.
  • compositions which can be polymerized by the radical route, in particular by photopolymerization, which results in a polymer material having a high impact resistance, good thermomechanical properties, a low water absorption and which can be used. for the manufacture of transparent substrates, in particular optical articles such as ophthalmic lenses.
  • composition which can be polymerized by the radical route comprising:
  • a first component A comprising at least one oligomer carrying at least two polymerizable radical functions and whose homopolymer has a glass transition temperature (T g ) below 50 ° C, this component A being capable of leading by polymerization to a polymer having a temperature of. glass transition (T g ) ⁇ at 50 ° C, preferably equal to or less than 0 ° C and better ranging from -50 ° C to -10 ° C, the oligomer of component A representing more than 15%, preferably at at least 20% of the total weight of the polymerizable species present in the composition; and
  • a second constituent B comprising at least one (meth) acrylic monomer carrying at least one promoter group of bond H, this (meth) acrylic monomer representing at least 15% of the total weight of the polymerizable species present in the composition when this monomer is a methacrylic monomer and at least 35% of the total weight of these polymerizable species when this monomer is an acrylic monomer.
  • the oligomer of component A is a difunctional compound.
  • the oligomer of component A has a number-average molar mass which varies from 100 to 5000, preferably 200 to 4000, better still from 300 to 2000 g. mole "1 .
  • the oligomer of the first constituent A is preferably chosen from poly (alkylene) glycols di (meth) acrylate, bisphenol-A di (meth) acrylate polyethoxylated, oligomers dithio (meth) acrylates and urethanes di (meth) acrylates , di (meth) acrylates thioruethanes, di (meth) acrylates polysulphides.
  • the polyalkylene glycol .. - di (meth) acrylates * • dates- are - polyethylene glycol and polypropylene glycol di (meth) acrylates, in particular polypropylene glycol di (meth) acrylates, and particularly, the polypropylene glycol dimethacrylates.
  • the preferred dimethacrylate oligomer is a polypropylene glycol dimethacrylate of number average molar mass of the order of 530 g. mol "1 (PPG 400 DMA) sold under the name SR6440P by the company CRAY VALLEY.
  • polyethylene or polypropylene glycol di (meth) acrylate oligomers suitable for the present invention can be represented by the formula:
  • A represents a divalent radical of formula:
  • mi, m 2 and m 3 are each an integer varying from 4 to 20.
  • S m represents the area of the peak corresponding to the monomer (I) comprising m propylene glycol unit in the divalent radical A
  • Stotai represents the total area of all the peaks corresponding to the monomers (I) for which m varies from 4 to 20.
  • mixtures of several oligomers (I) are preferably used for which the average value m as defined above varies between 5 and 10, preferably between 6 and 9.
  • oligomers (I) for which the average value is greater than 20 and preferably between 30 and 40.
  • the calculation of the average value is carried out as above, but for l 'all the oligometric fractions, including of course for the oligomers (I) for which the value m is greater than 20.
  • the monomers (I) have a branched structure, that is to say that the divalent radical A represents:
  • the monomers (I) are commercially available from the company CRAY VALLEY under the trade name SR6440P, CD6440P and from the company SHIN NAKAMURA under the name 9PG and with UCB under the trade name PPG400.
  • SR6440P is a mixture of several monomers (I) whose central motif is:
  • Another class of di (meth) acrylate oligomer suitable for constituent A of composition of the invention comprises polyalkoxylated bisphenol-A dimethacrylates (preferably ethoxylated or propoxylated) having from 10 to 80 alkoxy units (in average value).
  • R 1 and R 2 represent, independently of one another, H or CH 3
  • X represents - (CH 2 -CH 2 -0) -, - (CH 2 -CH 2 -CH 2 -0) - or - (CH 2 -CHCH 3 -O) -, preferably - (CH 2 -CH 2 -0) -, - and ni + n 2 has an average value of 10 to 50, preferably 10 to 40.
  • the preferred bisphenol-A ethoxylated di (meth) acrylate oligomers are bisphenol-A dimethacrylate with 30 ethoxy units (BPA30EODMA) marketed under the names BPE-1300N by SHIN NAKAMURA CHEMICALS and SR 9036 by CRAY VALLEY, bisphenol-A dimethacrylate with 32 propoxy units, bisphenol-A diacrylate with 32 propoxy units and bisphenol-A diacrylate with 16 propoxy units.
  • the particularly preferred bisphenol-A oligomer is BPA30EODMA.
  • the oligomer of component A of the compositions of the invention can also be a di [thio (meth) acrylate], that is to say an oligomer compound containing two functions:
  • n is an integer from 1 to 10, or a mixture of such dithiomethacrylates.
  • the oligomer of component A can also be a urethane di (meth) acrylate.
  • Mention will in particular be made of the aliphatic diacrylate urethanes marketed by the company CRAY VALLEY under the names CN934, 935, 965, 963, 966, 967, 981 and by the company UCB under the names EBECRYL 230, 244, 245, 270, 284, 285 , 4830, 4835, and 8800 and the aromatic diacrylate urethanes sold by the company CRAY VALLEY under the names CN 970, 972, 973 and 976 and the company UCB under the names EBECRYL 210, 215 and 4244.
  • oligomer of component A is a urethane di (meth) acrylate
  • component B at least 40% by weight of the polymerizable species present in the composition
  • Component A of the compositions of the invention may also comprise at least one other comonomer, non-oligomeric, comprising at least one radical polymerizable function and preferably two radical polymerizable functions.
  • the preferred comonomers for component A are mono or di (meth) acrylate comonomers such as alkyl (meth) acrylates like methyl (meth) acrylate and rethyl (meth) acrylate, cycloalkyl (meth) acrylate like cycloethyl (meth) acrylate and dicyclopentyl (meth) acrylate, aryl (meth) acrylates like phenyl (meth) acrylate, benzyl (meth) acrylate, naphthyl (meth) acrylates, phenoxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylate and phenoxybutyl (meth) acrylate, alkylene glycol dimethacrylate such as ethylene glycol di (meth) acrylate and propylene glycol di (meth) acrylate.
  • alkyl (meth) acrylates like methyl (meth
  • comonomers include vinyl or polyvinyl compounds as well. than,. allylic or polyallylic compounds such as divinylbenzene.
  • the choice of these comonomers must be such that the first constituent A leads, by polymerization, to a polymer or copolymer having a glass transition temperature Tg equal to or less than 50 ° C.
  • the second constituent B is preferably a monofunctional compound and in particular a compound of formula:
  • R denotes H or CH 3
  • Z represents a single covalent bond or a spacer group.
  • Z is preferably a divalent hydrocarbon chain, optionally interrupted by one or more heteroatoms, preferably chosen from O, S, N or by one or more groups
  • the hydrocarbon chain is a short chain and comprises 1 to 10 carbon atoms and better still 1 to 6 carbon atoms.
  • the spacer group Z can be a polyether, polyester, polyurethane, polyurea, polythiourethane group.
  • Z ' is a short monovalent chain, preferably comprising from 1 to 10 carbon atoms, and better still from 1 to 6 carbon atoms and comprises at least one promoter group of H bonds chosen from the groups: -COOH
  • R ', R ", R'", R ⁇ v , R v denote, independently of each other, H or an alkyl group of 1 to 10 carbon atoms or aryl of 6 to 10 carbon atoms.
  • the alkyl group can itself be aliphatic or cycloaliphatic.
  • the alkyl group represents CH 3 .
  • Z ′ represents a promoter group for binding H chosen from the groups COOH, OH and CONHR ′, preferably a group
  • R is a CH 3 group.
  • IV can also be, on its own, a carbonyl function and / or a tertiary amine function.
  • the carbonyl and tertiary amine functions can therefore be used in addition to the H-promoter functions previously mentioned.
  • the monofunctional monomers carrying preferred hydrogen bonding precursor groups are methacric acid (AMA), acrylic acid (AA) and the (meth) acrylic monoesters of dicarboxylic acids such as mono-2 (methacryloyloxy) ethylsuccinate (MA succinate) of formula:
  • component B is methacrylic acid. More preferably, the constituents A and B are only methacrylic compounds.
  • 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. These initiators are well known in the art and any conventional initiator can be used. Among the initiators of thermal polymerization which can be used in the present invention, mention may be made of peroxides such as benzoyl peroxide, cyclohexyl peroxydicarbonate, and isopropyl peroxydicarbonate. Among the photoinitiators, mention may be made in particular of
  • 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 the conventional proportions, namely agents mold release, inhibitors, dyes, UV absorbers, perfumes, deodorants, antioxidants, anti-yellowing agents and photochromic compounds.
  • the advantage of using the B promoter component B is to stiffen the very flexible network formed by the component A, without however introducing too high a crosslinking density which would be detrimental to the impact resistance of the final material.
  • the polymerized materials according to the invention have the required thermomechanical properties, namely good rigidity at 25 ° C., which is the temperature for using the glasses, and at 100 ° C., which is the temperature reached at various stages. of the glass manufacturing process and during subsequent treatments (coloring, varnishing).
  • the materials obtained from the compositions according to the invention have an elastic modulus (E ') at 100 ° C of at least 40 MPa, preferably 100 MPa and better still at least 120 MPa, or even 150 MPa.
  • compositions according to the invention are photopolymerizable compositions and the materials obtained by polymerization of the compositions according to the invention are preferably organic glasses obtained by conventional molding, preferably by photopolymerization.
  • the glass can be a semi-finished glass, that is to say that one of its faces remains to be surfaced to its final geometry, but of course, the method can also be applied to the manufacture of finished glass. , that is to say comprising their two optical surfaces at the desired geometry at the end of molding.
  • the glasses obtained have excellent impact resistance and very low water absorption.
  • BPA30EODMA 60 g of BPA30EODMA are mixed with 40 g of methacrylic acid at room temperature.
  • CGI 819 ® phosphine oxide photoinitiator from Ciba.
  • the composition is obtained in a room with controlled lighting in a smoked glass bottle.
  • composition thus prepared is poured into a mold in two parts of mineral glass previously cleaned with soda, assembled in parallel by a Barnier adhesive tape and spaced two millimeters apart.
  • the casting takes place as follows:
  • composition is withdrawn using a sterile syringe (20 ml);
  • composition is injected into the mold; and - the adhesive tape is replaced to seal the mold.
  • the filled mold is then placed in a photochemical polymerization oven consisting of two UV.prima lamps (mercury lamps) placed on either side, and at an equal distance from the parts of the mold, the mold receiving an illumination from each lamp. about 40 milliwatts for 30 seconds.
  • the infrared measurements make it possible to follow the conversion of the (meth) acrylic double bonds as a function of the UV irradiation time. After 30 seconds of irradiation, the conversion is complete.
  • the adhesive tape is removed.
  • the glasses are then removed from the mold and then checked with an arc lamp.
  • a final annealing at 120 ° C. makes it possible to perfect the polymerization and to relax the residual stresses of the substrate obtained.
  • Example 1 is repeated while varying the proportions of methacrylic acid and BPA 30EODMA.
  • the proportions of the starting constituents as well as the results are indicated in Table I below.
  • Comparative example C1 comprises as the only polymerizable monomer BPA30EODMA.
  • ZELECUN lubricant from DUPONT CHEMICALS
  • UV 541 1 2- (2-hydroxy-5'-t-octylphenyl) benzotriazole from the company AMERICAN CYANAMID.
  • CGI 819 ® from the company CIBA GEIGY.
  • the stiffening of the network is illustrated by the increasing values of E '(25 ° C), E' (100 ° C) and Tg during the introduction of methacrylic acid. From 50% methacrylic acid, the Tg obtained is greater than 150 ° C. which is particularly high for a thermoset acrylic network.
  • the density of the solid material is relatively high, which illustrates the intensity of the hydrogen bonding type interactions.
  • methacrylic acid limits the uptake of water from the network.
  • high function rates strongly polar acid should lead to increased hydrophilicity. This behavior shows that the acid bonds strongly interact within the polymer network and are no longer available for interactions with water molecules in the external environment.
  • Example 1 was repeated, replacing the BPA30EODMA with PPG 400 DMA in various proportions.
  • the compositions and the results are given in Table III below.
  • compositions as well as the results obtained are given in Table IV below.
  • component A a mixture of oligomer BPA30EODMA and of dithiomethacrylate W consisting of a mixture of a first component corresponding to formula III (with n 'varying from 1 to 10) and a second component corresponding to the formula:
  • component A a mixture of BPA30EODMA and mono-2- (methacryloyloxy) ethyl phthalate (MA phthalate) from the company ALDRICH.
  • the spherical lenses of power -2 diopters were produced from the composition of Example 2.
  • the glasses obtained were subjected to an impact resistance test by falling energy increasing ball (increasing the height of fall until rupture).
  • compositions according to the invention make it possible to obtain high impact strengths.
  • Example 2 of patent application WO 01/09205 is reproduced to form spherical glasses of power -2 diopters.
  • the PLEX 6661-0 from CRAY VALLEY has the formula
  • R ' 3 and R' denoting, independently of one another, H or CH 3 .

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
EP02799758A 2001-11-26 2002-11-26 Composition polymerisable par voie radicalaire conduisant a des verres organiques resistants au choc Withdrawn EP1453874A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0115273A FR2832717B1 (fr) 2001-11-26 2001-11-26 Composition polymerisable par voie radicalaire conduisant a des verres organiques resistants au choc
FR0115273 2001-11-26
PCT/FR2002/004050 WO2003046028A1 (fr) 2001-11-26 2002-11-26 Composition polymerisable par voie radicalaire conduisant a des verres organiques resistants au choc

Publications (1)

Publication Number Publication Date
EP1453874A1 true EP1453874A1 (fr) 2004-09-08

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EP02799758A Withdrawn EP1453874A1 (fr) 2001-11-26 2002-11-26 Composition polymerisable par voie radicalaire conduisant a des verres organiques resistants au choc

Country Status (6)

Country Link
US (1) US7393880B2 (enExample)
EP (1) EP1453874A1 (enExample)
JP (1) JP2005510594A (enExample)
AU (1) AU2002364405A1 (enExample)
FR (1) FR2832717B1 (enExample)
WO (1) WO2003046028A1 (enExample)

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US20090258974A1 (en) * 2008-02-06 2009-10-15 Edwin Slagel Optically transmissive resilient polymers and methods of manufacture
JP6519729B2 (ja) * 2014-12-19 2019-05-29 東亞合成株式会社 樹脂シート及びその製造方法
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Also Published As

Publication number Publication date
WO2003046028A1 (fr) 2003-06-05
US20050107537A1 (en) 2005-05-19
US7393880B2 (en) 2008-07-01
FR2832717A1 (fr) 2003-05-30
FR2832717B1 (fr) 2004-07-09
AU2002364405A1 (en) 2003-06-10
JP2005510594A (ja) 2005-04-21

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