# US 10,370,520 B2 · Composition for the manufacture of an ophthalmic lens comprising an UV-absorber and an anti-yellowing additive > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,370,520 B2 - Document ID: US10370520B2 - Status: Granted - Kind: B2 - Application number: 15/319,260 - Filed: 2015-06-23 - Published: 2017-05-04 - Granted: 2019-08-06 - Earliest claimed: 2014-06-24 - Assignees: Essilor International - Applicants: Essilor International (Compagnie Generale D'Optique) - Inventors: Pierre Fromentin - Web page: https://patentgrep.com/patent/US10370520B2 ## CPC - C08K 5/3435: Piperidines - C08K 5/3475: condensed with carbocyclic rings - C08K 5/34926: {also containing heterocyclic groups other than triazine groups} - C08K 5/372: Sulfides {, e.g. R-(S)x-R'} - G02B 1/041: {Lenses} - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) - G02B: OPTICAL ELEMENTS, SYSTEMS OR APPARATUS ## Abstract The present invention relates to a thermosetting composition for the manufacture of an ophthalmic lens which efficiently absorbs ultraviolet (UV) rays without exhibiting undesirable yellowing, said composition comprising an allyl monomer or oligomer, a catalyst, a UV-absorber and a specific anti-yellowing additive. The present invention also relates to the use of said composition and to the ophthalmic lens obtained from said composition. ## Claims ### Claim 1 A polymerizable composition for the manufacture of an ophthalmic lens, comprising: at least 20% by weight based on the total weight of the composition of at least one allyl monomer or oligomer selected from diethylene glycol bis(allyl carbonate), ethylene glycol bis(allyl carbonate), oligomers of diethylene glycol bis(allyl carbonate), oligomers of ethylene glycol bis(allyl carbonate), and mixtures thereof; at least one catalyst suitable for initiating the polymerization of said allyl monomer or oligomer; at least one UV absorber; at least one anti-yellowing additive, wherein said anti-yellowing additive corresponds to general formula (I): wherein: F represents a function selected from sulfide, disulfide or a substituted piperidinyl group; A is a bond or represents a linear or branched C1-C10 alkylene group, wherein 1 to 4 non adjacent carbon atom(s) may independently be replaced by an oxygen atom, a sulphur atom or an amino group, and may comprise from 1 to 4 carbon-carbon double bond(s); Y3—C(Y1)—Y2 is a polar group in which: Y1 represents O or S; Y2 and Y3 are similar or different and represent O, S, NH or a bond; R99 is any group, which may include at least one function F and/or at least one polar group as defined hereinabove. ### Claim 2 (depends on 1) The polymerizable composition according to claim 1, wherein Y1 is O. ### Claim 3 (depends on 1) The polymerizable composition according to claim 1, wherein the molecular weight of the anti-yellowing additive divided by the number of Y3—C(Y1)—Y2 polar groups of the anti-yellowing additive is in the range of about 75 g/mol to about 1000 g/mol. ### Claim 4 (depends on 1) The polymerizable composition according to claim 1, wherein the anti-yellowing additive is a substituted piperidinyl group having the following formula (VI) wherein: R10 represents a group selected from H, —Ra, aryl, —XH, —C(X)—Ra, —C(X)—Y—Ra and —(Re)—Z, in which: Ra represents a linear or branched C1-C20 alkyl group, or a linear or branched C2-C20 alkenyl group; aryl represents a monocyclic or bicyclic C6-C14 hydrocarbyl group, which may optionally be substituted with 1 to 4 substituents independently selected from halogen, linear or branched C1-C8 alkyl, linear or branched C1-C8 alkoxy, linear or branched C1-C8 alkylthio, amino, linear or branched C1-C8 monoalkylamino, and linear or branched C1-C8 dialkylamino; X represents oxygen or sulphur atom; Y represents oxygen atom, sulphur atom or a group —NRb wherein Rb represents hydrogen atom or a linear or branched C1-C20 alkyl group; Re represents a linear or branched C1-C20 alkylene group, wherein 1 to 4 non adjacent carbon atom(s) may independently be replaced by an oxygen atom, a sulphur atom or an amino group —NRb as defined above, and may comprise from 1 to 4 carbon-carbon double bond(s); and Z represents a hydrogen atom or an aryl group as defined above; R20 represents a group selected from linear or branched C1-C8 alkyl, linear or branched C2-C8 alkenyl, linear or branched C1-C8 alkoxy, linear or branched C1-C8 alkylthio, and —(Re)—Z wherein Re and Z are defined as hereinbefore; n is an integer from 1 to 4 inclusive; Y1 represents O or S; Y2 and Y3 are similar or different and represent O, S, NH or a bond; and R99 is any group. ### Claim 5 (depends on 4) The polymerizable composition according to claim 4, wherein R99 is a group selected from linear or branched C1-C8 alkyl, substituted piperidinyl or a linear or branched C1-C10 alkylene carrying a —COO—C1-C10alkyl or a —COO-(substituted piperidinyl) group. ### Claim 6 (depends on 5) The polymerizable composition according to claim 5, wherein the anti-yellowing additive is a substituted 2,2,6,6-tetramethylpiperidine. ### Claim 7 (depends on 5) The polymerizable composition according to claim 5, wherein the anti-yellowing additive is a compound having the following formula (VII): wherein: R1 is hydrogen, linear or branched C1-C15 alkyl, linear or branched C1-C15 acyl or linear or branched C1-C15 alkoxy; Y3 represents O or a bond; B is a group selected from linear or branched C1-C8 alkyl, substituted piperidinyl or a linear or branched C1-C10 alkylene carrying a —COO-alkyl or —COO-(substituted piperidinyl) group. ### Claim 8 (depends on 1) The polymerizable composition according to claim 1, wherein the anti-yellowing additive corresponds to the following formula (X): wherein: each R2 is independently a linear or branched or cyclic C1-C20 alkyl group wherein 1 to 4 non adjacent carbon atom(s) may be replaced by oxygen atom, sulphur atom, and amino group, and may comprise from 1 to 4 carbon-carbon double bond(s); each n is an integer from 1 to 17 inclusive; and m is 1 or 2. ### Claim 9 (depends on 1) The polymerizable composition according to claim 1, wherein the anti-yellowing additive is a cyclic sulphide having the following formula (XIII) wherein R20 represents a group selected from linear or branched C1-C8 alkyl, linear or branched C2-C8 alkenyl, linear or branched C1-C8 alkoxy, linear or branched C1-C8 alkylthio, and —(Re)—Z wherein Re represents a linear or branched C1-C20 alkylene group, wherein 1 to 4 non adjacent carbon atom(s) may independently be replaced by an oxygen atom, a sulphur atom or an amino group —NRb wherein Rb represents hydrogen atom or a linear or branched C1-C20 alkyl group, and may comprise from 1 to 4 carbon-carbon double bond(s); and Z represents a hydrogen atom or an aryl group, wherein aryl represents a monocyclic or bicyclic C6-C14 hydrocarbyl group, which may optionally be substituted with 1 to 4 substituents independently selected from halogen, linear or branched C1-C8 alkyl, linear or branched C1-C8 alkoxy, linear or branched C1-C8 alkylthio, amino, linear or branched C1-C8 monoalkylamino, and linear or branched C1-C8 dialkylamino; n is an integer from 1 to 5 inclusive; B represents a 3 to 12-membered monocyclic heterocycloalkyl which comprises, in addition to the sulphur atom of the cycle, from 1 to 3 heteroatoms independently selected from oxygen and sulphur; Y1 represents O or S; Y2 and Y3 are similar or different and represent O, S, NH or a bond; and R99 is any group. ### Claim 10 (depends on 1) The polymerizable composition according to claim 1, comprising: a mixture of an anti-yellowing additive of formula (VII): wherein: R1 is hydrogen, linear or branched C1-C15 alkyl, linear or branched C1-C15 acyl or linear or branched C1-C15 alkoxy; Y3 represents O or a bond; B is a group selected from linear or branched C1-C8 alkyl, substituted piperidinyl or a linear or branched C1-C10 alkylene carrying a —COO-alkyl or —COO-(substituted piperidinyl) group; and an anti-yellowing additive of formula (X): wherein: each R2 is independently a linear or branched or cyclic C1-C20 alkyl group wherein 1 to 4 non adjacent carbon atom(s) may be replaced by oxygen atom, sulphur atom, and amino group, and may comprise from 1 to 4 carbon-carbon double bond(s); each n is an integer from 1 to 17 inclusive; and m is 1 or 2. ### Claim 11 (depends on 1) The polymerizable composition according to claim 1, wherein the UV-absorber is a benzotriazole, a benzophenone, a triazine, an oxalanilide, and mixtures thereof. ### Claim 12 (depends on 1) The polymerizable composition according to claim 1, wherein the catalyst is diisopropyl peroxydicarbonate. ### Claim 13 (depends on 1) The polymerizable composition according to claim 1, wherein the catalyst represents from 1.0 to 5.0% by weight based on the total weight of the composition. ### Claim 14 (depends on 1) The polymerizable composition according to claim 1, wherein the catalyst represents from 2.5 to 4.5% by weight based on the total weight of the composition. ### Claim 15 (depends on 1) The polymerizable composition according to claim 1, wherein the anti-yellowing additive represents from 0.05 to 1% by weight based on the total weight of the composition. ### Claim 16 (depends on 1) An ophthalmic lens obtained by filling the composition according to claim 1 in a mould and then heating it, wherein it has a Yellow Index lower than or equal to 2.0, as measured immediately after manufacture. ### Claim 17 (depends on 16) The ophthalmic lens according to claim 16, wherein it has a Yellow Index lower than or equal to 1.7, as measured immediately after manufacture. ### Claim 18 (depends on 17) The ophthalmic lens according to claim 17, wherein the variation in the Yellow Index after exposing said lens to UV light for 80 h does not exceed 0.5 in absolute value. ### Claim 19 An ophthalmic lens obtained by filling in a mould then polymerizing: at least 20% by weight based on the total weight of the composition of at least one allyl compound selected from diethylene glycol bis(allyl carbonate), ethylene glycol bis(allyl carbonate), oligomers of diethylene glycol bis(allyl carbonate), oligomers of ethylene glycol bis(allyl carbonate), and mixtures thereof; at least one catalyst suitable for initiating the polymerization of said allyl compound; at least one UV absorber; and at least one anti-yellowing additive; wherein said ophthalmic lens has a Yellow Index lower than or equal to 2.0, as measured immediately after manufacture and wherein the variation in the Yellow Index after exposing said lens to UV light for 80 h does not exceed 0.5 in absolute value. ### Claim 20 A polymerizable composition for the manufacture of an ophthalmic lens, comprising: at least one allyl monomer or oligomer; at least one catalyst suitable for initiating the polymerization of said allyl monomer or oligomer; at least one UV absorber; and at least one anti-yellowing additive selected from: a dialkyl thiodipropionate corresponding to formula (XXIa) or a dialkyl 3,3′-dithiodipropionate corresponding to formula (XXIb): wherein each R22 is methyl, ethyl, ethyl-hexyl or octyl; or a dialkyl thiodiglycolate corresponding to formula (XXIIa) or a dialkyl dithiodiacetate corresponding to formula (XXIIb): wherein each R22 is independently methyl, ethyl, ethyl-hexyl or octyl; or a cyclic sulphide having the following formula (XIII): wherein R20 represents a group selected from linear or branched C1-C8 alkyl, linear or branched C2-C8 alkenyl, linear or branched C1-C8 alkoxy, linear or branched C1-C8 alkylthio, and —(Re)—Z wherein Re represents a linear or branched C1-C20 alkylene group, wherein 1 to 4 non adjacent carbon atom(s) may independently be replaced by an oxygen atom, a sulphur atom or an amino group —NRb wherein Rb represents hydrogen atom or a linear or branched C1-C20 alkyl group, and may comprise from 1 to 4 carbon-carbon double bond(s); and Z represents a hydrogen atom or an aryl group, wherein aryl represents a monocyclic or bicyclic C6-C14 hydrocarbyl group, which may optionally be substituted with 1 to 4 substituents independently selected from halogen, linear or branched C1-C8 alkyl, linear or branched C1-C8 alkoxy, linear or branched C1-C8 alkylthio, amino, linear or branched C1-C8 monoalkylamino, and linear or branched C1-C8 dialkylamino; n is an integer from 1 to 5 inclusive; B represents a 3 to 12-membered monocyclic heterocycloalkyl which comprises, in addition to the sulphur atom of the cycle, from 1 to 3 heteroatoms independently selected from oxygen and sulphur; Y1 represents O or S; Y2 and Y3 are similar or different and represent O, S, NH or a bond; and R99 is any group.