Liquid polymerizable allyl composition comprising lake pigments

Abstract

The present invention relates to a polymerizable liquid composition for the manufacture of an optical article, comprising: a) at least one allyl monomer or oligomer, b) at least one initiator for the polymerization of the allyl monomer or oligomer, and c) at least one lake pigment comprising an organic ionic colorant and at least one compound comprising a metal atom having an opposite charge to that of the organic ionic colorant, d) wherein even if the lake pigment is in the form of particles dispersed in the composition, the lake pigment is not comprised in nanoparticles, which are not the lake pigment itself.

Description

[0001] This invention relates to optical articles containing light-absorbing additives, and more particularly to polymerizable compositions containing light-absorbing additives that can be polymerized into optical articles.

[0002] Light-absorbing additives (LAAs) are often incorporated into optical products such as ophthalmic lenses. This may be due to reasons related to the health, comfort, or aesthetics of the user of the optical product.

[0003] It has been demonstrated that, for example, ultraviolet (UV) light (particularly the UVB and UVA ranges corresponding to wavelengths between 280 and 315 nm and between 315 and 380 nm, respectively), high-energy visible (HEV) light (particularly the violet and blue light ranges corresponding to wavelengths between 380 and 450 nm), and near-infrared light (NIR; corresponding to wavelengths from 780 to 1400 nm) have adverse effects on the eye when exposed to excessive radiation in those wavelength ranges.

[0004] Therefore, ophthalmic lenses containing UV LAA, HEV LAA, or NIR LAA can be used to protect the health of the wearer of the ophthalmic lens.

[0005] HEV LAA, and in most cases UV LAA or NIR LAA, are absorbed in the visible range, giving the lens an unattractive tint. This is detrimental to the wearer's color perception and aesthetics. The resulting lens may not be acceptable to the wearer, especially when considering non-solar products. LAA that absorbs in the visible range can be added to neutralize the tint caused by UV LAA, HEV LAA, or NIR LAA. In this case, the LAA absorbed in the visible range acts as a color balancer.

[0006] Different methods can be used to incorporate LAA into optical articles. For example, impregnation or absorption methods involve immersing a polymeric substrate, such as a lens substrate, in a bath containing LAA dissolved or dispersed in an organic solvent. LAA can also be contained in a coating deposited on the surface of the optical article substrate.

[0007] However, directly incorporating LAA into the polymerizable composition to obtain the substrate remains a preferred technique because it does not require additional processing steps to incorporate LAA and it allows for incorporation at relatively low concentrations. When LAA is confined to a relatively thin layer in the article (which is the case when LAA is included in a coating or impregnation layer), higher concentrations are required, which may degrade, for example, the mechanical properties of the article.

[0008] One known class of substrate materials is allyl substrates, which are composed of allyl monomers and / or allyl oligomers such as The polymerization or copolymerization of these substrate materials is produced. The polymerization or copolymerization of these substrate materials requires the polymerizable composition to contain an initiator for initiating the polymerization or copolymerization, such as a peroxide, for example, diisopropyl peroxydicarbonate (IPP).

[0009] Under the reaction conditions used to polymerize allyl substrates, initiators or other reactive intermediates generated during the polymerization reaction can react with and degrade LAA. Therefore, imparting color to allyl substrates or balancing the color of allyl substrates by directly incorporating LAA into the polymerizable composition to obtain the substrate remains challenging.

[0010] WO 2019 / 110264 discloses the use of LAA contained in nanoparticles as a color balancer in polymerizable compositions used to prepare allyl lens substrates. The fact that these LAAs are contained within the nanoparticles protects them from degradation under the reaction conditions used to polymerize the allyl lens substrates. However, the preparation of the nanoparticles requires additional processing steps.

[0011] EP 3382428 discloses the use of specific peroxide initiators (and thus different from, for example, IPP) having a single peroxycarbonate group in polymerizable compositions for preparing allyl lens substrates. The use of these initiators prevents the degradation of some LLAs (which in this case act as color balancers) under the reaction conditions used to polymerize the allyl lens substrate. However, these initiators only provide a solution to the problem for some dyes, while others will still degrade when using these initiators.

[0012] Therefore, the industry needs alternative polymerizable compositions for the preparation of allyl substrates (such as allyl lens substrates) containing LAA, so that LAA is not degraded during the polymerization process.

[0013] Inorganic pigment particles are known to resist degradation when exposed to peroxide initiators. However, they have proven unsuitable for use in polymerizable compositions for preparing allyl lens substrates containing LAA because large pigment particles diffuse light and increase lens turbidity.

[0014] Less is known about the stability of organic pigments to peroxide initiators. Typically, organic dyes and pigments contain molecules with electron-rich moieties and donor groups. Therefore, organic dyes and some organic pigments are expected to be particularly sensitive to oxidation.

[0015] Therefore, it is not apparent to those skilled in the art that, under the reaction conditions used to polymerize the allyl substrate, organic pigments will not degrade and / or will not diffuse light in a manner that increases the turbidity of optical articles such as lenses.

[0016] The applicant's advantage lies in the discovery that certain types of organic pigments (referred to as lake pigments) exhibit unexpected resistance to degradation when used as LAAs in polymerizable compositions for preparing allyl substrates, even in the presence of peroxide initiators. Furthermore, the applicant has found that optical articles obtained from such polymerizable compositions containing LAAs exhibit unexpectedly low levels of haze. Summary of the Invention

[0017] One aspect of the present invention relates to a polymerizable liquid composition for manufacturing optical articles, the polymerizable liquid composition comprising:

[0018] a) At least one allyl monomer or allyl oligomer

[0019] b) at least one initiator for polymerizing the allyl monomer or allyl oligomer, and

[0020] c) At least one lake pigment comprising an organic ionic colorant and at least one compound containing metal atoms having a charge opposite to that of the organic ionic colorant.

[0021] In some embodiments, the present invention relates to a polymerizable liquid composition for manufacturing optical articles, the polymerizable liquid composition comprising:

[0022] a) At least one allyl monomer or allyl oligomer

[0023] b) At least one initiator for polymerizing the allyl monomer or allyl oligomer.

[0024] c) At least one lake pigment comprising an organic ionic colorant and at least one compound containing metal atoms having a charge opposite to that of the organic ionic colorant, and

[0025] d) At least one light-absorbing additive other than the at least one lake pigment, selected from the group consisting of: colorants such as dyes or pigments; colorless light-absorbing additives; and mixtures thereof; preferably, the light-absorbing additive is a UV absorber and / or a HEV-light absorber.

[0026] Another aspect of the present invention relates to a method for preparing the polymerizable liquid composition of the present invention, the method comprising the following steps:

[0027] a) Provide allyl monomers or allyl oligomers;

[0028] b) Provide an initiator for polymerizing the allyl monomer or allyl oligomer;

[0029] c) Provide at least one lake pigment;

[0030] d) Optionally, a light-absorbing additive other than the at least one lake pigment is provided, selected from the group consisting of: colorants such as dyes or pigments, colorless light-absorbing additives, and mixtures thereof; preferably, the light-absorbing additive other than the at least one lake pigment is a UV absorber and / or a HEV-light absorber;

[0031] d) Mix the allyl monomer or allyl oligomer, the initiator, the at least one lake pigment, and, where applicable, the light-absorbing additives other than the at least one lake pigment.

[0032] Another aspect of the invention relates to the use of lake pigments dispersed in the polymerizable liquid compositions of the invention as colorants resistant to initiators used to polymerize allyl monomers or allyl oligomers.

[0033] Another aspect of the invention relates to an optical article obtained by a method comprising curing the polymerizable liquid composition of the invention. Detailed Implementation

[0034] The object of this invention is a polymerizable liquid composition for manufacturing optical articles, the polymerizable liquid composition comprising:

[0035] a) At least one allyl monomer or allyl oligomer

[0036] b) at least one initiator for polymerizing the allyl monomer or allyl oligomer, and

[0037] c) At least one lake pigment comprising an organic ionic colorant and at least one compound containing metal atoms having a charge opposite to that of the organic ionic colorant.

[0038] In the polymerizable liquid composition of the present invention, the at least one lake pigment can be used to provide color to the finished product and / or act as a color balancing agent.

[0039] In the following text, it should be understood that the term "light-absorbing additive" or the abbreviation LAA refers to light-absorbing additives other than at least one lake pigment.

[0040] The applicant has discovered that lake pigments are more resistant to initiators used to polymerize allyl monomers and / or oligomers than is expected with typical organic colorants. Furthermore, compared to what has been observed with other types of pigments known to be resistant to initiators used to polymerize allyl monomers and / or oligomers, optical articles, such as lenses, with low levels of haze can be obtained by curing the compositions of the present invention.

[0041] Not wanting to be bound by theory, it is believed that the presence of compounds containing metal atoms in pigments plays a role in their unexpected tolerance to initiators used to polymerize allyl monomers and / or oligomers.

[0042] As defined herein, lake pigments, also known as "lakes," are water-insoluble colorants comprising an organic ionic colorant and at least one compound containing metal atoms having a charge opposite to that of the organic ionic colorant.

[0043] The organic ionic colorant is an anion and the at least one compound containing a metal atom is a non-alkali metal cation, or

[0044] The organic ionic colorant is cationic and the at least one compound containing a metal atom is an anionic coordination complex containing a metal atom.

[0045] As defined in this article, a mixture of lake pigments is also a lake pigment.

[0046] As defined herein, a metal atom can be an alkali metal atom (Li, Na, K, Rb, Cs, and Fr), an alkaline earth metal (Be, Mg, Ca, Sr, Ba, and Ra), a transition metal atom, a lanthanide atom, an actinide atom, Al, Ga, In, Sn, Tl, Pb, Bi, Po, or a metalloid atom (B, Si, Ge, As, Sb, Te). Therefore, non-alkali metal cations can include any cation obtained by removing one or more electrons from an alkaline earth metal (Be, Mg, Ca, Sr, Ba, and Ra), a transition metal atom, a lanthanide atom, an actinide atom, Al, Ga, In, Sn, Tl, Pb, Bi, Po, or a metalloid atom (B, Si, Ge, As, Sb, Te).

[0047] Lake pigments can be obtained by adding at least one compound containing a metal atom, or in acidic or basic form, to a solution of an ionic organic colorant, a solution of its conjugate acid, or a solution of its conjugate base, sufficient to make the ionic organic colorant, its conjugate acid, or its conjugate base insoluble.

[0048] As defined herein, the acid form of a compound refers to the stable form of the compound in acidified water, and the basic form of a compound refers to the stable form of the compound in alkaline water.

[0049] When obtaining lake pigments according to the method described above, it is preferable that at least one compound containing metal atoms, used to make the ionic organic colorant insoluble in the preparation of the lake pigment, is itself soluble in the solvent in which the preparation takes place. Preferably, this solvent is water.

[0050] According to the present invention, it is preferred that at least one compound containing metal atoms in the lake pigment is such that at least one alkali metal salt of the compound containing metal atoms, or a halide salt of the compound, or an acidic form or a basic form of the compound is soluble in water.

[0051] According to the present invention, it is preferred that the ionic organic colorant contained in the lake pigment is such that the alkali metal salt of the ionic organic colorant, or the halide salt of the ionic organic colorant, or the conjugate base of the ionic organic colorant, or the conjugate acid of the ionic organic colorant is soluble in water.

[0052] In a given amount of lake pigment, the total charge of a certain amount of ionic organic colorant contained in the lake pigment does not need to be precisely balanced with the total charge of a certain amount of at least one compound containing metal atoms contained in the lake pigment.

[0053] According to the present invention, preferably, the total charge of the at least one compound containing metal atoms contained in the composition is between 50% and 150% of the opposite charge of the total charge of the ionic organic colorant contained in the composition, preferably between 80% and 120%.

[0054] Alternatively or additionally, the total charge of a certain amount of at least one compound containing metal atoms contained in a certain amount of lake pigment contained in the composition may be between 50% and 150%, preferably between 80% and 120%, of the opposite charge of the total charge of a certain amount of ionic organic colorant contained in a certain amount of lake pigment contained in the composition.

[0055] According to the present invention, it should be understood that organic ionic colorants can be single chemical compounds or mixtures of chemical compounds.

[0056] Preferred organic ionic colorants can be derived from azo dyes, polymethazine dyes, arylmethazine dyes, pyrazolone dyes, anthraquinone dyes, isoindolineone dyes, quinolineone dyes, naphthyldiamine dyes, and carbonyl dyes.

[0057] According to the present invention, when the ionic organic colorant is anionic, it is preferably the conjugate base of an acidic colorant. Preferably, the anionic organic colorant contained in the lake pigment in the polymerizable liquid composition of the present invention contains a carboxylate group (RCO2). - ) and / or sulfonate groups (RSO3) - ).

[0058] According to the present invention, when the ionic organic colorant is cationic, it is preferably a basic colorant, such as a colorant containing one or more amino groups or a conjugate acid of a colorant containing one or more tetravalent nitrogen atoms.

[0059] According to the present invention, the non-alkali metal cations contained in the lake pigment may include the same non-alkali metal cations or a mixture of non-alkali metal cations.

[0060] Preferably, when the ionic organic colorant contained in the lake pigment in the polymerizable liquid composition of the present invention is anionic, these compounds containing metal atoms are selected from the following non-alkali metal cations: Mg 2+ Al 3+ Ca 2 + Cr 3+ Mn 2+ Fe 2+ Fe 3+ Co 3+ Ni 2+ Cu 2+ Zn 2+ Ba 2+ 、Sr 2+ The non-alkali metal cations and their mixtures. Preferably, the non-alkali metal cations do not contain alkaline earth cations; more preferably, the non-alkali metal cations are trivalent cations; and even more preferably, the non-alkali metal cations are Al. 3+ .

[0061] Indeed, the applicant has observed that in some lake pigments containing anionic organic colorants, when the non-alkali metal cations contained in the lake pigments are alkaline earth cations, the lake pigments are less resistant to degradation under the reaction conditions used for polymerizing allyl substrates than when the non-alkali metal cations contained in the lake pigments are not alkaline earth cations.

[0062] According to the present invention, the anionic coordination complex containing metal atoms contained in the lake pigment can be a single chemical compound or a mixture of anionic coordination complexes containing metal atoms.

[0063] Preferably, when the ionic organic colorant contained in the lake pigment in the polymerizable liquid composition of the present invention is cationic, at least one compound containing a metal atom is selected from the following anionic coordination complexes containing metal atoms: polyoxometalates, copper(I) iron(II) cyanides ([Cu3Fe(CN)6]). - ), and their mixtures.

[0064] As defined herein, a polyoxometalate is a polyatomic anion comprising three or more transition metal atoms selected from Mo, W, V, and mixtures thereof, in their highest oxidation state, linked together by oxygen atoms. Polyoxometalates may also contain heteroatoms (i.e., atoms that are neither oxygen nor V, Nb, Ta, Mo, or W) such as phosphorus, silicon, cobalt, aluminum, manganese, chromium, nickel, or mixtures thereof. When present, these heteroatoms and the network formed by the oxygen atoms, along with the three or more transition metal atoms selected from Mo, W, V, and mixtures thereof, are linked together by oxygen atoms. Polyoxometalates containing heteroatoms are called heteropolyoxometalates.

[0065] Polyoxometalates are typically obtained by acidifying solutions of tungstates, molybdates, and / or vanadates in the form of alkali metal salts and / or ammonium salts. When this acidification is carried out in the presence of heteroatoms, for example, phosphates and / or water-soluble silicates, heteropolyoxometalates, can be obtained. Various polyoxometalates can be synthesized by selecting the ratio of tungstates, molybdates, vanadates, and optionally the ratio of phosphates and silicates.

[0066] Preferred examples of polyoxometalates that may be included in lake pigments contained in the polymerizable liquid compositions of the present invention include phosphotungstate, phosphotomolybdate, silicomolybdate, silicotungstate, phosphotomolybdate, phosphotomolybdate, phosphotomolybdate, silicomolybdate, phosphotomo ...

[0067] In the polymerizable liquid composition of the present invention, at least one lake pigment is preferably selected from:

[0068] ·Phosphomothiotungstate of N-methyl derivatives of 4-[(4-aminophenyl)-(4-methyliminocyclohexyl-2,5-diene-1-yl)methyl]aniline,

[0069] A mixture of aluminum 7-hydroxy-8-[(4-sulfonyl-1-naphthyl)azo]-1,3-naphthalenedisulfonic acid complex and (E)-3,3'-dioxy-1H,1'H,3H,3'H-[2,2'-bis(dihydroindoleyl)-5,5'-disulfonic acid aluminum complex.

[0070] A mixture of dihydro(ethyl)[4-[[4-[ethyl(3-sulfonate benzyl)amino]phenyl](2-sulfonate benzyl)methylene]cyclohexyl-2,5-diene-1-ylidene](3-sulfonate benzyl)ammonium, aluminum salt and tris[2-(2,4,5,7-tetrabromo-6-oxo-3-oxoxanthen-9-yl)-3,4,5,6-tetrachlorobenzoic acid]dialuminiumtris[2-(2,4,5,7-tetrabromo-6-oxido-3-oxoxanthen-9-yl)-3,4,5,6-tetrachlorobenzoate]

[0071] A mixture of tris[5-amino-4-hydroxy-3-(phenylazo)naphthyl-2,7-disulfonic acid 2-]dialuminum and dihydro(ethyl)[4-[[4-[ethyl(3-sulfonic acid 2-benzyl)amino]phenyl](2-sulfonic acid 2-benzyl)methylene]cyclohexyl-2,5-diene-1-ylidene](3-sulfonic acid 2-benzyl)ammonium, aluminum salt.

[0072] In some embodiments, the lake pigment is completely dissolved in the composition of the present invention. In other embodiments, the lake pigment is partially or completely insoluble in the composition of the present invention. In these embodiments, the undissolved portion of the lake pigment is dispersed in the composition.

[0073] In some embodiments, the lake pigment is completely soluble in the allyl monomer or allyl oligomer contained in the composition of the present invention. In other embodiments, the lake pigment is partially or completely insoluble in the allyl monomer or allyl oligomer contained in the composition of the present invention.

[0074] In these embodiments, the portion of the lake pigment that is not dissolved in the allyl monomer or allyl oligomer contained in the composition is then preferably present in the polymerizable liquid composition of the present invention in the form of particles dispersed in the composition. Preferably, these particles have a size of less than 1 μm, more preferably less than 500 nm, and even more preferably less than 300 nm (e.g., the diameter in the case of spherical particles). When using dynamic light scattering to measure the particle size, the particle size is preferably measured using an output parameter called the Z-mean. Preferably, the Z-mean of the lake pigment particles contained in the polymerizable liquid composition of the present invention is less than 1 μm, more preferably less than 500 nm, and even more preferably less than 300 nm, as measured by dynamic light scattering.

[0075] In the polymerizable liquid composition of the present invention, it is preferred that the amount of lake pigment is from 1 to 40 ppm by weight relative to the total weight of the composition, more preferably from 1 to 25 ppm, even more preferably from 5 to 25 ppm, and most preferably from 5 to 15 ppm.

[0076] In some embodiments, the polymerizable liquid composition of the present invention further comprises at least one light-absorbing additive other than the at least one lake pigment selected from the group consisting of: colorants such as dyes or pigments; colorless light-absorbing additives; and mixtures thereof; preferably the light-absorbing additive is a UV absorber and / or a HEV-light absorber.

[0077] Therefore, according to these embodiments, the present invention is a polymerizable liquid composition for manufacturing optical articles, the polymerizable liquid composition comprising:

[0078] a) At least one allyl monomer or allyl oligomer

[0079] b) At least one initiator for polymerizing the allyl monomer or allyl oligomer.

[0080] c) At least one lake pigment comprising an organic ionic colorant and at least one compound containing metal atoms having a charge opposite to that of the organic ionic colorant, and

[0081] d) At least one light-absorbing additive other than the at least one lake pigment, selected from the group consisting of: colorants such as dyes or pigments; colorless light-absorbing additives; and mixtures thereof; preferably, the light-absorbing additive is a UV absorber and / or a HEV-light absorber.

[0082] Preferably, the light-absorbing additive, other than at least one lake pigment, has the following structure.

[0083]

[0084] Where R 3 and R 4 Each is independently selected from H or an alkyl chain having 1 to 12 carbons, preferably wherein R 3 and R 4 It is a methyl group.

[0085] In the polymerizable liquid composition of the present invention, it is preferred that the amount of light-absorbing additives, other than at least one lake pigment, is less than 2% by weight relative to the total weight of the composition, more preferably less than 1%, and even more preferably less than 0.5%.

[0086] In the polymerizable liquid composition of the present invention comprising LAA other than at least one lake pigment, it is preferred that the amount of LAA is from 0.01% to 2% by weight relative to the total weight of the composition, more preferably less than from 0.02% to 1%, and even more preferably from 0.05% to 0.5%.

[0087] In one embodiment of the polymerizable liquid composition of the present invention, a light-absorbing additive other than at least one lake pigment is contained in nanoparticles dispersed in an allyl monomer or an allyl oligomer.

[0088] At least one lake pigment contained in the polymerizable liquid composition of the present invention is not, where applicable, contained in nanoparticles, which are not the lake pigment particles themselves.

[0089] As used herein, the expressions “LAA contained in nanoparticles” (according to one embodiment of the invention) or “lake pigment contained in nanoparticles” (not according to the invention) mean any one of the following: LAA or lake pigment uniformly dispersed in nanoparticles, LAA or lake pigment located at the core of nanoparticles, LAA or lake pigment located at the surface of nanoparticles, and LAA or lake pigment located inside the pores of nanoparticles.

[0090] When the polymerizable liquid composition according to the invention contains LAA contained in nanoparticles, the nanoparticles are dispersed in the polymerizable composition.

[0091] The nanoparticles behave like capsules, within which the light-absorbing additives are protected. Indeed, active reactants from the compositions according to the invention, such as initiators used to polymerize allyl monomers or allyl oligomers or other reactive intermediates generated during polymerization, will not be able to diffuse into the interior portions of the nanoparticles. If the light-absorbing additives are located on the surface or in the pores of the nanoparticles, the active reactants may be able to access them, but the likelihood of reaction is reduced due to the hindered movement of the grafted or trapped additives, and the additives are also protected.

[0092] In the context of this invention, the term "nanoparticle" is intended to mean an individualized particle having a Z-average in the range of 1 nm to 10 μm, preferably in the range of 10 nm to 5 μm, more preferably in the range of 10 nm to 1 μm, and even more preferably in the range of 10 nm to 500 nm, as measured by dynamic light scattering.

[0093] If LAA is readily degraded as an initiator for polymerizing allyl monomers or allyl oligomers, then including LAA in the nanoparticles of the polymerizable liquid compositions of the present invention may be useful.

[0094] In the polymerizable liquid composition according to the invention, the allyl monomer or allyl oligomer is preferably selected from the group consisting of: diethylene glycol bis(allyl carbonate), ethylene glycol bis(allyl carbonate), oligomers of diethylene glycol bis(allyl carbonate), oligomers of ethylene glycol bis(allyl carbonate), bisphenol A bis(allyl carbonate), diallyl phthalate, diallyl isophthalate, diallyl terephthalate, and mixtures thereof.

[0095] In the polymerizable liquid composition of the present invention, it is preferred that the amount of allyl monomer or allyl oligomer is from 70% to 99% by weight relative to the total weight of the composition, more preferably from 80% to 98%, and even more preferably from 90% to 97%.

[0096] In the polymerizable liquid composition according to the invention, the initiator for polymerizing the allyl monomer or allyl oligomer is preferably selected from peroxydicarbonate, peroxycarbonate, peroxyester, perketal, and mixtures thereof. More preferably, the initiator used to polymerize the allyl monomer or allyl oligomer is selected from diisopropyl peroxydicarbonate, 1,1-dimethylpropyl-1-methoxycyclohexyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, di-tert-butyl peroxide, lauroyl peroxide, acetyl peroxide, bis(4-tert-butylcyclohexyl) peroxydicarbonate, tert-butyl peroxy-2-ethylhexanoate, tert-hexyl peroxy-2-ethylhexanoate, 1,1-bis(tert-butylperoxy)cyclohexane, 1,1-bis(tert-pentylperoxy)cyclohexane, (2-ethylhexyl)monoperoxypentyl ester, (2-ethylhexyl)monoperoxytert-butyl ester, tert-butylmonoperoxyisopropyl ester, poly(tert-butylperoxycarbonate) polyether, and mixtures thereof. Even more preferably, the initiator used to polymerize the allyl monomer or allyl oligomer is diisopropyl peroxydicarbonate.

[0097] In the polymerizable liquid composition of the present invention, it is preferred that the amount of initiator used to polymerize the allyl monomer or allyl oligomer is from 0.5% to 20% by weight relative to the total weight of the composition, more preferably from 1% to 10%, and even more preferably from 1.5% to 5%.

[0098] According to a preferred embodiment of the present invention, the polymerizable liquid composition of the present invention comprises:

[0099] - Diethylene glycol bis(allyl carbonate) from 90% to 97%;

[0100] - Diisopropyl peroxide dicarbonate from 1.5% to 5%;

[0101] -Optionally, a light-absorbing additive having the following structure, present in amounts between 0.05% and 0.5%, which is not contained in the nanoparticles,

[0102]

[0103] Where R 3 and R 4 Each is independently selected from H or an alkyl chain having 1 to 12 carbons, preferably wherein R 3 and R 4 It is methyl;

[0104] - At least one lake pigment ranging from 1 to 25 ppm;

[0105] These quantities are expressed by weight relative to the total weight of the composition.

[0106] Another object of the present invention is a method for preparing polymerizable liquid compositions as described above.

[0107] Therefore, the present invention also relates to a method for preparing the polymerizable liquid composition of the present invention, the method comprising the following steps:

[0108] a) Provide allyl monomers or allyl oligomers;

[0109] b) Provide an initiator for polymerizing the allyl monomer or allyl oligomer;

[0110] c) Provide at least one lake pigment;

[0111] d) Optionally, a light-absorbing additive other than the at least one lake pigment is provided, selected from the group consisting of: colorants such as dyes or pigments, colorless light-absorbing additives, and mixtures thereof; preferably, the light-absorbing additive other than the at least one lake pigment is a UV absorber and / or a HEV-light absorber.

[0112] e) Mix the allyl monomer or allyl oligomer, the initiator, the at least one lake pigment, and, where applicable, the light-absorbing additives other than the at least one lake pigment.

[0113] In the method of the present invention, steps a), b), c), and d) are performed in any order prior to step e).

[0114] All the features described above for the different elements (alone or in combination) of the polymerizable liquid composition are of course applicable to the methods used to prepare the polymerizable liquid composition.

[0115] In the method of the present invention, it is preferred that in step c), at least one lake pigment is provided in the form of a mixture of at least one lake pigment and an allyl monomer or an allyl oligomer, wherein the lake pigment content of the mixture is between 0.01% and 1% by weight relative to the total weight of the mixture, and preferably the allyl monomer or allyl oligomer provided in step c) has the same properties as the allyl monomer or allyl oligomer provided in step a), i.e., a mixture containing the same compounds therewith.

[0116] The method of the present invention may further include step c0) preparing a mixture of at least one lake pigment and an allyl monomer or an allyl oligomer provided in step c).

[0117] This step c0) can help improve the haze of articles obtained from compositions obtained by the method of the present invention.

[0118] Step c0) may include mixing at least one lake pigment from step c) with an allyl monomer or an allyl oligomer and recovering the mixture. Preferably, the mixing step is carried out in the presence of milled microspheres under stirring, or under ultrasonic treatment, or both. Stirring in the presence of milled microspheres is preferred. The milled microspheres may have a diameter of 0.1 mm to 4 mm, preferably 0.2 mm to 3 mm, more preferably 1 mm to 2.5 mm. Preferably, the milled microspheres are zirconia microspheres. More preferably, stirring in the presence of milled microspheres is carried out at a stirring speed of at least 300 rpm and lasts for at least 1 hour. Even more preferably, stirring in the presence of milled microspheres is carried out using a basket mill (lasting 1 hour to 6 hours) and at a stirring speed of 500 rpm to 3000 rpm, most preferably 700 rpm to 1500 rpm.

[0119] Preferably, step e) of the method of the present invention includes the following steps in the following order:

[0120] e1) The step of cooling the allyl monomer or allyl oligomer provided in step a) and, when applicable, mixing it with the light-absorbing additive provided in step d), wherein the cooling is such that the temperature of the mixture at the end of step e1) is below or equal to 5°C, preferably below or equal to 2°C.

[0121] e2) Add the initiator to the cooled mixture obtained after step e) while maintaining it at the temperature reached at the end of step e1);

[0122] e3) Adding at least one lake pigment, or, where applicable, a mixture of at least one lake pigment provided in step c) with an allyl monomer or an allyl oligomer, to the mixture obtained after step e2) while maintaining it at the temperature reached at the end of step e1).

[0123] The method of the present invention may further include a filtration step of the mixture obtained after step e), preferably wherein a filter of 1 μm or smaller is used for filtration.

[0124] Another object of the present invention is the use of lake pigments dispersed in the polymerizable liquid compositions described above as colorants resistant to initiators used to polymerize allyl monomers or allyl oligomers. Preferably, lake pigments are used as color balancers, and more preferably, lake pigments are used to prevent yellowing of optical articles or optical article substrates containing allyl polymers.

[0125] All the features described above for the different elements (alone or in combination) of polymerizable liquid compositions certainly apply to polymerizable liquid compositions in which lake pigments are used.

[0126] Another object of the present invention is a first optical article which can be obtained or acquired by a method comprising curing a polymerizable liquid composition as described above.

[0127] All the features described above for the different elements (alone or in combination) of polymerizable liquid compositions are of course applicable to polymerizable liquid compositions that can produce or produce optical products.

[0128] In some embodiments, the first optical article of the present invention includes an optical substrate that can be obtained or acquired by a method comprising curing a polymerizable liquid composition as described above.

[0129] In some other embodiments, the first optical article of the present invention may include:

[0130] a) Optical substrate;

[0131] b) A coating that can be obtained or acquired by curing the polymerizable liquid composition of the present invention onto the optical substrate.

[0132] In the context of this invention, substrate should be understood to mean an uncoated substrate and typically has two main surfaces. In particular, the substrate can be an optically transparent material having the shape of an optical article (e.g., an ophthalmic lens destined for mounting on eyeglasses). The substrate can serve as a support for a stack of one or more coatings.

[0133] The optical articles of the present invention may have a haze value of less than 0.5%, preferably less than 0.4%, and more preferably less than 0.3%.

[0134] Haze is the percentage of transmitted light that deviates from the incident beam due to forward scattering as it passes through a sample. Haze is measured by light transmission according to ASTM D1003.00. As haze increases, a loss of contrast occurs until the object becomes invisible.

[0135] The optical articles of the present invention may have a light cutoff value of more than 380 nm, preferably more than 390 nm, and even more preferably more than 395 nm.

[0136] Optical cutoff is defined as the lowest wavelength at which the transmittance of an optical article is higher than 1%.

[0137] When the optical component is a lens, the light cutoff of light incident perpendicularly at the center of the lens is measured.

[0138] The optical articles of the present invention may have a yellow index of -4 to 4, preferably -1 to 4, and more preferably -0.5 to 3.

[0139] The Yellow Index (YI) is a colorimetric calculation based on the tri-stimulus values ​​(X, Y, Z) according to ASTM E313.

[0140] The optical article of the present invention may have a relative light transmittance factor T of 85% or higher, preferably 86% or higher, more preferably 87% or higher, and even better 88% or higher in the visible spectrum. v .

[0141] The optical article of the present invention may have an anti-reflective coating applied to one or both air / substrate interfaces. In such embodiments, T v The range of the factor is preferably from 90% to 99%, more preferably from 90% to 98%, and even better from 90% to 97%.

[0142] T v The factor, also known as the system’s “light transmittance,” is defined as in standard NF EN 1836 and is associated with an average value in the wavelength range of 380–780 nm, which is weighted according to the eye’s sensitivity at each wavelength in that range and is measured under D65 illumination conditions (daylight).

[0143] The optical articles of the present invention may have a colorimetric coefficient b* as defined in the CIE (1976) L*a*b* International Colorimetric System, which is less than or equal to 2.5, preferably less than or equal to 2, more preferably less than or equal to 1.5, and even more preferably less than or equal to 1 (for an optical material thickness of 2 mm), and generally greater than or equal to 0. The low colorimetric coefficient b* of the optical material may be related to its non-yellow appearance.

[0144] For light transmitted through the material at an incident angle ranging from 0° to 15°, especially 0°, the colorimetric coefficients a*, b*, C*, and h of a given material are calculated between 380 and 780 nm for a material thickness of 2 mm, using a standard observer of 10° and a standard light source D65 as defined in the International Colorimetric System CIE L*a*b*.

[0145] The optical product of the present invention is preferably an ophthalmic lens.

[0146] Non-limiting examples of ophthalmic lenses include corrective and uncorrective lenses, including single-vision or multi-vision lenses (i.e., afocal lenses, single-vision lenses, bifocal lenses, trifocal lenses, and progressive lenses), which may be segmented or non-segmented, and other elements for correcting, protecting, or enhancing vision, including but not limited to contact lenses, intraocular lenses, lenses for augmented reality or virtual reality devices, protective lenses (such as sunglasses or sunglass lenses), goggles (such as goggles for skiing, cycling, and motorcycling), and visors (such as helmet visors).

[0147] In some embodiments, the optical article of the present invention is an ophthalmic lens having the following: a haze of less than 0.5%, preferably less than 0.4%, more preferably less than 0.3%, a center thickness of less than 3 mm, a light cutoff of more than 390 nm, preferably more than 395 nm, and a yellow index between -1 and 4, preferably between -0.5 and 3.

[0148] Another object of the present invention is a second optical article comprising a material that can be obtained or acquired by curing an allyl monomer or an allyl oligomer, wherein the material comprises at least one lake pigment dispersed therein, and wherein even if the lake pigment is in the form of particles dispersed in the material, the lake pigment is not contained in nanoparticles that are not the lake pigment itself.

[0149] In some embodiments, the material included in the second optical article of the present invention further comprises a light-absorbing additive other than the at least one lake pigment, selected from the group consisting of: colorants such as dyes or pigments, colorless light-absorbing additives, and mixtures thereof; preferably, the light-absorbing additive other than the at least one lake pigment is a UV absorber and / or a HEV-light absorber.

[0150] All features described above for the first optical article of the present invention (alone or in combination) are applicable to the second optical article of the present invention.

[0151] All the features described above for allyl monomers or allyl oligomers (alone or in combination) apply to allyl monomers or allyl oligomers of the material contained in the second optical article of the present invention, which can be obtained by curing.

[0152] All the features described above for lake pigments and light-absorbing additives (alone or in combination) other than at least one lake pigment are applicable to the elements contained in the second optical article of the present invention.

[0153] In the materials included in the second optical article of the present invention, it is preferred that the amount of lake pigment is from 1 to 40 ppm by weight relative to the total weight of the materials, more preferably from 1 to 25 ppm, even more preferably from 5 to 25 ppm, and most preferably from 5 to 15 ppm.

[0154] In the second optical article of the present invention, the material comprising LAA other than at least one lake pigment is preferably less than 2% by weight, more preferably less than 1% by weight, and even more preferably less than 0.5% by weight relative to the total weight of the composition.

[0155] In the second optical article of the present invention, the material comprising LAA other than at least one lake pigment is preferably in an amount of LAA from 0.01% to 2% by weight relative to the total weight of the composition, more preferably less than from 0.02% to 1%, and even more preferably from 0.05% to 0.5%.

[0156] In some embodiments, the second optical article of the present invention comprises an optical substrate, which is made substantially of the material that can be obtained by curing an allyl monomer or an allyl oligomer and contains a lake pigment dispersed therein.

[0157] In some embodiments, the second optical article of the present invention includes an optical substrate and a coating, the coating being made substantially of the material which can be obtained by curing an allyl monomer or an allyl oligomer and which contains a lake pigment dispersed therein.

[0158] Example

[0159] The optical characteristics of the lens were determined using a CARY 60 spectrophotometer from Agilent Technologies.

[0160] All the lenses produced are plano lenses with a center thickness of 2mm.

[0161] Light transmittance factor T in the visible spectrum v It is measured from the wearer's perspective using a transmission mode. T v It was measured under D65 lighting conditions (daylight).

[0162] The wavelength of light cutoff is determined by the transmission spectrum.

[0163] The yellowness index Yi of the prepared lens is calculated as described above by measuring the CIE trichromatic stimulus values ​​X, Y, and Z on a white background using a spectrophotometer equipped with the aforementioned reflectance, as described in standard ASTM E 313-05. From the observer's perspective, this method of measuring Yi most closely approximates the actual wearing situation.

[0164] Haze was measured using a Hazeguard XL-211 via light transmission measurement according to ASTM D1003-00.

[0165] lake pigments

[0166] In the following examples, three lake pigments with purple hues were used. These three lake pigments are referred to below as M1 (a mixture of blue and red lakes), M2 (containing a purple lake), and M3 (a mixture of blue and red lakes), respectively. Their compositions are described in Table 1.

[0167] Table 1

[0168]

[0169]

[0170] Masterbatch

[0171] The following method was used to prepare a lake pigment and an allyl monomer. Masterbatch.

[0172] Lake pigments and allyl monomers The mixture was then combined with 2 mm diameter zirconium microspheres from RETSCH. This mixture was then stirred at 400 rpm for at least 12 hours in a flask with a magnetic stir bar, or at 1100 rpm for 3 hours in a 2 L basket mill. The zirconium microspheres were then removed from the mixture to recover the masterbatch.

[0173] The concentration of masterbatch in lake pigments is 0.1% by mass relative to the total mass of masterbatch.

[0174] The average diameter of the particles in the masterbatch and their polydispersity index (PDI) were measured by dynamic light scattering (DLS; 10 mm cuvette; masterbatch diluted 10 times). The results of the DLS measurements are given in Table 2, where the average particle diameter is expressed as Z-mean.

[0175] Table 2

[0176] lake pigments Stirring method Stirring time Z-mean PDI M1 Magnetic stirring rod 12 hours 234nm 0.31 M3 Magnetic stirring rod 24 hours 250nm 0.12

[0177] polymerizable compositions

[0178] Four polymerizable compositions for manufacturing ophthalmic lenses capable of suppressing UV light transmission were prepared: three compositions C1, C2 and C3 according to the invention, which respectively contain M1, M2 and M3 as color balancers, and a comparative composition C0 that does not contain any color balancer.

[0179] Table 3 details the composition of C0-C3, where the amounts are given as % by mass relative to the total mass of the composition.

[0180] Table 3

[0181]

[0182] The procedure for preparing polymerizable compositions is as follows:

[0183] i. at room temperature CR39E and Mix BP6 for 1 hour until the UV absorber is completely dissolved;

[0184] ii. Cool the mixture to a temperature below 2°C;

[0185] iii. Add IPP and continue stirring the mixture for 10 minutes, while keeping the temperature below 2°C;

[0186] iv. Add color masterbatch and continue stirring the mixture for 10 minutes, while keeping the temperature below 2°C;

[0187] v. Use a stirring plate to vent the air at a mixing speed of 200 rpm for 30 minutes, and then vent the air for 15 minutes without stirring, always keeping the temperature below 2°C;

[0188] vi. To filter preparations using a 1μm filter at 4°C.

[0189] lens

[0190] Four lenses L0-L3 were prepared from compositions C0-C3 using the following procedures.

[0191] The composition was filled into a 77mm diameter glass matte mold using a syringe. The polymerization reaction was carried out in an adjustable electronic oven according to the following cycle: the temperature was set at 48°C for 8 hours, then gradually increased to 85°C over 9 hours, and then kept constant at 85°C for 3 hours.

[0192] The mold was disassembled at 65°C. The resulting lens was then annealed at 100°C for 1 hour.

[0193] Table 5 details the optical characteristics of lenses L0-L3.

[0194] Table 4

[0195] lens Optical cutoff (nm) <![CDATA[T v (%)]]> YI L* a* b* C* h° Haze L0 396 92.2 3.2 96.9 -1.3 2.6 2.9 116.8 0.2％ L1 396 90.8 2.8 96.3 -1.3 2.4 2.7 118.4 0.4％ L2 396 87.5 -0.3 95.0 -0.9 0.6 1.1 148.5 0.4％ L3 396 90.8 2.1 96.3 -1.2 2.0 2.3 121.1 0.3％

[0196] Stability of optical features

[0197] Polymerization stability

[0198] The extent to which lake pigments degrade during the polymerization process is measured by measuring the liquid composition (A liq ) and solid lenses (A) obtained from the composition sol The absorbance is evaluated at a specific wavelength corresponding to the maximum absorption value. sol and A liq The measurements were taken using a 2mm thick sample. The percentage of absorbance loss between the absorbance of the liquid and the absorbance of the solid (loss % L - S = (A)) liq -A sol ) / A liq (x 100) is given in Table 6.

[0199] Table 5

[0200]

[0201] These loss %L- and -S values ​​are much better than those obtained with common organic dyes.

[0202] Light stability

[0203] Lenses L0-L3 were tested using the Q-sun xenon arc test chamber via Q-LAB to evaluate their optical characteristics and photostability after 80 hours of exposure to light (a xenon arc lamp with an irradiance setting of 0.68 W / m² at 340 nm).

[0204] Tables 7 to 9 present the optical characteristics of the lenses at three different measurement times (0, 40, and 80 hours of light exposure). Each value given in the table corresponds to the average of 12 measurements performed on 12 different lenses prepared in the same manner (one measurement per lens).

[0205] The optical stability of a lens is evaluated by calculating the parameter ΔE using the following formula:

[0206]

[0207] If the ΔE value is less than 1, the optical characteristics of the lens are considered to be optically stable.

[0208] Table 6

[0209]

[0210] Table 7

[0211]

[0212] Table 9

[0213]

[0214] Table 10

[0215]

Claims

1. A polymerizable liquid composition for manufacturing optical articles, said polymerizable liquid composition comprising: a) at least one allyl monomer or allyl oligomer b) At least one initiator for polymerizing the allyl monomer or allyl oligomer, wherein the initiator is selected from peroxydicarbonate, peroxycarbonate, peroxyester, perketal, and mixtures thereof, and c) At least one lake pigment The lake pigment is either completely dissolved in the composition, or partially or completely insoluble in the composition, and the undissolved portion of the lake pigment is dispersed in the composition in particulate form. The lake pigments therein are insoluble in water, and The lake pigment comprises anionic organic colorant and non-alkali metal cation, or the lake pigment comprises a cationic organic colorant and anionic coordination complex containing metal atoms.

2. The polymerizable liquid composition according to claim 1, wherein, -The lake pigment contains an anionic organic colorant and a non-alkali metal cation selected from the following: Mg 2+ Al 3+ Ca 2+ Cr 3+ Mn 2+ Fe 2+ Fe 3+ Co 3+ Ni 2+ Cu 2+ Zn 2+ Ba 2+ 、Sr 2+ , and their mixtures, or - The lake pigment comprises a cationic organic colorant and an anionic coordination complex containing metal atoms selected from the following: polyoxometalates, [Cu3Fe(CN)6] - , and their mixtures.

3. The polymerizable liquid composition according to claim 1, wherein, The lake pigment contains anionic organic colorants and trivalent cations.

4. The polymerizable liquid composition according to claim 1, wherein, The lake pigment contains anionic organic colorants, which contain carboxylate groups (RCO2). - ) and / or sulfonate groups (RSO3) - ).

5. The polymerizable liquid composition according to claim 1, wherein, The at least one lake pigment is selected from: Phosphomothite of N-methyl derivatives of 4-[(4-aminophenyl)-(4-methyliminocyclohexyl-2,5-diene-1-yl)methyl]aniline, A mixture of aluminum 7-hydroxy-8-[(4-sulfonyl-1-naphthyl)azo]-1,3-naphthalenedisulfonic acid complex and (E)-3,3'-dioxy-1H,1'H,3H,3'H-[2,2'-bis(dihydroindoleyl)-5,5'-disulfonic acid aluminum complex. A mixture of dihydro(ethyl)[4-[[4-[ethyl(3-sulfonate benzyl)amino]phenyl](2-sulfonate benzyl)methylene]cyclohexyl-2,5-diene-1-ylidene](3-sulfonate benzyl)ammonium, aluminum salt and tris[2-(2,4,5,7-tetrabromo-6-oxo-3-oxyxanthracene-9-yl)-3,4,5,6-tetrachlorobenzoic acid]dialuminum, A mixture of tri[5-amino-4-hydroxy-3-(phenylazo)naphthyl-2,7-disulfonic acid 2-]dialuminum and dihydro(ethyl)[4-[[4-[ethyl(3-sulfonic acid 2-benzyl)amino]phenyl](2-sulfonic acid 2-benzyl)methylene]cyclohexyl-2,5-diene-1-ylidene](3-sulfonic acid 2-benzyl)ammonium, aluminum salt.

6. The polymerizable liquid composition according to any one of claims 1 to 5, wherein, At least a portion of the at least one lake pigment is not dissolved in the at least one allyl monomer or allyl oligomer contained in the composition, and the portion of the at least one lake pigment is in the form of particles dispersed in the composition, and the particle size of the at least one lake pigment is less than 1 µm.

7. The polymerizable liquid composition according to any one of claims 1 to 5, wherein, The amount of lake pigment is from 1 to 40 ppm by weight relative to the total weight of the composition.

8. The polymerizable liquid composition according to any one of claims 1 to 5, further comprising a light-absorbing additive other than the at least one lake pigment selected from the group consisting of: a colorant; a colorless light-absorbing additive; and mixtures thereof.

9. The polymerizable liquid composition according to claim 8, wherein, The light-absorbing additive has the following structure Where R 3 and R 4 Each is independently selected from H or an alkyl chain having 1 to 12 carbons.

10. The polymerizable liquid composition according to claim 9, wherein R 3 and R 4 It is a methyl group.

11. The polymerizable liquid composition according to claim 9 or 10, wherein, The light-absorbing additive is contained in nanoparticles dispersed in the allyl monomer or allyl oligomer.

12. The polymerizable liquid composition according to any one of claims 1 to 5, wherein, The allyl monomer or allyl oligomer is selected from the group consisting of: diethylene glycol bis(allyl carbonate), ethylene glycol bis(allyl carbonate), oligomers of diethylene glycol bis(allyl carbonate), oligomers of ethylene glycol bis(allyl carbonate), bisphenol A bis(allyl carbonate), diallyl phthalate, diallyl isophthalate, diallyl terephthalate, and mixtures thereof.

13. The polymerizable liquid composition according to any one of claims 1 to 5, wherein, The initiator is selected from diisopropyl peroxydicarbonate, 1,1-dimethylpropyl-1-methoxycyclohexyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, di-tert-butyl peroxide, lauroyl peroxide, acetyl peroxide, bis(4-tert-butylcyclohexyl) peroxydicarbonate, tert-butyl peroxy-2-ethylhexanoate, tert-hexyl peroxy-2-ethylhexanoate, 1,1-bis(tert-butylperoxy)cyclohexane, 1,1-bis(tert-pentylperoxy)cyclohexane, tert-pentyl (2-ethylhexyl) monoperoxycarbonate, tert-butyl (2-ethylhexyl) monoperoxycarbonate, tert-butyl isopropyl monoperoxycarbonate, poly(tert-butylperoxycarbonate) polyether, and mixtures thereof.

14. A method for preparing a polymerizable liquid composition as described in any one of claims 1 to 13, the method comprising the following steps: a) Provide the allyl monomer or allyl oligomer; b) Provide an initiator for polymerizing the allyl monomer or allyl oligomer, wherein the initiator is selected from peroxydicarbonate, peroxycarbonate, peroxyester, perketal and mixtures thereof; c) Provide at least one lake pigment; d) Mix the allyl monomer or allyl oligomer, the initiator, and the at least one lake pigment.

15. Use of a lake pigment dispersed in a polymerizable liquid composition as described in any one of claims 1 to 13 as a colorant resistant to an initiator used to polymerize an allyl monomer or an allyl oligomer.

16. An optical article obtained by a method comprising curing a polymerizable liquid composition as described in any one of claims 1 to 13.

17. The optical article of claim 16, wherein the optical article comprises an optical substrate, wherein the optical substrate is obtained by a method comprising curing a polymerizable liquid composition as described in any one of claims 1 to 13.

18. The optical article according to claim 16 or 17, wherein, The optical product in question is an ophthalmic lens.

Images