阅读说明：本技术 储存稳定的可热固化的混杂环氧官能组合物和由其制备的透明的热固化的涂层 (Storage stable thermally curable hybrid epoxy-functional compositions and transparent thermally cured coatings prepared therefrom ) 是由 郑海鹏 于 2019-10-04 设计创作，主要内容包括：本发明涉及一种可热固化的组合物,其包含：至少一种具有两个或三个环氧基团的环氧单体,其不是具有至少一个与硅原子直接连接的可水解基团的硅化合物；至少一种带有至少一个硅原子的环氧化合物,其具有至少一个与所述硅原子直接连接的可水解基团以及至少一个通过碳原子与所述硅原子连接的包含环氧官能团的基团,和/或其水解物；至少一种环氧开环催化剂；以及至少一种包含以下的化合物：至少两个(2,2,6,6-四甲基-4-哌啶基)-基团,其中氮原子可以被烷基、烷氧基或烃氧基取代。(The present invention relates to a heat-curable composition comprising: at least one epoxy monomer having two or three epoxy groups, which is not a silicon compound having at least one hydrolyzable group directly bonded to a silicon atom; at least one epoxy compound with at least one silicon atom having at least one hydrolysable group directly attached to the silicon atom and at least one group containing an epoxy functional group attached to the silicon atom via a carbon atom, and/or a hydrolysate thereof; at least one epoxy ring opening catalyst; and at least one compound comprising: at least two (2, 2, 6, 6-tetramethyl-4-piperidyl) -groups, where the nitrogen atom may be substituted by alkyl, alkoxy or hydrocarbyloxy.)

1. A heat-curable composition comprising:

(a) at least one epoxy monomer having two or three epoxy groups, which is not a silicon compound having at least one hydrolyzable group directly bonded to a silicon atom,

(b) at least one epoxy compound with at least one silicon atom, which has at least one hydrolysable group directly attached to the silicon atom and at least one group containing an epoxy function attached to the silicon atom via a carbon atom, and/or a hydrolysate thereof,

(c) at least one epoxy ring opening catalyst, and

at least one compound (e) comprising at least two groups having the formula:

wherein R is⁴Represents a hydrogen atom, an alkyl group, an alkoxy group or a hydrocarbyloxy group.

2. The composition of claim 1, further comprising at least one organic solvent selected from glycol monoethers.

3. The composition of any one of the preceding claims, further comprising:

(d) at least one epoxy monomer comprising from 4 to 8 epoxy groups, which is not a silicon compound having at least one hydrolysable group directly attached to a silicon atom.

4. The composition of any one of the preceding claims, wherein compound (b) is a compound having the formula:

R_n′Y_mSi(X)_4-n′-m (II)

wherein the R groups are the same or different and represent a monovalent organic group which is attached to the silicon atom through a carbon atom and does not contain any epoxy group, the Y groups are the same or different and represent a monovalent organic group which is attached to the silicon atom through a carbon atom and contains at least one epoxy group, the X groups are the same or different and represent a hydrolyzable group or a hydrogen atom, m and n 'are integers such that m is equal to 1 or 2 and n' + m is 1 or 2.

5. The composition of any one of the preceding claims, further comprising:

(f) at least one UV absorber.

6. The composition of any one of the preceding claims, further comprising:

(g) at least one antioxidant.

7. The composition of any one of the preceding claims, further comprising:

(h) at least one absorbing dye at least partially inhibiting the transmission of light in at least one selected wavelength range comprised in the wavelength ranges of 100-380nm, 380-780nm, and/or 780-1400 nm.

8. Composition according to any one of the preceding claims, in which the composition comprises at least 50% by weight, preferably at least 75% by weight, relative to the total weight of polymerizable compounds present in the composition, of compounds having at least one epoxy group.

9. Composition according to any one of the preceding claims, comprising from 1% to 15% by weight of compound (b) relative to the total weight of the composition.

10. The composition according to any one of the preceding claims, comprising from 10 to 60% by weight of monomers (a) and (d) (if present) relative to the total weight of the composition.

11. Composition according to any one of the preceding claims, in which compound (e) is present in an amount ranging from 0.05% to 3% relative to the total weight of the composition.

12. Composition according to any one of the preceding claims, in which the epoxide groups are chosen from glycidyl and cycloaliphatic epoxide groups.

13. Composition according to any one of the preceding claims, in which the ratio: the weight of the dry extract of monomers (a) and (d) (if present) per weight of the dry extract of compound (b) ranges from 97/3 to 70/30.

14. An optical article comprising a substrate having at least one major surface bearing a coating resulting from thermal curing of the thermally curable composition according to any one of the preceding claims.

15. The optical article of claim 14, further defined as an optical lens, preferably an ophthalmic lens.

Detailed Description

As used herein, when an article comprises one or more layers or coatings on its surface, "depositing a layer or coating on the article" means depositing a layer or coating on the uncovered (exposed) surface of the outer coating (i.e., the coating furthest from the substrate) of the article.

As used herein, a coating "on" or already deposited on a substrate/coating is defined as a coating that: the coating (i) is disposed over the substrate/coating, (ii) does not have to be in contact with the substrate/coating, that is, one or more intermediate coatings may be interposed between the substrate/coating and the associated coating (however, it preferably contacts the substrate/coating), and (iii) does not have to completely cover the substrate/coating. When "coating 1 is said to be located below coating 2," it is understood that coating 2 is further from the substrate than coating 1.

The optical article according to the invention is preferably a transparent optical article, in particular an optical lens or lens precursor, more preferably an ophthalmic lens or lens precursor.

The term "ophthalmic lens" is used to mean a lens adapted to a spectacle frame to protect the eye and/or correct vision. The lens may be selected from afocal, monofocal, bifocal, trifocal and progressive lenses. Although ophthalmic optics is a preferred field of the invention, it will be understood that the invention may be applied to other types of optical elements where it may be advantageous to filter specific wavelengths, such as, for example, lenses for optical instruments, safety glasses, filters particularly for the photographic, astronomical or automotive industries, optical sighting lenses, eye goggles, optics of lighting systems, screens, glazing, etc.

If the optical article is an optical lens, it may be coated with the coating of the present invention on its front major surface, its back major side, or both. As used herein, the rear of the substrate is intended to mean the face closest to the wearer's eye when the article is used. The face is generally concave. In contrast, the front face of the substrate is the face furthest from the wearer's eye when the article is in use. The face is typically convex. The optical article may also be a flat optical article.

In the sense of the present invention, a substrate is understood to mean an uncoated substrate and generally has two main faces. The substrate may in particular be an optically transparent material having the shape of an optical article, such as an ophthalmic lens destined to be mounted on spectacles. In this context, the term "substrate" is understood to mean the base constituent material of an optical lens and more particularly an ophthalmic lens. This material acts as a support for the stack of one or more functional coatings or layers.

The substrate of the optical article coated on at least one main face with a coating according to the invention may be an inorganic or organic glass, for example an organic glass made of thermoplastic or thermosetting plastic, generally chosen from ophthalmic grade transparent materials used in the ophthalmic industry.

As a particularly preferred class of substrate materials, mention may be made of polycarbonates, polyamides, polyimides, polysulfones, copolymers of polyethylene terephthalate and polycarbonate, polyolefins such as polynorbornene, polymers and copolymers of resins resulting from the polymerization or (co) polymerization of alkylene glycol bisallyl carbonate, such as diethylene glycol bis (allyl carbonate) (for example, under the trade name PPG Industries company)And (4) selling. The lenses sold by polymerization of diethylene glycol bis (allyl carbonate) are known as from the company Emersoni (ESSILOR)Lenses), polycarbonates such as those derived from bisphenol a, (meth) acrylic or thio (meth) acrylic polymers and copolymers such as Polymethylmethacrylate (PMMA), urethane and thiourethane polymers and copolymers, epoxy polymers and copolymers, episulfide polymers and copolymers.

Prior to deposition of the coating, the substrate surface is typically subjected to a physical or chemical surface activation and cleaning treatment in order to improve the adhesion of the layer to be deposited, as disclosed in WO 2013/013929.

The optical article comprises a substrate having at least one major surface bearing a coating resulting from thermal curing of the thermally curable composition according to the invention. The coating is an epoxy coating resulting from the polymerization of compounds (a), (b) and optionally (d) each comprising at least one epoxy group. In the present invention, by using the epoxy compound (a) and optionally (d) free of reactive silicon atoms according to the present invention, together with the organosilane (b), a coating containing the hybrid epoxy copolymer will be produced.

The epoxy compounds according to the invention are cyclic ethers and preferably epoxides (oxiranes). As used herein, the term epoxide refers to a subclass of epoxy compounds containing saturated tricyclic ethers. The epoxy groups of compounds (a), (b) and (d) are preferably selected from glycidyl and cycloaliphatic epoxy groups, more preferably from alkyl glycidyl ether groups and cycloaliphatic epoxy groups.

In the present patent application, the term "alkyl" means a linear or branched, saturated or unsaturated, monovalent hydrocarbon radical preferably containing from 1 to 25 carbon atoms. The term alkyl includes acyclic radicals preferably containing from 1 to 8 carbon atoms, more preferably from 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, butyl and n-hexyl, preferably alicyclic and cycloalkyl radicals containing from 3 to 7 carbon atoms, preferably cycloalkylmethyl radicals containing from 4 to 8 carbon atoms.

In embodiments, the alkyl group is attached via an sp3 carbon atom and may be substituted with one or more aryl groups and/or may contain one or more heteroatoms such as N, S, O or halogen. Examples which may be mentioned include aralkyl groups such as trityl (-CPh)₃) Benzyl or 4-methoxybenzyl, alkoxyalkyl, especially dialkoxymethyl such as diethoxymethyl or dimethoxymethyl, CH₂CO₂R¹¹Group, wherein R¹¹Represents an optionally substituted alkyl or aryl group.

The term "cycloalkyl" also includes "heterocycloalkyl" groups, i.e., non-aromatic mono-or polycyclic rings in which one or more carbon atoms in one or more of the rings has been replaced with a heteroatom such as nitrogen, oxygen, phosphorus, or sulfur. The heterocycloalkyl group preferably contains 1 to 4 internal ring heteroatoms. Heterocycloalkyl groups can be structures containing one or more non-aromatic rings.

The term "alicyclic" denotes a saturated or unsaturated, but non-aromatic, carbocyclic group comprising one or several optionally fused rings, which may optionally be substituted by one or more of the groups cited above for aryl. The term "alicyclic" also includes "heteroalicyclic" groups, i.e., non-aromatic mono-or polycyclic rings in which one or more carbon atoms in one or more of the rings has been replaced with a heteroatom such as nitrogen, oxygen, phosphorus, or sulfur. The cycloaliphatic group is preferably a cycloalkyl group.

The term "aryl" denotes an aromatic carbocyclic group comprising only one ring (e.g. phenyl) or several optionally fused rings (e.g. naphthyl or terphenyl), which may optionally be substituted by one or more groups such as, but not limited to, alkyl (e.g. methyl), hydroxyalkyl, aminoalkyl, hydroxy, thiol, amino, halogen (fluoro, bromo, iodo or chloro), nitro, alkylthio, alkoxy (e.g. methoxy), aryloxy, monoalkylamino, dialkylamino, acyl, carboxy, alkoxycarbonyl, aryloxycarbonyl, hydroxysulfonyl, alkoxysulfonyl, aryloxysulfonyl, alkylsulfonyl, alkylsulfinyl, cyano, trifluoromethyl, tetrazolyl, carbamoyl, alkylcarbamoyl or dialkylcarbamoyl. Alternatively, two adjacent positions of the aromatic ring may be substituted with methylenedioxy or ethylenedioxy.

The term "aryl" also includes "heteroaryl" groups, i.e., aromatic rings in which one or more carbon atoms in one or more aromatic rings have been replaced with a heteroatom such as nitrogen, oxygen, phosphorus, or sulfur.

The compound (a) according to the present invention is a di-or tri-functional epoxy monomer having two or three epoxy groups per molecule, which is not a silicon compound having at least one hydrolyzable group directly bonded to a silicon atom. In the present application, Si-O-Si groups are not considered to be hydrolysable groups. In one embodiment, compound (a) does not contain any silicon atoms. In this application, oligomers are considered monomers.

More preferably, compound (a) according to the invention does not contain other reactive functional groups than the epoxy group or groups, which are capable of reacting with other polymerizable functional groups present in the composition and which will be linked to the polymer matrix of the coating. In other words, the preferred epoxy compound is a "pure" epoxy compound.

The compound (a) preferably contains two or three glycidyl ether groups and/or cycloaliphatic epoxy groups. The glycidyl ether group is preferably an alkyl glycidyl ether group.

Glycidyl ethers are synthetic compounds characterized by the following group, wherein R₁Represents a monovalent group:

preferred cycloaliphatic epoxy groups are shown below, wherein the hydrogen atoms in the structure may be substituted with one or more substituents, such as those cited above as aryl substituents:

and

in one embodiment, compound (a) comprises a β - (3, 4-epoxycyclohexyl) alkyl group such as a β - (3, 4-epoxycyclohexyl) methyl group and a β - (3, 4-epoxycyclohexyl) ethyl group.

Compound (a) may be selected from the group consisting of: trimethylolethane triglycidyl ether (Erisys from CVC thermosetting Specialties)^TMGE-31), trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether (Erisys from CVC thermoset specialty materials division)^TMGE-30), trishydroxyphenylmethane triglycidyl ether, trisphenol triglycidyl ether, tetrahydroxyphenylethane triglycidyl etherOleyl ether, tetraglycidyl ether of tetrahydroxyphenylethane, p-aminophenol triglycidyl ether, 1, 2, 6-hexanetriol triglycidyl ether, glycerol triglycidyl ether, diglycerol triglycidyl ether, glycerol ethoxylate triglycidyl ether, castor oil triglycidyl ether, propoxylated glycerol triglycidyl ether, ethylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether (from CVC Specialty Chemicals)5000) 3 ', 4' -epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate (from UCB Chemicals, Inc.)1500. From Union CarbideUVR-6110 and6105) bis (3, 4-epoxycyclohexylmethyl) adipate (UVR-6128 from Dow Chemical Company), limonene diepoxide (6-methyl-3- (2-methyloxiran-2-yl) -7-oxabicyclo [ 4.1.0)]Heptane, Celloxide 3000 from Daicel Chemical Industries Ltd.), 1, 3-bis [2- (3, 4-epoxycyclohexyl) ethyl]Tetramethyldisiloxane (SIB 1092.0 from Gelest, formula Xr), bisphenol A diglycidyl ether resin (n is typically in the range of 0 to 25, Epon 828 from Shell Chemical), hexahydrophthalic anhydride diglycidyl ether (Ciba from Ciba)184) And derivatives thereof having the formula Xn and Xo, and mixtures thereof. It is also possible to use those from CVC specialty Chemicals5001 by increasing the functionality of the epoxy (two-component mixtures, functionality 2.4)5000 faster curing profile.

In one embodiment of the invention, the composition further comprises at least one compound (d) which is a multifunctional epoxy monomer comprising from 4 to 8 epoxy groups (preferably 4 to 6), which is not a silicon compound having at least one hydrolysable group directly attached to a silicon atom. In one embodiment, compound (d) does not contain any silicon atoms.

Compound (a) provides a coating having a lower crosslink density after final post-cure than highly functionalized compound (d). Thus, the presence of compound (d) may improve the mechanical properties of the substrate, such as abrasion and/or scratch resistance.

More preferably, the compound (d) according to the invention does not contain other reactive functional groups than the epoxy group or groups, which are capable of reacting with other polymerizable functional groups present in the composition and which will be linked to the polymer matrix of the coating. In other words, the preferred epoxy compound is a "pure" epoxy compound.

The compound (d) preferably contains 4 to 8 glycidyl ether groups and/or cycloaliphatic epoxy groups. The glycidyl ether group is preferably an alkyl glycidyl ether group.

Preferred alicyclic epoxy groups are the same as those shown for compound (a). In one embodiment, compound (d) comprises a β - (3, 4-epoxycyclohexyl) alkyl group such as a β - (3, 4-epoxycyclohexyl) methyl group and a β - (3, 4-epoxycyclohexyl) ethyl group.

The compound (d) may be selected from the group consisting ofGroup (b): diglycerol tetraglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol polyglycidyl ether (Erisys from CVC thermoset specialty department)^TMGE-60), 1, 1, 1-tris- (p-hydroxyphenyl) ethane triglycidyl ether (from CVC specialty Chemicals Co., Ltd.)9000) 1, 1, 1-tris- (p-hydroxyphenyl) methane triglycidyl ether (Tactix 742 from Ciba, Inc.), tetra (4-hydroxyphenyl) ethane tetraglycidyl ether (Epon 1031 from Shell, Inc., formula Xi), epoxy cyclohexylCageMixture (EP 0408 from Hybrid Plastics, having 8 epoxy groups, formula Xd), a 2- (3, 4-epoxycyclohexyl) ethyl compound having the formula Xs (available from Gelest), and mixtures thereof.

Compounds corresponding to the formulae cited in the preceding paragraphs are represented below:

the composition preferably comprises from 10% to 60%, more preferably from 20% to 55%, even more preferably from 30% to 50% by weight of monomers (a) and (d) (if present) relative to the total weight of the composition.

The composition preferably comprises from 10% to 50%, more preferably from 15% to 50%, even more preferably from 20% to 45% by weight of compound (a) relative to the total weight of the composition.

When compounds (d) are present, they preferably represent from 1% to 25% by weight of the composition, preferably from 5% to 20% by weight.

The thermally curable composition comprises at least one compound (b) which is an epoxy compound having at least one silicon atom, which has at least one hydrolysable group directly attached to the silicon atom and at least one group comprising an epoxy function attached to the silicon atom via a carbon atom, and/or a hydrolysate thereof. The compound (b) preferably has from 2 to 6, more preferably 2 or 3 functional groups which generate silanol groups upon hydrolysis. The compounds are considered to be organic compounds and preferably have the formula (II):

R_n′Y_mSi(X)_4-n′-m (II)

wherein the R groups are the same or different and represent a monovalent organic group which is attached to the silicon atom through a carbon atom and does not contain any epoxy group, the Y groups are the same or different and represent a monovalent organic group which is attached to the silicon atom through a carbon atom and contains at least one epoxy group, the X groups are the same or different and represent a hydrolyzable group or a hydrogen atom, m and n 'are integers such that m is equal to 1 or 2 and n' + m is 1 or 2.

The integers n and m define the three groups of compound II: having the formula RYSi (X)₂Of the formula Y₂Si(X)₂And compounds of the formula YSi (X)₃The compound of (1). Among these compounds, having the formula YSi (X)₃The epoxy silane of (3) is preferred.

The monovalent R group attached to the silicon atom through an Si-C bond is an organic group. These groups may be, without limitation, saturated or unsaturated hydrocarbon groups, preferably C₁-C₁₀Radical and preferably C₁-C₄Radicals, e.g. alkyl, preferably C₁-C₄Alkyl, e.g. methyl or ethyl, aminoalkyl, alkenyl, e.g. vinyl, C₆-C₁₀Aryl, e.g. optionally substituted phenyl, especially by one or more C₁-C₄Alkyl-substituted phenyl, benzyl, (meth) acryloyloxyalkyl.

Most preferred R groups are alkyl groups, especially C₁-C₄Alkyl, and desirably methyl.

The x group upon hydrolysis produces an OH group. It is noteworthy that the SiOH bond may be initially present in the compound having formula II, which in this case is considered to be a hydrolysate. The hydrolysate also includes a siloxane salt.

The X groups may independently and without limitation represent alkoxy-O-R¹Wherein R is¹Preferably represents a linear or branched alkyl or alkoxyalkyl group, preferably C₁-C₄An alkyl group; acyloxy-O-C (O) R³Wherein R is³Preferably represents an alkyl group, preferably C₁-C₆Alkyl, and more preferably methyl or ethyl; halogen groups such as Cl and Br; amino optionally substituted by one or two functional groups, e.g. alkyl or silane groups, e.g. NHSiMe₃A group; alkyleneoxy groups such as isopropenyloxy. Hydroxyl groups are considered hydrolyzable groups.

The most preferred epoxy silanes are those wherein in formula II, n' ═ 0, m ═ 1 and X is C1-C5 alkoxy, preferably OCH₃Those of (a).

The monovalent Y groups attached to the silicon atom via Si-C bonds are organic groups in that they contain at least one epoxy functional group, preferably one epoxy functional group. By epoxy functional group is meant a group of atoms in which an oxygen atom is directly attached to two adjacent carbon atoms or non-adjacent carbon atoms contained in a carbon-containing chain or a ring carbon-containing system. Among the epoxy functional groups, oxirane functional groups are preferred, i.e., saturated three-membered cyclic ether groups.

Preferred Y groups are groups having the formulae III and IV:

wherein R is²Is an alkyl group, preferably a methyl group, or a hydrogen atom, ideally a hydrogen atom, a and c are integers ranging from 1 to 6, and b is 0, 1 or 2.

A preferred group having the formula III is gamma-glycidoxypropyl (R)²H, a ═ 3, b ═ 0) and a preferred (3, 4-epoxycyclohexyl) alkyl group of formula IV is β - (3, 4-epoxycyclohexyl) ethyl (c ═ 1). Gamma-glycidoxyethoxypropyl (R2 ═ H, a ═ 3, b ═ 1) can also be used.

Preferred epoxy silanes of formula II are the alkylene oxide oxysilanes, and most preferred are those having one Y group and three alkoxy X groups. Particularly preferred epoxytrialkoxysilanes are those having the formulae V and VI:

wherein R is¹Is an alkyl group having 1 to 6 carbon atoms, preferably methyl or ethyl, and a, b and c are as defined above.

Examples of such epoxy silanes include, but are not limited to, gamma-glycidoxymethyltrimethoxysilane, gamma-glycidoxymethyltriethoxysilane, gamma-glycidoxymethyltripropoxysilane, gamma-glycidoxyethyltrimethoxysilane, gamma-glycidoxyethyltriethoxysilane, gamma-glycidoxyethyltripropoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropyltripropoxysilane, gamma-glycidoxypropylmethyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane. Other useful epoxytrialkoxysilanes are described in patents US 4,294,950, US 4,211,823, US 5,015,523, EP 0614957, US 2009/0311518, US 2011/0058142 (compounds having formulae I, VII and VIII) and WO 94/10230. Among those silanes, gamma-Glycidoxypropyltrimethoxysilane (GLYMO) is preferred.

According to one aspect of the invention, the hydrolytically polymerizable compound (b) is typically hydrolyzed prior to mixing into the other components of the composition. Hydrolysis may be carried out by using an acidic catalyst (e.g., hydrochloric acid, acetic acid) in the presence of water as is known in the art.

The composition preferably comprises from 1% to 15%, more preferably from 2% to 10%, even more preferably from 3% to 8% by weight of compound (b) relative to the total weight of the composition.

In one embodiment, the composition comprises less than 50% by weight, more preferably less than 40%, 30% or 20% by weight of compound (b) relative to the total weight of polymerizable compounds present in the composition.

Although the epoxy silane is generally in hydrolyzed form, the amount of epoxy silane is conventionally defined as the weight of the initial precursor prior to its hydrolysis. Hydrolysis of the alkoxy group releases the associated alcohol to form a silanol group which will condense spontaneously. Preferably, the alkoxysilane is reacted with a stoichiometric amount of water to hydrolyze hydrolyzable groups, typically alkoxy groups.

In some aspects of the invention, the composition comprises from 25% to 60% by weight, more preferably from 30% to 55% by weight, of compounds (a), (d) (if present) and (b), relative to the total weight of the composition. The dry extract weight of those epoxy compounds preferably constitutes at least 50% of the dry extract weight of the composition, preferably at least 60%, at least 70%, at least 80%, at least 85%, at least 90%, at least 92% or at least 95% of the dry extract weight of the composition.

In embodiments, the composition is such that the ratio: the weight of the dry extract of monomers (a) and (d) (if present) per weight of the dry extract of compound (b) ranges from 97/3 to 70/30, more preferably from 95/5 to 80/20.

In another embodiment, the composition is such that the weight ratio: monomer (a)/monomer (d) ranges from 100/0 to 50/50, more preferably from 100/0 to 60/40, even more preferably from 95/5 to 63/37.

It is also possible to add to the composition a low amount of additional polymerizable epoxy compounds other than the epoxy compounds (a), (b) or (d) according to the invention, typically less than 20% by weight, more preferably less than 15% by weight, relative to the total weight of the composition. This amount may be less than 10% or less than 5% and even 0% by weight. Their dry extract weight preferably comprises less than 30%, more preferably less than 20%, 15%, 10%, and 5% of the dry extract weight of the composition. This amount may also be 0%. Examples of such compounds are monooxyoxetane compounds such as 3-ethyl-3-hydroxymethyloxetane.

The thermally curable composition comprises at least 50%, preferably at least 60%, more preferably at least 75%, 80%, 85%, 90%, 95% or 100% by weight of compounds having at least one epoxy group (preferably compounds (a), (b) and (d), when present) relative to the total weight of polymerizable compounds (or epoxy compounds) present in the composition.

The heat-curable composition according to the invention preferably comprises less than 25% by weight, more preferably less than 20% by weight of acrylic and/or methacrylic monomers, and more preferably non-epoxy group containing monomers, relative to the total weight of the composition. This amount may be less than 10% or less than 5% and even 0% by weight. In other words, in embodiments, the composition does not contain any non-epoxy functional monomers.

The weight of the dry extract of acrylic and/or methacrylic acid monomers preferably represents less than 30%, more preferably less than 25%, 20%, 10%, 5% of the weight of the dry extract of the composition. This amount may also be 0%. These amounts also preferably apply to the non-epoxy group containing monomers.

The dry extract weight may be calculated as the theoretical dry extract weight, as disclosed in US 2012/0295084 or EP 614957.

The dry extract weight can also be obtained experimentally. The dry extract of the compound or composition is the total weight of the compound or composition after complete removal of the one or more volatile solvents in an oven at 100 ℃ to 110 ℃. The dry extract is also referred to as the solids content, weight percent of non-volatile material or% NVM. The conventional procedure for determining solids takes 60min at 105 ℃ to 110 ℃ in an oven and requires pre-and post-weighing of the sample trays and samples (ASTM Standard Nos.: D2369 and D2926-80). Using a commercial Mark 3 solid Analyzer from Sartorius or SMART Turbo from CEM^TMDepending on the volatility/moisture content and viscosity of the material, it takes only 2 to 10 minutes.

The composition according to the invention generally contains from 25% to 75% by weight, preferably from 35% to 55% by weight of solids (weight of dry extract relative to the weight of the composition).

The compositions of the invention advantageously further contain a small amount, preferably from 0.005% to 1%, more preferably from 0.02% to 0.5%, still more preferably from 0.05% to 0.3% by weight, based on the total weight of the composition, of at least one surface-active compound (surfactant). Good wetting of the substrate by the surfactant is important to produce a satisfactory appearance of the final coating. The surfactant may include, for example, poly (alkylene glycol) modified polydimethylsiloxane or polyheptamethylsiloxane or fluorocarbon modified polysiloxane. Preferred surfactants are fluorinated surfactants, such as those from 3M companyFC-4434 (nonionic surfactant comprising fluoroaliphatic polymeric ester), Unidyne^TMNS-9013 and from Ciba3034 (fluorocarbon-modified polysiloxanes).

The epoxy compound of the composition is subjected to a polycondensation and/or crosslinking reaction in the presence of an epoxy ring-opening catalyst (compound (c)). Preferred catalysts that have been found to be capable of curing the epoxy composition at a sufficiently low temperature (preferably 125 ℃ C. or less, more preferably 110 ℃ C.) without damaging the underlying substrate or adversely affecting other coatings or coating components include (strong) acid catalysts designed for ring-opening polymerization of cyclic ether groups, ammonium salts of metal anions, and aluminum-based compounds.

In order to obtain a storage stable heat curable composition, the catalyst should not catalyze the epoxy ring opening at room temperature to prevent premature polymerization or formation of the prepolymer in the coating composition over time during storage or during production, thereby extending its shelf life and shelf life without changing properties over time. In this regard, the catalyst is preferably a blocked catalyst or a latent catalyst (e.g., a buffered acid catalyst), with a blocked catalyst being preferred because the latent catalyst can still react at ambient temperature and cause slight changes in composition over time. The blocked catalysts do not react until their respective unblocking temperatures are reached. Preferred catalysts are inactive at ambient temperature (20 ℃) and are only activated upon heating (generally to 70 ℃ to 80 ℃ or higher) to catalyze epoxy ring opening.

Exemplary blocked or latent catalysts are based on trifluoromethanesulfonic acid (triflic acid), dinonylnaphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid (DNNDSA), and/or metal salts thereof, and ammonium tellurium hexafluoride (Lewis acid), and are available from King Industries, Inc. (King Industries), for exampleSuper A233 (diethylamine salt of trifluoromethanesulfonic acid),155 (DNNDSA-based blocked acid catalysts),Super XC-7231 (now namedCXC 1612 sold as blocked ammonium tellurofluoride catalyst), andsuper XC-A218 (25% solids) (now under the nameSold by CXC-1613), metal salts of trifluralic acid (lewis acid) buffered to reduce its reactivity at ambient temperature), the latter being one of the preferred catalysts. Other useful catalysts include carboxylic acid anhydrides such as hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, or Lewis acid catalysts including BF₃And BCl₃An amine complex.

In another embodiment, catalyst (c) is selected from the group consisting of aluminum chelates, aluminum acylates, and aluminum alcoholates. When those aluminum compounds are used, the composition preferably does not contain other epoxide opening catalysts, such as acid catalysts or ammonium salts of metal anions.

In addition, aluminum-based catalysts cure the compositions of the present invention at lower temperatures and in shorter times than the other catalysts cited above (pre-cure and post-cure).

The aluminum acylates and aluminum alcoholates have the preferred general formula Al (OC (O) R)_n(OR′)_3-nAnd Al (OSiR ″)₃)_n(OR′)_3-nWherein R and R 'are linear or branched alkyl groups containing from 1 to 10 carbon atoms, R' is a linear or branched alkyl group containing from 1 to 10 carbon atoms, a phenyl moiety, an acylate moiety of the formula OC (O) R, wherein R is as defined above, and n is an integer from 1 to 3. Preferably, R 'is isopropyl or ethyl and R' are methyl.

The aluminum chelate compound may be formed by reacting an aluminum alkoxide or acylate with a chelating agent containing no nitrogen or sulfur, containing oxygen as a coordinating atom (e.g., acetylacetone, ethyl acetoacetate, or diethyl malonate). They may be chosen from those described as Al (AcAc)₃Aluminum acetylacetonate, ethyl mono (acetoacetate) aluminum bisacetylacetonate, ethyl bis (acetoacetate) aluminum monoacetylacetonate, di-n-butoxyaluminum ethyl mono (acetoacetate), and diisopropoxyaluminum ethyl mono (acetoacetate). Further examples of such compounds are given in patent EP 0614957. When the epoxy ring-opening catalyst is an aluminum chelate, the coating composition preferably comprises an organic solvent having a boiling temperature at atmospheric pressure in the range of from 70 ℃ to 140 ℃, such as ethanol, isopropanol, ethyl acetate, methyl ethyl ketone, or tetrahydropyran.

The amount of catalyst used typically ranges from 0.01% -5% by weight, preferably from 0.1% to 3.5% by weight, more preferably from 0.2% to 3% by weight, based on the weight of the composition.

The composition generally contains at least one solvent, which is preferably a glycol monoether. The glycol monoether solvent generally exhibits low surface tension and is preferably selected from alkylene glycol C1-4The alkyl monoether is more preferably selected from the group consisting of ethylene glycol C1-4 alkyl monoether, propylene glycol C1-4 alkyl monoether, diethylene glycol C1-4 alkyl monoether, triethylene glycol C1-4 alkyl monoether, propylene glycol C1-4 alkyl monoether, dipropylene glycol C1-4 alkyl monoether, triethylene glycol C1-4 alkyl monoether, and tripropylene glycol C1-4 alkyl monoether. The most preferred glycol monoether is propylene glycol methyl ether. Such compounds are known under the name Dowanol by the Dow Chemical companyCommercially available as a mixture of 1-methoxy-2-propanol (major isomer) and 2-methoxy-1-propanol.

The total amount of solvent depends on the resin used, the type of optical article and the coating process. The purpose of the solvent is to achieve good surface wetting and a specific coating viscosity range determined by the coating equipment used to achieve the specific coating thickness range. The solvent typically constitutes from 25% to 75%, preferably from 35% to 70%, more preferably from 40% to 65% by weight of the composition. Low amounts of solvents, especially glycol monoethers, may not satisfactorily dissolve dyes, which are generally hydrophobic compounds.

It has been found that there is a need for glycol monoethers in compositions that provide good solubility of dyes that can be incorporated therein, provide longer shelf life for coating solutions, and achieve better appearance characteristics (e.g., low haze) for the resulting articles. Due to the high solubility of the dye in existing sol-gel compositions, a high level of photo-protection can be achieved.

Additional solvents such as alkanols (methanol, ethanol, propanol), ketones, propylene carbonate or water may be used. Hydrochloric acid, which can be used as an acidic catalyst for the compound (b), is counted as a solvent.

In one embodiment of the invention, the composition comprises from 30 to 55% by weight of monomer (a), (d) (if present) and compound (b) relative to the total weight of the composition, and from 35 to 65% by weight of at least one organic solvent selected from glycol monoethers relative to the total weight of the composition.

Said compositionMay further comprise at least one compound of the formula M (Z)_yWherein M represents a metal or metalloid, preferably Si, the Z groups, which are the same or different, are hydrolyzable groups, and y is equal to or greater than 4, is the valence of the metal or metalloid M. Such compounds are described in detail in US 2011/0058142. Preferred compounds are of the formula Si (Z)₄Wherein the Z groups, which may be the same or different, are hydrolyzable groups, such as tetraethoxysilane.

According to the invention, the coating composition may comprise at least one absorbing dye as compound (h) which at least partially inhibits the transmission of light in at least one selected wavelength range comprised in the wavelength ranges of 100-. The dye may refer to both pigments and colorants, i.e., may or may not be soluble in its vehicle. The dyes may be water-based or (organic) solvent-based.

In a preferred embodiment, the selected spectral range in the region of 380-780nm of the electromagnetic spectrum is 400nm to 500nm, i.e. the blue wavelength range, more preferably the 415-455nm range or the 420-450nm range.

In the present disclosure, when the selected wavelength range is 400-500nm, the (absorbing) dye will be referred to as a blue blocking dye, and is typically a yellow dye.

The optical article comprising the dye inhibits transmission of incident light through at least one geometrically defined surface, preferably the entire major surface, of the substrate of the optical article. In this specification, unless otherwise specified, light blocking is defined with respect to an incident angle ranging from 0 ° to 15 °, preferably 0 °.

The dye preferably at least partially inhibits transmission of light in the 415-455nm wavelength range, more preferably in the 420-450nm range, by absorption, to provide a high level of retinal cell protection against retinal cell apoptosis or age-related macular degeneration.

It may be particularly desirable in some cases to selectively filter a relatively small portion of the blue light spectrum, i.e., the 420nm-450nm region. Indeed, blocking too much of the blue light spectrum may interfere with scotopic vision and the mechanism that regulates biological rhythms, known as "circadian cycles". Thus, in a preferred embodiment, the dye blocks less than 5% of light having a wavelength in the range from 465 to 495nm, preferably from 450 to 550 nm. In this embodiment, the dye selectively inhibits phototoxic blue light and transmits blue light involved in circadian rhythms. Preferably, the optical article transmits at least 95% of light having a wavelength ranging from 465 to 495 nm. This transmission is the average of the transmitted light in the 465-495nm range, not weighted according to the sensitivity of the eye at each wavelength of said range. In another embodiment, the dye does not absorb light in the range of 465-495nm, preferably 450-550 nm. In the present description, unless otherwise specified, the transmission (transmission) is measured at an incidence angle ranging from 0 ° to 15 °, preferably 0 °, at the center of an optical article having a thickness ranging from 0.5 to 2.5mm, preferably 0.7 to 2.0mm, more preferably 0.8 to 1.5 mm.

In one embodiment, the dye does not absorb or absorbs very little in the visible region of the spectrum outside the selected wavelength range, preferably in the 400-500nm wavelength range, to minimize the appearance of multiple colors. In this case, the dye selectively inhibits the transmission of light in a selected wavelength range, preferably in the 400-500nm wavelength range, more preferably in the 415-455nm or 420-450nm range. As used herein, a dye "selectively inhibits" a selected wavelength range if the dye inhibits at least some transmission within the range while having little or no effect on transmission of wavelengths outside of the range (unless it is expressly configured for use herein).

The dye preferably has an absorption peak, ideally a maximum absorption peak, in the range of 380-780nm, more preferably in the range of 400-500 nm. Certain dyes are of interest because they have narrow absorption peaks, thus providing selective absorption filters having (in some cases) bandwidths of, for example, 20nm or less over a selected wavelength range. The selectivity characteristics may be provided in part by the symmetry of the dye molecules. Such selectivity helps limit distortion of visual perception of color, limit adverse effects of light filtering on scotopic vision, and limit effects on circadian rhythms.

The dyes according to the invention are generally compatible with most coating components. They are processed in such a way that they are well and stably distributed or dispersed in the matrix of the coating, thereby providing transparent clear optical articles with low haze.

The chemical nature of such a dye is not particularly limited, provided that it has an absorption peak, ideally a maximum absorption peak, in the range of 400-500 nm.

In certain embodiments, the dye comprises one or more porphyrin compounds, porphyrin complexes, other heterocyclic rings associated with porphyrin compounds, including corrins, chlorides, and porphins, derivatives thereof, or perylenes, coumarins, acridines, indolenine (also known as 3H-indole), anthraquinones, azobenzenes, phthalocyanines, cyanines, quinolines, benzotriazoles, nitrobenzenes, isoquinolines, isoindolines, diarylmethanes, or indol-2-ylidene groups. Derivatives are substances which are usually released by addition or substitution. Preferred dyes are diarylmethane dyes such as auramine O and porphyrin dyes.

The dye may comprise one or more dyes from the group consisting of: coumarin 343; coumarin 314; nitrobenzoxadiazole; fluorescein, CH; 9, 10 bis (phenylethynyl) anthracene; proflavine; 4- (dicyanomethylene) -2-methyl-6- (4-dimethylaminostyryl) -4H-pyran; 2- [4- (dimethylamino) styryl]-1-methylpyridine iodide; lutein; zeaxanthin;f Yellow 083; t890; and yellow dyes with narrow absorption peaks, available from Exciton, Inc., such asOr

The amount of dye used in the present invention is an amount sufficient to provide satisfactory inhibition of light in the wavelength range of 100-380nm, 380-780nm and/or 780-1400 nm. For example, the dye may be used at a level of 0.005% to 0.50% or 0.01% to 0.2% based on the weight of the coating composition depending on the strength of the dye and the amount of inhibition/protection desired. It will be appreciated that the invention is not limited to these ranges, which are given by way of example only.

In one embodiment, the composition further comprises at least one color balancing agent and/or optical brightener in order to obtain an optical article having an aesthetically acceptable appearance (particularly perceived as a predominantly neutral color) to the wearer/user and when observed by an external observer. Indeed, blue light blocking means, such as dyes or specific UV absorbers, which may be present in the polymerizable composition, tend to produce a color hue in the optical article as a "side effect", the latter appearing yellow, brown or amber if no color balancing means are used.

In the present invention, the color balancing agent used to at least partially counteract the undesired yellow color is preferably a bluing agent, i.e. a compound having an absorption band in the visible spectrum of the orange to yellow wavelength region and exhibiting a color from blue to violet. Color balancing agents are well described in WO 2017/077358 in the name of the applicant.

Further details regarding this embodiment, such as the arrangement of the color-balancing component with respect to the system that blocks blue wavelengths, and further exemplary systems comprising a blue-light-blocking component and a color-balancing component, may be found, for example, in US 8,360,574, WO 2007/146933, WO 2015/097186, WO 2015/097492.

The color balancing component is generally used in an amount sufficient to adjust the tint of the optical material, typically from 0.01% to 5%, more preferably from 0.02% to 2%, even more preferably from 0.03% to 0.5% by weight relative to the weight of the coating composition.

The optical articles of the present invention limit or avoid photodegradation of optical filtering means such as dyes that are sensitive to light and heat in general, and to UV light in particular.

The thermally curable composition comprises at least one compound (e) which is a Hindered Amine Light Stabilizer (HALS) comprising at least two groups having the formula:

wherein R is⁴Represents a hydrogen atom, an alkyl group, preferably a C1-C6 alkyl group, an alkoxy group, preferably a C1-C12 alkoxy group, or a hydrocarbyloxy group. The dotted line shows the position where the group is attached.

Specific examples of the alkyl group include methyl and ethyl. Specific examples of the alkoxy group include cyclohexyloxy, n-undecyloxy and n-octyloxy. Preferred R⁴The radicals are H, methyl and cyclohexyloxy.

In one embodiment, compound (e) comprises at least two (1, 2, 2, 6, 6-pentamethyl-4-piperidinyl) -groups. In another embodiment, compound (e) comprises at least two (2, 2, 6, 6-tetramethyl-4-piperidinyl) -groups.

In another embodiment, compound (e) is a compound having the formula:

wherein R is⁴Has been previously defined and n represents an integer ranging from 4 to 12, preferably from 5 to 10 and ideally equal to 8.

Preferred hindered amine light stabilizers are malonate, sebacate or triazine derivatives, such as bis (1, 2, 2, 6, 6-pentamethyl-4-piperidinyl) -2-n-butyl- (3, 5-di-tert-butyl-4-hydroxy-benzyl) malonate (from BASF)144) Bis (1, 2, 2, 6, 6-pentamethyl-4-piperidinyl) sebacate (ex basf corporation)292. From chemical industries of North City, Inc. (Jojooku C)JF-95 of chemical)), 2, 4-bis [ N-butyl-N- (1-cyclohexyloxy-2, 2, 6, 6-tetramethylpiperidin-4-yl) amino]-6- (2-hydroxyethylamine) -1, 3, 5-triazine (from basf Corp.)152) Bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate (from basf corporation)770. Lowilite 77 from Chemtura, Inc., bis (1-octyloxy-2, 2, 6, -tetramethyl-4-piperidyl) sebacate from Pasteur123 present), bis (2, 2, 6, 6-tetramethyl-4-piperidinyl-1-oxy) sebacate, from basf corporation622 (dimethyl succinate polymer of 4-hydroxy-2, 2, 6, 6-tetramethyl-1-piperidineethanol), tetrakis (1, 2, 2, 6, 6-pentamethyl-4-piperidinyl) butane-1, 2, 3, 4-tetracarboxylate (ADK STAB LA-52 from Adeka), tetrakis (2, 2, 6, 6-tetramethyl-4-piperidinyl) butane-1, 2, 3, 4-tetracarboxylate (ADK STAB LA-57 from Adeka), and bis (1-undecyloxy-2, 2, 6, 6-tetramethylpiperidin-4-yl) carbonate (ADK STAB LA-81 from Adeka).

Compound (e) gives the resulting optical article protection against light degradation and acts as a light stabilizer. In fact, most dyes that may be present, and in particular yellow dyes, are sensitive to UV light, with some degree of photodegradation after irradiation with UV light. The coating composition of the present invention exhibits low yellow change over time.

Compound (e) also has an unexpected advantage in the stability of the epoxy coating composition, as shown in the experimental section. The coating composition according to the invention shows a significantly improved storage stability or pot life stability.

HALS are generally used in an amount ranging from 0.05% to 3%, more preferably from 0.07% to 2%, even more preferably from 0.1% to 1% by weight relative to the weight of the coating composition.

In one embodiment of the invention, the composition further comprises at least one antioxidant (g) which confers protection against thermal oxidation.

Preferred antioxidants are sterically hindered phenols, thioethers or phosphites, preferably sterically hindered phenols. They are available under the trade name BASFAndcommercially available.

Antioxidants are generally used in amounts ranging from 0.05% to 5%, more preferably from 0.1% to 2%, even more preferably from 0.2% to 1% by weight relative to the weight of the coating composition.

Free radical scavengers inhibit the formation of free radicals or scavenge their presence and include Hindered Amine Light Stabilizers (HALS) and antioxidants. The combination of two radical scavengers, namely the antioxidant (g) and the HALS compound (e), provides the optical filtration means with optimal protection against thermal and photo-degradation. The amount of free radical scavenger used is an amount effective to stabilize the coating composition, which will depend on the particular composition selected and can be readily adapted by one skilled in the art.

Protection of the optical filtering means against photodegradation can also be enhanced by the presence of an antireflective coating comprising at least one mineral/dielectric layer on the optical article.

In one embodiment of the invention, the composition further comprises at least one UV absorber (f) in order to reduce or prevent UV light from reaching the retina (particularly in ophthalmic lens materials), and also to protect the substrate material itself from weathering and becoming brittle and/or yellow. The UV absorber also limits or even avoids photo-degradation of the dyes and absorbers contained in the substrate. The absorber may also be incorporated into a coating present at the surface of the optical article.

The UV spectrum has many bands, especially the UVA, UVB and UVC bands. Among those UV bands reaching the earth's surface, the UVA band ranging from 315nm to 380nm, and the UVB band ranging from 280nm to 315nm are particularly harmful to the retina.

The UV absorbers which can be used in the present invention preferably have the ability to at least partially block light having a wavelength shorter than 400nm, preferably a UV wavelength lower than 385 or 390 nm.

Most preferred ultraviolet light absorbers have a maximum absorption peak in the range from 350nm to 370nm and/or do not absorb light in the range 465-495nm, preferably 450-550 nm. In one embodiment, the UV absorber does not absorb any substantial amount of visible light.

In a preferred embodiment, the UV absorber has the ability to at least partially intercept blue light and thus exhibits an absorption spectrum extending into a selected wavelength range (400-500nm region) within the visible blue light range of the electromagnetic spectrum, in particular a wavelength band with increased risk, i.e. the 415-455nm range, preferably the 420-450nm range.

Suitable UV absorbers include, but are not limited to, substituted benzophenones such as 2-hydroxybenzophenone, substituted 2-hydroxybenzophenones disclosed in U.S. Pat. No. 4,304,895, 2-hydroxy-4-octoxybenzophenone (Seesorb))2, 7-bis (5-methylbenzoxazol-2-yl) -9, 9-dipropyl-3-hydroxyfluorene, 1, 4-bis (9, 9-dipropyl-9H-fluorenone [3, 2-d ]]Oxazol-2-yl) -2-hydroxyphenyl, hydroxyphenyl-triazines such as 2-hydroxyphenyl-s-triazine and benzotriazole compounds such as hydroxyphenyl benzotriazoles.

The UV absorber is preferably a benzotriazole compound. Suitable UV absorbers from this family include, but are not limited to, 2- (2-hydroxyphenyl) -benzotriazoles, such as 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) chlorobenzotriazole, n-octyl-3- [ 3-tert-butyl [ ] -4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl]Propionate (Eversorb))2- (2 ' -hydroxy-5 ' -tert-octylphenyl) benzotriazole, 2- (3 ' -methallyl-2 ' -hydroxy-5 ' -methylphenyl) benzotriazole, or other allylhydroxymethylphenylbenzotriazoles, 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole ((B))701) 2- (3, 5-di-tert-amyl-2-hydroxyphenyl) benzotriazole, and 2-hydroxy-5-acryloyloxyphenyl-2H-benzotriazole disclosed in U.S.4,528,311. Preferred UV absorbers belong to the benzotriazole group. Commercially available products include those from basf corporationAndcompounds, e.g.326、477、479、1130; from Shipro Kasei Kaisha701 and 703; viosorb from Kyodo Chemicals IncAnd comeKemisorb from ChemiproAnd TCP Tinuvin Carbo Protect from basf corporation.

The UV absorber is preferably used in an amount of from 0.05% to 5%, and preferably from 0.1% to 2.5%, more preferably from 0.2 to 2% by weight of the composition.

The coating composition may further comprise particles of at least one metal oxide or metalloid oxide (filler) (e.g. silica) to increase the hardness of the coating and optionally adjust the refractive index of the resulting coating. They are preferably used in colloidal form. More details about this embodiment may be found

The composition may also comprise various additives such as curing/crosslinking agents (e.g. silane coupling agents or comonomers such as polyamines, polythiols, polyols, polycarboxylic acids), internal mold release agents (e.g. as described in US 2014/252282), rheology modifiers, flow and leveling additives, wetting agents, defoamers, and stabilizers. The composition may be a solution or dispersion.

The invention also relates to a method of manufacturing an optical article, the method comprising:

(i) depositing a thermally curable composition according to the invention on at least one main surface of a substrate of an optical article,

(ii) heating the optical article coated with the thermally curable composition to a temperature greater than or equal to 60 ℃ to form a tack-free coating,

(iii) (iii) heating the optical article coated with the tack-free coating to a temperature higher than or equal to the temperature of step (ii) so as to obtain a fully cured coating.

The epoxy coating of the present invention is formed on a substrate of an optical article and may be in direct contact with the substrate. In another embodiment, at least one coating is interposed between the substrate and the epoxy coating of the present invention.

The deposition is typically by spin coating, dip coating, spray coating, 3D printing, roll-to-roll coating, or inkjet printing, preferably by dip coating or spin coating, and more preferably by dip coating. The excellent storage stability and good viscosity properties of the heat-curable compositions allow coating optical articles by simply dipping them into a bath containing the heat-curable compositions.

Curing the heat-curable composition is typically carried out in two steps: a first pre-curing step (partial curing, step (ii)) to a temperature of at least 60 ℃, preferably at least 70 ℃, more preferably at least 75 ℃, typically from 60 ℃ to 100 ℃ or from 75 ℃ to 90 ℃ for generally at least 5 minutes, preferably from 10 to 25 or 30 minutes, typically 15 minutes, to form a tack-free coating (to the touch), and a second step (post-curing step (iii)) of heating the optical article coated with the tack-free coating to a temperature higher than or equal to the temperature of the pre-curing step, preferably at least 90 ℃ or 95 ℃, more preferably at least 100 ℃, typically from 100 ℃ to 140 ℃, preferably from 100 ℃ to 115 ℃ for 1 to 4 hours, usually at least two hours, preferably from 2.5 to 3.5 hours, typically 3 hours, to obtain a higher level of cure, preferably a fully cured coating. The method produces a transparent clear coating with low haze.

The thickness of the cured coating may be adapted to the specific application desired and typically ranges from 0.5 to 50 μm, preferably from 1 to 20 μm, more preferably from 2 to 10 μm. The coating thickness can be easily adjusted by varying the solvent concentration of the claimed composition and the coating conditions (e.g. take-off speed in case of deposition by dip coating). The longer the removal time, the thinner the final dry coating will be.

The main face of the substrate may be coated with several functional coatings to improve its optical and/or mechanical properties. The term "coating" is understood to mean any layer, stack of layers or film that can be in contact with a substrate and/or with another coating (for example, a sol-gel coating or a coating made of an organic resin). The coating may be deposited or formed by various methods, including wet processing, gas processing, and film transfer. The functional coating used herein may be selected from, but is not limited to, these coatings: an impact-resistant coating, an abrasion and/or scratch-resistant coating, an antireflective coating, a polarizing coating, a photochromic coating, an antistatic coating, an antifouling coating (hydrophobic and/or oleophobic coating), an antifogging coating, a precursor of an antifogging coating or a stack made of two or more such coatings.

The primer coating that improves the impact resistance and/or adhesion of the additional layer in the final product is preferably a polyurethane latex or an acrylic latex. The primer coating and the abrasion and/or scratch resistant coating may be chosen from those described in application WO 2007/088312.

The abrasion-and/or scratch-resistant coating (hard coating) is preferably a hard coating based on poly (meth) acrylates or silanes. The hard abrasion and/or scratch resistant coatings recommended in the present invention comprise coatings obtained from compositions based on silane hydrolysates (sol-gel process), in particular epoxy silane hydrolysates, such as those described in US patent application US 2003/0165698 and in US 4,211,823 and EP 614957.

The antireflective coating may be any antireflective coating conventionally used in the field of optics, in particular ophthalmic optics. As is also well known, antireflective coatings conventionally comprise a single layer or a stack of layers consisting of dielectric materials (typically one or more metal oxides) and/or sol-gel materials and/or organic/inorganic layers as disclosed in WO 2013/098531. These are preferably multilayer coatings comprising a layer with a high refractive index (HI) and a layer with a low refractive index (LI).

The structure and preparation of antireflective coatings are described in more detail in patent applications WO 2010/109154, WO 2011/080472 and WO 2012/153072.

The antifouling top coat is preferably deposited on the outer layer of the antireflection coating. Generally, the thickness is less than or equal to 10nm, preferably ranging from 1 to 10nm, more preferably from 1 to 5 nm. The antifouling top coat is typically a fluorosilane or fluorosilazane type coating, preferably comprising fluoropolyether moieties and more preferably perfluoropolyether moieties. More detailed information on these coatings is disclosed in WO 2012076714.

Coatings such as primers, hardcoats, antireflective coatings, and antisoiling coatings can be deposited using methods known in the art, including spin coating, dip coating, spray coating, evaporation under vacuum, sputtering, chemical vapor deposition, and lamination.

In an embodiment, the method comprises forming an epoxy coating, an impact-resistant coating, an abrasion and/or scratch-resistant coating, and optionally an antireflective coating and an antifouling coating according to the invention on a substrate. The epoxy coating can also be applied in different coating configurations to maintain or improve general coating performance while still showing low haze and good adhesion, such as forming a polyurethane reactive hot melt adhesive on the substrate (optional), an epoxy coating according to the invention, an impact resistant coating, an abrasion and/or scratch resistant coating, and an antireflective coating (optional). In one embodiment, the epoxy coating of the present invention is interposed between the impact resistant coating and the wear and/or scratch resistant coating.

Since the epoxy coating of the present invention provides corrosion resistance, it can also be used as an outer layer deposited directly on a substrate or functional coating. In another embodiment, it is used as a protective coating to prevent scratches or similar appearance defects resulting from physical treatment of an underlying layer or substrate, such as a photochromic layer, as disclosed in WO 2011/075128 or US 6,268,055.

The coatings are preferably deposited directly on each other. These coatings may be deposited one after the other or may form a stack of one or more coatings on a substrate, for example by lamination.

In one embodiment, the optical article of the present invention is prepared by forming an epoxy coating on a substrate in a first manufacturing location, while forming other coatings in a second manufacturing location.

The coating according to the invention has improved color properties, especially when it is color balanced, which can be quantified by the yellowness index YI. The whiteness of the coatings of the invention can be quantified by colorimetric measurements based on the CIE tristimulus value X, Y, Z (as described in standard ASTM E313, using illuminant C observer 2 °). The optical material forming the coating according to the invention preferably has a low yellowness index YI as measured according to the above standard, i.e. lower than 10, more preferably lower than 5. The yellowness index YI is calculated according to ASTM method E313 by the relation YI ═ (127.69x-105.92Z))/Y, where X, Y and Z are CIE tristimulus values.

The optical article according to the invention preferably has a relative light transmission factor Tv in the visible spectrum greater than or equal to 85% or 87%, preferably greater than or equal to 90%, more preferably greater than or equal to 92%, and better still greater than or equal to 95%. The Tv factor preferably ranges from 87% to 98.5%, more preferably from 88% to 97%, even better from 90% to 96%. The Tv factor, also called the "light transmission" of the system, is as defined in the standard NF EN 1836 and is related to the average value in the 380-780nm wavelength range, weighted according to the sensitivity of the eye at each wavelength of said range and measured under D65 lighting conditions (daylight).

The following examples illustrate the invention in more detail but not by way of limitation. All thicknesses disclosed in this application refer to physical thicknesses unless otherwise indicated. The percentages given in the table are percentages by weight. Unless otherwise indicated, the refractive indices mentioned in the present invention are expressed at 25 ℃ at a wavelength of 550 nm.

Examples of the invention

1. Material

Optical articles used in the examples include those from VIEW ROUTINEA lens substrate having a diameter of 65mm, a refractive index of 1.50, a power of-2.00 diopters, and a thickness of 1.2 mm.

Various coating compositions of the epoxy copolymer were prepared and are shown in the following table. The composition comprises at least one non-silicon containing di-or tri-functional epoxy monomer comprising two or three epoxy groups (compound (a)), gamma-glycidoxypropyltrimethoxysilane prehydrolyzed with 0.10N HCl as compound (b) (from Evonik Industries), a metal chelate catalyst (compound (c), aluminum acetylacetonate, Al (AcAc)₃) Hindered aminesLight stabilizer (Compound (e)), surfactant (sold by 3M Co., Ltd.)FC-4434, which is a nonionic surfactant comprising a fluoroaliphatic polymeric ester, 25% wt. in dipropylene glycol monomethyl ether), Savinyl Blue RS (solvent soluble metal complex dye, color balancing dye supplied by Clariant International Ltd.), and,(blue-blocking yellow dye with narrow absorption peak supplied by Exciton Co., Ltd.), D&C Violet #2 (1-hydroxy-4- (p-tolylamino) anthracene-9, 10-dione, color balancing dye from Sensist), propylene glycol methyl ether (available from the Dow chemical company)PM) and methanol as solvent.

The following hindered amine light stabilizers were used:144 (bis (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) 2-n-butyl- (3, 5-di-tert-butyl-4-hydroxy-benzyl) malonate),292 (a mixture of bis (1, 2, 2, 6, 6-pentamethyl-4-piperidinyl) sebacate and methyl (1, 2, 2, 6, 6-pentamethyl-4-piperidinyl) sebacate), and152(2, 4-bis [ N-butyl-N- (1-cyclohexyloxy-2, 2, 6, 6-tetramethylpiperidin-4-yl) amino]-6- (2-hydroxyethylamine) -1, 3, 5-triazine), all available from basf.

The following non-silicon-containing di-or tri-functional epoxy monomers (compounds) containing two or three epoxy groups were investigated(a))：Erisys^TMGE-31 (Trimethylolethane triglycidyl ether from CVC thermoset specialty materials, abbreviated GE-31), Erisys^TMGE-30 (trimethylolpropane triglycidyl ether from the CVC thermoset specialty sector, abbreviated to GE-30) andUVR-6110(3 ', 4' -epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate, abbreviated UVR-6110, cycloaliphatic diepoxy compound from the Dow chemical company).

The following non-silicon containing multifunctional epoxy monomers containing from 4 to 8 epoxy groups (compound (d)) are used in some examples: erisys^TMGE-60 (sorbitol polyglycidyl ether from CVC thermoset specialty materials section, abbreviated GE-60).

Other optional compounds may be included in some compositions, such as245 (triethylene glycol bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, an antioxidant available from basf corporation), and UV absorbers from basf corporation such as477 (hydroxyphenyl-triazines),479 (hydroxyphenyl triazine) or1130 (hydroxyphenyl triazole).

The structures of some of the various epoxy compounds and hindered amine light stabilizers used are reviewed below:

2. evaluation of coating Properties and composition stability

a) The abrasion resistance and haze of the coating were determined as disclosed in WO 2012/173596. Specifically, abrasion resistance was measured by the sand Bayer test according to ASTM F735-81. Haze was measured according to standard ASTM D1003-00 on a Haze-Gard XL-211Plus instrument from Bick-Gardner company (BYK-Gardner). Since haze is a measure of the percentage of transmitted light scattered from the axis of the incident light by more than 2.5 °, the lower the haze value, the lower the haze. Generally, haze values of less than or equal to 0.3% are acceptable for the optical articles described herein, more preferably less than or equal to 0.2%.

b) Protection from phototoxic blue light by the coating of the invention is demonstrated by calculating the average blue light protection factor BVC between 400nm and 450nm, weighted by the light hazard function B' (λ) based on the transmission spectrum. This factor is defined by the following relation and is measured at 0 ° incidence:

where T (λ) denotes the lens transmission factor at a given wavelength, measured at an angle of incidence between 0 ° and 17 °, preferably 0 °, and B' (λ) denotes the light hazard function (relative spectral function efficiency) shown on figure 1 of publication WO 2017/077359 in the name of the applicant. The light hazard function is generated by work between the Paris Vision Institute and the International of Vision International, Inc. of Vision. It can be seen on this figure that blue light is most dangerous to the human eye at 428-431 nm. Several values of the B' (λ) function between 400 and 450nm are given below:

wavelength (nm)	Weighting factor B' (λ)
		400	0.1618
410	03263
		420	0.8496
430	1.00
		440	0.6469
450	0.4237

c) The yellowness index YI of the prepared lenses was calculated as described above by measuring the CIE tristimulus value X, Y, Z (as described in standard ASTM E313-05) with a Cary 4000 spectrophotometer from Hunter corporation on a white background by reflectance measures, with the front (convex) side of the lens facing the detector and light entering on said front side. This way of measuring YI from the viewer's perspective is closest to the actual wearing situation.

The resistance of the coatings of the invention to photodegradation was evaluated under light conditions of exposure to the Q-sun test. The Q-sun test involves the introduction of the prepared articleXe-3 xenon gas cells reproduce the full spectrum of sunlight purchased from Q-LAB at a relative humidity of 20% (+ -5%) and a temperature of 23 deg.C (+ -5 deg.C) and expose their convex surface to the irradiation for 40h or 80 h. The preparation was again measured by Cary 4000 spectrophotometer to obtain new YI parameters and YI loss caused by the Q-sun test.

d) According to ISTM 02-010, using 3Mn ° 600 scotch tapes (as disclosed in US 7476415 and US 2014/037964) were subjected to a dry adhesion test called the cross-line tape peel adhesion test after the coated articles had been subjected to the Q-Sun test described above.

e) The pot life test procedure for the coating solution is described herein.

The solids content of the coating solution was measured by a Smart System 5 microwave moisture analyzer, purchased from CEM. The Smart System 5 is set to use a fixed program of 100% power and 100 ℃. The weighing paper was first placed on a microbalance to dry in the chamber and then approximately 2g of the test solution was applied over the paper. After 2 minutes, the volatile/moisture content was dried out in the chamber and the remaining content remained on the paper, with the final percent solids (%) shown on the screen. Three measurements were made for each solution to obtain an average result.

The viscosity of the coating solution was recorded by a programable DV-II + viscometer purchased from Brookfield Engineering Laboratories, Inc. The test solution was applied in the range of 15-20 grams to a stainless steel tube with a specific main axis inside and then at 25 deg.CHeating in a heating circulating bath to a constant temperature. The spindle speed is set to suit the viscosity range, such as 30, 50, 60 or 100rpm, which can produce a numerical display reading between 10% and 100% torque. After about 5 minutesThe viscosity reading on the screen became constant with a small centipoise change over time (± 0.02), and this centipoise (cPs) value was recorded as the solution viscosity. Two to three measurements were made for each solution to obtain an average result.

When the solution was fully blended in an amber Nalgene container, the solids content (%) and viscosity of the test solution were measured simultaneously on the first day (day 1). The solution was then continuously stirred during the stirring phase and kept in a closed container at room temperature for 5 days (21 ℃ -23 ℃ and-50% humidity). At the sixth day (day 6), the solid content (%) and the viscosity of the test solution were measured again.

3. Preparation, deposition and curing of coating compositions

The epoxy compounds (a) and (d) (when present) were mixed in a Nalgene vessel. Adding a solvent (PM and methanol) and the solution was stirred for 60 minutes. The surfactant, dye, compound (e) and optional components (e.g. UV absorber) are added and the mixture is mixed for a further 30-60 minutes.

Compound (b) (typically Glymo) was mixed with 0.1N HCl for 0.5-1 hour and then added to the other ingredients. Sonication or stirring processes are sometimes added to obtain a more homogeneous solution. Finally, Al (AcAc)₃(after addition of hydrolyzed Glymo to the epoxide/solvent/dye mixture).

Cleaned (500rpm for 5s, then 1000rpm for 10s) previously with diluted NaOH by dip-coating in the coating composition (at a take-off speed of 2.0-2.5 mm/s)Both sides of the lens were deposited with each of the coating compositions except coating compositions C4, C4-1 and C4-2, which were cleaned in advance using corona treatment for 20-30 seconds, then rinsed with soapy water and deionized water and dried in air or by a lens dryerSpin coating (400rpm for 6 minutes followed by 800rpm for 10 minutes) was performed on the lenses for deposition. The pre-curing step is then carried out at 75-80 ℃ for 20 minutes overall, followed by a post-curing step at 100 ℃ for 3 hours. The (dry) coating thickness is 4.5-5.5 μm.

The formulations prepared and the characterization of these formulations are shown in the table below.

(f1)477(UV absorber). (e1)144(HALS)。

(f2)479(UV absorbers).

(f3)1130(UV absorber). (g1)245 (antioxidant).

(f1)477(UV absorber). (e1)144(HALS)。

(e2)292(HALS)。

(f1)477(UV absorber). (e1)144(HALS)。

(f1)477(UV absorber). (e1)144(HALS)。

(e3)152(HALS)。

Stability of the composition

Four reference epoxy compositions (C1, C2, C3 and C4) were prepared showing poor stability to which one or more additives (HALS, UV absorbers and/or antioxidants) were added.

The viscosity and weight solids content parameters of these compositions were recorded on the same day (day 1). Each of these compositions was then continuously stirred and kept in a closed plastic bottle for 5 days at room temperature (21 ℃ -23 ℃ and-50% humidity). Their viscosity and solids weight content parameters were again recorded on day 6.

Comparison of example C1 with C1-1 to C1-6 shows that only HALS additives292 and144 improved the storage stability of the control composition C1. The viscosity increase between day 1 and day 6 was much lower (Δ)_{Viscosity of the oil}Delta < 0.2cPs vs reference composition C1_{Viscosity of the oil}0.88) and lower weight gain of solids between day 1 and day 6 (probably due to polymerization). The other additives studied (UV absorbers, antioxidants) either maintained the change of the reference composition or made the composition change even worse (examples C1-1 to C1-4).

In a second study, different HALS, UV absorbers and antioxidants were combined together and added to reference composition C1 to examine how they affect the stability of the composition (storage)Period). It was found that (HALS + UV absorber), (HALS + antioxidant) or a combination of (HALS + antioxidant + UV absorber) can achieve a small increase in both viscosity and solids content. It is noted that for the C1-8 composition,292(HALS) significantly stabilizes the viscosity of the composition (. DELTA._{Viscosity of the oil}＝0.01cPs)。

By adding additives in selected combinations in different reference compositions (C2, C3 and C4) comprising higher amounts of catalyst (C)477、144、152 and245 demonstrate these aging improvement effects.

Coating Properties

Several coating configurations were tested to show that the epoxy coating of the present invention can be used as an intermediate functional layer for different coating configurations and maintain or improve general coating properties such as mechanical properties:

configuration 1: lens/epoxy coating (no surrounding coating).

Configuration 2: lens/epoxy coating/primer coating/hard coating.

Configuration 3: lens/epoxy/primer/hard coat/anti-reflective coating.

The primer coating (polyurethane) and the hard coating (polysiloxane, refractive index: 1.5) are those used in the examples of WO 2013/013929 and were deposited by dip coating. The antireflection coating is that of example 6 of patent application WO 2008/107325. The antireflection coating is formed by evaporation under vacuumDeposited, comprising 150nm thick SiO₂Sublayer and stack ZrO₂/SiO₂/ZrO₂/ITO/SiO₂(the respective thicknesses of the layers: 29, 23, 68, 7 and 85 nm). The ITO layer is indium oxide (In) doped with tin₂O₃: sn).

The results are shown below.

Example C2 and C2-3 coatings did not contain blue cut dyes.

The coating according to the invention shows a low haze (typically 0.1%). After the 80h Q-sun test exposure, they passed the adhesion test. Comparison with reference lenses (examples C1, C2, C3) shows that coatings containing additives (UV absorbers, HALS, antioxidants) maintain similar coating properties such as haze, sand bayer and adhesion in configurations 1, 2 or 3. However, in configuration 3, the lenses showed less change in yellowness than the control lenses (lower% loss of YI after the 40h Q-sun test).

Blue light cut performance was good, ranging from 20% to 26% (for coatings containing blue light cut dyes), with low photodegradation after 40h Q-sun exposure. Higher concentrations of blue-cutting dyes can be used to obtain articles with high protection from blue light.

The properties of the coating according to the invention are almost identical when the coating composition is deposited for 6 days after its preparation.