Polymerizable composition for optical article and optical article

Abstract

Provided is a polymerizable composition for an optical article, said composition including a photochromic compound and two or more (meth)acrylates. The two or more (meth)acrylates include at least a polyfunctional (meth)acrylate having a molecular weight of 500 or more and containing a polyalkylene glycol moiety, and the content of (meth)acryloyl groups in the polymerizable composition for an optical article is 3.50 mmol / g or more.

Description

[Technical Field]

[0001] The present invention relates to a polymerizable composition for an optical article and an optical article. [Background technology]

[0002] A photochromic compound is a compound that exhibits a property (photochromic property) of developing a color when irradiated with light in a photoresponsive wavelength range and fading when not irradiated with light. One method of imparting photochromic property to optical articles such as eyeglass lenses is to provide a coating containing a photochromic compound and a polymerizable compound on a substrate, and then harden this coating to form a hardened layer (photochromic layer) having photochromic property (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] WO2003 / 011967 Summary of the Invention [Problem to be solved by the invention]

[0004] It is desirable for the above-described photochromic optical article to exhibit a fast fading rate after color development upon exposure to light, for example, outdoors. Another desirable property of the optical article is excellent weather resistance. However, according to the inventor's investigations, there is a trade-off between the fading rate and weather resistance, and it has been difficult to achieve both a fast fading rate and excellent weather resistance in the past.

[0005] An object of one aspect of the present invention is to provide a polymerizable composition for an optical article that can form a photochromic layer that fades quickly and has excellent weather resistance. [Means for solving the problem]

[0006] One aspect of the present invention relates to a polymerizable composition for optical articles (hereinafter also referred to simply as "composition") that includes two or more (meth)acrylates and a photochromic compound. The two or more (meth)acrylates include at least a polyfunctional (meth)acrylate (hereinafter also referred to as "Component A") that contains a polyalkylene glycol moiety and has a molecular weight of 500 or more. Furthermore, the polymerizable composition for optical articles has a (meth)acryloyl group content of 3.50 mmol / g or more.

[0007] For example, photochromic compounds undergo a structural change upon irradiation with light such as sunlight, passing through an excited state. The structure after structural change upon irradiation with light can be called a "colored body." In contrast, the structure before irradiation with light can be called a "colorless body." Note that "colorless" in the colorless body does not necessarily mean completely colorless, but also encompasses a state in which the color is lighter than the colored body. After structural change to a colored body upon irradiation with light and color development, the faster the rate of structural change from the colored body to the colorless body, the faster the fading rate. In the photochromic layer, the easier the molecular movement of the photochromic compound in the matrix formed by the polymerization reaction of the polymerizable compound is thought to be the faster the rate of the structural change. From the perspective of accelerating this rate, a flexible matrix is ​​considered desirable. In relation to the above points, the inventors speculate that component A contributes to making the matrix flexible. Specifically, the molecular weight of component A being 500 or more and the presence of a polyalkylene glycol moiety in component A are thought to be the reasons why a flexible matrix can be formed by component A. The present inventors also speculate that the (meth)acryloyl group content of the composition of 3.50 mmol / g or more contributes to the formation of a rigid polymer network between molecules in a matrix formed from the composition. The present inventors believe that the reason why the composition can form a photochromic layer with excellent weather resistance is that the diffusion of active species that can cause a decrease in weather resistance can be suppressed in a matrix having a rigid polymer network. The present inventors believe that the composition described above enables the formation of a photochromic layer that fades quickly and has excellent weather resistance, although the present invention is not limited to the speculations described herein. [Effects of the Invention]

[0008] According to one aspect of the present invention, there is provided a polymerizable composition for an optical article capable of forming a photochromic layer that exhibits a rapid color fading rate after color development upon exposure to light and has excellent weather resistance. Also, according to another aspect of the present invention, there is provided an optical article having a photochromic layer that exhibits a rapid color fading rate after color development upon exposure to light and has excellent weather resistance. [Brief explanation of the drawings]

[0009] [Figure 1] 1 shows a graph in which the ΔDarkness value is plotted against the (meth)acryloyl group content for each of the polymerizable compositions of Examples and Comparative Examples. DETAILED DESCRIPTION OF THE INVENTION

[0010] [Polymerizable composition for optical articles] The polymerizable composition for an optical article according to one embodiment of the present invention will be described in further detail below.

[0011] In the present invention and this specification, a polymerizable composition refers to a composition containing a polymerizable compound. A polymerizable compound is a compound having a polymerizable group. A polymerizable composition for an optical article according to one embodiment of the present invention is a polymerizable composition used for producing an optical article, and can be a coating composition for an optical article, more specifically, a coating composition for forming a photochromic layer of an optical article. A coating composition for an optical article refers to a composition that is applied to a substrate or the like for producing an optical article. Examples of optical articles include various lenses such as eyeglass lenses and goggle lenses, visors for sun visors, and helmet shields. For example, eyeglass lenses produced by applying the above composition to a lens substrate have a photochromic layer and can exhibit photochromic properties.

[0012] In the present invention and this specification, the term "(meth)acrylate" is used to encompass both acrylate and methacrylate. An "acrylate" is a compound having one or more acryloyl groups in one molecule. A "methacrylate" is a compound having one or more methacryloyl groups in one molecule. The functionality of a (meth)acrylate is the number of groups selected from the group consisting of acryloyl groups and methacryloyl groups contained in one molecule. In the present invention and this specification, a "methacrylate" refers to a compound containing only methacryloyl groups as (meth)acryloyl groups, and a compound containing both acryloyl and methacryloyl groups as (meth)acryloyl groups is called an acrylate. The acryloyl group may be contained in the form of an acryloyloxy group, and the methacryloyl group may be contained in the form of a methacryloyloxy group. The term "(meth)acryloyl group" used below encompasses both acryloyl and methacryloyl groups, and the term "(meth)acryloyloxy group" encompasses both acryloyloxy and methacryloyloxy groups. Unless otherwise specified, the groups described herein may be substituted or unsubstituted. When a group has a substituent, examples of the substituent include an alkyl group (e.g., a linear alkyl group having 1 to 6 carbon atoms or a branched alkyl group having 1 to 6 carbon atoms), a hydroxyl group, an alkoxy group (e.g., an alkoxy group having 1 to 6 carbon atoms), a halogen atom (e.g., a fluorine atom, a chlorine atom, or a bromine atom), a cyano group, an amino group, a nitro group, an acyl group, a carboxy group, an aryl group, and a polyether group. Regarding a substituted group, the "carbon number" refers to the number of carbon atoms in the portion excluding the substituent. In the present invention and this specification, the term "linear alkyl group or branched alkyl group" does not encompass cycloalkyl groups. The linear alkyl group or branched alkyl group may be unsubstituted or may have a substituent. It is permissible for a linear or branched alkyl group to have a cycloalkyl group (e.g., a cyclohexyl group) as a substituent. In one embodiment, it is preferred that a linear or branched alkyl group does not have a cycloalkyl group as a substituent.

[0013] <(Meth)acryloyl group content> From the viewpoint of improving weather resistance, the (meth)acryloyl group content of the composition is 3.50 mmol / g or more, preferably 3.55 mmol / g or more, more preferably 3.60 mmol / g or more, even more preferably 3.65 mmol / g or more, even more preferably 3.70 mmol / g or more, and even more preferably 3.75 mmol / g or more. The (meth)acryloyl group content of the composition can be, for example, 5.00 mmol / g or less, 4.50 mmol / g or less, or 4.00 mmol / g or less, or may exceed the values ​​exemplified herein.

[0014] The "(meth)acryloyl group content" of a polymerizable composition containing a (meth)acrylate is calculated as follows. The content of each (meth)acrylate is calculated by taking the total amount of (meth)acrylate contained in the polymerizable composition as "1" on a mass basis. For each (meth)acrylate, the "(meth)acryloyl group content x the above content" is calculated. The sum of the values ​​thus calculated for all (meth)acrylates contained in the polymerizable composition is taken as the (meth)acryloyl group content of the polymerizable composition.

[0015] <Polymerizable compound> The composition contains two or more types of (meth)acrylates as polymerizable compounds, and the two or more types of (meth)acrylates include at least a polyfunctional (meth)acrylate (component A) containing a polyalkylene glycol moiety and having a molecular weight of 500 or more.

[0016] Component A will be described in more detail below.

[0017] (Component A) Component A is a polyfunctional (meth)acrylate containing a polyalkylene glycol moiety and having a molecular weight of 500 or more. In the present invention and this specification, the term "polyalkylene glycol moiety" refers to a polyfunctional (meth)acrylate having a molecular weight of 500 or more and having a molecular weight of 500 or more. [ka] In Formula 2, R represents an alkylene group, n represents the number of repeating alkoxy groups represented by RO and is 2 or more. * represents the bonding position where the partial structure represented by Formula 2 is bonded to an adjacent atom. The number of carbon atoms in the alkylene group represented by R can be 1 or more or 2 or more, and can be, for example, 5 or less or 4 or less. Specific examples of the alkylene group represented by R include an ethylene group, a propylene group, and a tetramethylene group. n is 2 or more and can be, for example, 30 or less, 25 or less, or 20 or less. In one embodiment, Component A can have the above partial structure in which R represents an ethylene group, i.e., a polyethylene glycol moiety. In another embodiment, Component A can have the above partial structure in which R represents a propylene group, i.e., a polypropylene glycol moiety.

[0018] The molecular weight of component A is 500 or more. In the present invention and this specification, the molecular weight of the multimer is determined by the structural formula determined by structural analysis of the compound or the theoretical molecular weight calculated from the raw material charging ratio during production. The molecular weight of component A is 500 or more, preferably 510 or more, more preferably 520 or more, preferably 550 or more, more preferably 570 or more, even more preferably 600 or more, even more preferably 630 or more, and even more preferably 650 or more. From the viewpoint of increasing the hardness of the photochromic layer, the molecular weight of component A is preferably, for example, 2000 or less, 1500 or less, 1200 or less, 1000 or less, or 800 or less.

[0019] Component A is a polyfunctional (meth)acrylate, and may be, for example, a difunctional, trifunctional, tetrafunctional, or pentafunctional (meth)acrylate, and is preferably a difunctional or trifunctional (meth)acrylate. Component A may contain only acryloyl groups, only methacryloyl groups, or both acryloyl and methacryloyl groups as (meth)acryloyl groups. That is, Component A may be an acrylate or methacrylate.

[0020] In one embodiment, component A can be an acyclic polyfunctional (meth)acrylate. In the present invention and this specification, "acyclic" means not containing a cyclic structure. In contrast, "cyclic" means containing a cyclic structure. An acyclic polyfunctional (meth)acrylate refers to a bifunctional or higher functional (meth)acrylate that does not contain a cyclic structure. A specific example of such component A is a polyalkylene glycol di(meth)acrylate represented by the following formula 3.

[0021] [ka]

[0022] In formula 3, R 1 and R 2 each independently represents a hydrogen atom or a methyl group, R represents an alkylene group, and n represents the number of repetitions of the alkoxy group represented by RO and is 2 or more. R and n are as described above for the partial structure represented by formula 2. The polyalkylene glycol di(meth)acrylate represented by formula 3 may contain only acryloyl groups, only methacryloyl groups, or both acryloyl and methacryloyl groups as (meth)acryloyl groups. Specific examples of the polyalkylene glycol di(meth)acrylate represented by formula 3 include polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and polytetramethylene glycol di(meth)acrylate.

[0023] Specific examples of component A include tri(meth)acrylates represented by the following formula 4. The tri(meth)acrylates represented by formula 4 may contain only acryloyl groups, only methacryloyl groups, or both acryloyl and methacryloyl groups as (meth)acryloyl groups.

[0024] [ka]

[0025] In formula 4, R 40 , R 41 , R 44 , R 45 , R 47 and R 48 each independently represents an alkylene group, R 43 represents an alkyl group, and R 42 , R 46 and R 49 each independently represents a hydrogen atom or a methyl group; 41 n2 represents the number of repeating alkoxy groups represented by the formula: 45 n3 represents the number of repeating alkoxy groups represented by the formula: 48 The number of repetitions of the alkoxy group represented by the formula (I) is 2 or more.

[0026] Equation 4 will be explained in more detail below.

[0027] R in Equation 4 41 , R 45 and R 48 In Formula 4, n1, n2, and n3 are as described above for n in Formula 2. In Formula 4, R 41 , R 45 and R 48 may be the same, or two or three may be different. The same applies to n1, n2, and n3.

[0028] R42 , R 46 and R 49 each independently represents a hydrogen atom or a methyl group. The tri(meth)acrylate represented by formula 4 may contain only acryloyl groups, only methacryloyl groups, or both acryloyl groups and methacryloyl groups as (meth)acryloyl groups.

[0029] R 43 The number of carbon atoms in the alkyl group represented by R can be 1 or more, or 2 or more, and can be, for example, 5 or less, or 4 or less. 43 The alkyl group represented by R can be a straight chain alkyl group or a branched alkyl group. 43 Specific examples of the alkyl group represented by the formula include a methyl group and an ethyl group.

[0030] R 40 , R 44 and R 47 each independently represents an alkylene group. The number of carbon atoms in such an alkylene group can be 1 or more or 2 or more, and can be, for example, 5 or less or 4 or less. Specific examples thereof include an ethylene group, a propylene group, and a tetramethylene group.

[0031] Specific examples of the tri(meth)acrylate represented by formula 4 include trimethylolpropane polyoxyethylene ether tri(meth)acrylate.

[0032] (Monofunctional (meth)acrylate) From the viewpoint of increasing the (meth)acryloyl group content of a polymerizable composition containing a (meth)acrylate, a (meth)acrylate having a high ratio of (meth)acryloyl groups in the molecule is preferred. From this viewpoint, a low-molecular-weight monofunctional (meth)acrylate is preferred, and a monofunctional (meth)acrylate having a molecular weight of 150 or less is more preferred. The monofunctional (meth)acrylate having a molecular weight of 150 or less may be a cyclic monofunctional (meth)acrylate or an acyclic monofunctional (meth)acrylate. A specific example of a cyclic monofunctional (meth)acrylate having a molecular weight of 150 or less is glycidyl (meth)acrylate. A specific example of an acyclic monofunctional (meth)acrylate having a molecular weight of 150 or less is n-butyl (meth)acrylate. The molecular weight of a monofunctional (meth)acrylate having a molecular weight of 150 or less may be, for example, 100 or more, but is not limited thereto.

[0033] (Multifunctional (meth)acrylate) As described above, from the viewpoint of increasing the (meth)acryloyl group content of a polymerizable composition containing a (meth)acrylate, a (meth)acrylate with a high ratio of (meth)acryloyl groups in the molecule is preferred. From this viewpoint, a polyfunctional (meth)acrylate having a molecular weight smaller than that of Component A is also preferred. As such a polyfunctional (meth)acrylate, a polyfunctional (meth)acrylate having a higher functionality than the polyfunctional (meth)acrylate used as Component A is also preferred. The molecular weight of such a polyfunctional (meth)acrylate is preferably less than 500, 400 or less, 300 or less, or 200 or less. The molecular weight can be, for example, 100 or more, but is not limited thereto. Furthermore, such a polyfunctional (meth)acrylate can be, for example, a polyfunctional (meth)acrylate having 10 or more functionalities (e.g., 10 to 15 functionalities). Specific examples include poly[(3-methacryloyloxypropyl)silsesquioxane] derivatives described in the Examples section below.

[0034] Examples of (meth)acrylates that can be included in the composition include a monofunctional (meth)acrylate represented by the following formula 1 (hereinafter also referred to as "component B") and a bifunctional (meth)acrylate represented by the following formula 5 (hereinafter also referred to as "component C"). In one embodiment, the composition can be a polymerizable composition containing one or more (meth)acrylates selected from the group consisting of a monofunctional (meth)acrylate represented by the following formula 1 and a bifunctional (meth)acrylate represented by the following formula 5. In another embodiment, the composition can be a polymerizable composition that does not contain one or more (meth)acrylates selected from the group consisting of a monofunctional (meth)acrylate represented by the following formula 1 and a bifunctional (meth)acrylate represented by the following formula 5. In one embodiment, the composition can also contain component B as a monofunctional (meth)acrylate having a molecular weight of 150 or less.

[0035] (Component B) Component B is a monofunctional (meth)acrylate represented by the following formula 1.

[0036] [ka]

[0037] Formula 1 will be explained in more detail below.

[0038] In formula 1, R 10 represents a hydrogen atom or a methyl group. The monofunctional (meth)acrylate represented by formula 1 may be an acrylate or a methacrylate.

[0039] R 11 R represents a linear alkyl group having 3 or more carbon atoms or a branched alkyl group having 3 or more carbon atoms. These alkyl groups may be unsubstituted or may have a substituent. The substituent is not particularly limited, and examples thereof include the various substituents described above. 11The number of carbon atoms in the linear or branched alkyl group represented by the formula (I) is 3 or more, preferably 4 or more, more preferably 5 or more, and further preferably 6 or more, 7 or more, 8 or more, 9 or more, 10 or more, and 11 or more in that order. On the other hand, from the viewpoint of the solubility of the photochromic compound in the composition, the number of carbon atoms is preferably 15 or less, more preferably 14 or less, and further preferably 13 or less, and 12 or less in that order.

[0040] The molecular weight of the monofunctional (meth)acrylate represented by Formula 1 can be, for example, 100 or more, or, for example, 300 or less. However, it is not limited to the above range. As described above, in one embodiment, the monofunctional (meth)acrylate represented by Formula 1 can be a monofunctional (meth)acrylate having a molecular weight of 150 or less. Specific examples of the monofunctional (meth)acrylate represented by Formula 1 include n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, and n-lauryl (meth)acrylate.

[0041] (Component C) Component C is represented by the following formula 5: [ka] It is a (meth)acrylate represented by the formula:

[0042] In formula 5, R 3 and R 4 each independently represents a hydrogen atom or a methyl group, and m represents an integer of 1 or greater. m is 1 or greater and can be, for example, 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less.

[0043] The molecular weight of component C can be, for example, 400 or less, and from the viewpoint of further increasing the color density of the photochromic layer, it is preferably 350 or less, more preferably 300 or less, and even more preferably 250 or less. The molecular weight of component C can be, for example, 100 or more, 150 or more, or 200 or more.

[0044] Component C may contain only acryloyl groups, only methacryloyl groups, or both acryloyl and methacryloyl groups as (meth)acryloyl groups. Specific examples of component C include 1,9-nonanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and 1,10-decanediol di(meth)acrylate.

[0045] In the composition, the content of component A is preferably 50% by mass or more, more preferably 55% by mass or more, and even more preferably 60% by mass or more, based on 100% by mass of the total amount of polymerizable compounds contained in the composition. In one embodiment, component A can be the component that accounts for the largest proportion of the multiple polymerizable compounds contained in the composition. Furthermore, the content of component A can be 90% by mass or less, 85% by mass or less, or 80% by mass or less, based on 100% by mass of the total amount of polymerizable compounds contained in the composition. In one embodiment, the composition can contain only one type of component A, and in another embodiment, it can contain two or more types. When two or more types of component A are contained, the content of component A mentioned above is the total content of the two or more types. This also applies to the contents of the other components.

[0046] The composition may contain the various (meth)acrylates described above in an amount such that the (meth)acryloyl group content of the composition is 3.50 mmol / g or more. For example, the composition preferably contains 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more of monofunctional (meth)acrylates having a molecular weight of 150 or less, based on 100% by mass of the total amount of polymerizable compounds contained in the composition. Furthermore, the content of monofunctional (meth)acrylates having a molecular weight of 150 or less is preferably 30% by mass or less, more preferably 25% by mass or less, based on 100% by mass of the total amount of polymerizable compounds contained in the composition.

[0047] The content of the polymerizable compound in the composition (i.e., the total content of the multiple polymerizable compounds) can be, for example, 80% by mass or more, 85% by mass or more, or 90% by mass or more, based on 100% by mass of the total amount of the composition. Furthermore, the content of the polymerizable compound in the composition can be, for example, 99% by mass or less, 95% by mass or less, 90% by mass or less, or 85% by mass or less, based on 100% by mass of the total amount of the composition. In the present invention and this specification, the term "total amount of the composition" in relation to the content refers to the total amount of all components excluding the solvent, in the case of a solvent-containing composition. The composition may or may not contain a solvent. When a solvent is contained, any solvent can be used in any amount as long as it does not inhibit the polymerization reaction of the polymerizable composition.

[0048] <Photochromic compounds> The composition contains a photochromic compound in addition to the polymerizable compound. The photochromic compound contained in the composition can be a known compound exhibiting photochromic properties. The photochromic compound can exhibit photochromic properties, for example, when exposed to ultraviolet light. Examples of photochromic compounds include azobenzenes, spiropyrans, spirooxazines, naphthopyrans, indenonaphthopyrans, phenanthropyrans, hexaarylbisimidazoles, donor-acceptor Stenhouse adducts (DASA), salicylideneanilines, dihydropyrenes, anthracene dimers, fulgides, diarylethenes, phenoxynaphthacenequinones, and stilbenes. Preferred photochromic compounds include fulgimide compounds, spirooxazine compounds, chromene compounds, and indeno-fused naphthopyran compounds. Further, the photochromic compound may be one or more compounds selected from the group consisting of photochromic compounds represented by general formula A, photochromic compounds represented by general formula B, and photochromic compounds represented by general formula C, as described in WO2022 / 138966. The photochromic compounds may be used alone or in combination of two or more. The content of the photochromic compound in the composition may be, for example, about 0.1 to 15% by mass, with the total amount of the composition being 100% by mass, but is not limited to this range.

[0049] <Other ingredients> In addition to the polymerizable compound and the photochromic compound, the composition may contain one or more of various additives that can be usually contained in polymerizable compositions, at any content. Examples of additives that can be contained in the composition include a polymerization initiator for promoting the polymerization reaction.

[0050] For example, a known polymerization initiator can be used as the polymerization initiator, a radical polymerization initiator is preferred, and it is more preferred that the polymerization initiator contains only a radical polymerization initiator. Furthermore, a photopolymerization initiator or a thermal polymerization initiator can be used as the polymerization initiator, and a photopolymerization initiator is preferred from the viewpoint of progressing the polymerization reaction in a short time. Examples of the photoradical polymerization initiator include benzoin ketals such as 2,2-dimethoxy-1,2-diphenylethan-1-one; α-hydroxyketones such as 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one; α-aminoketones such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one and 1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one; oxime esters such as 1-[(4-phenylthio)phenyl]-1,2-octadione-2-(benzoyl)oxime; bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, and the like. phosphine oxides such as 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer; benzophenone compounds such as benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, and 4-methoxy-4'-dimethylaminobenzophenone;quinone compounds such as 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, and 2,3-dimethylanthraquinone; benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; benzoin compounds such as benzoin, methylbenzoin, and ethylbenzoin; benzyl compounds such as benzil dimethyl ketal; acridine compounds such as 9-phenylacridine and 1,7-bis(9,9'-acridinylheptane); N-phenylglycine, coumarin, and the like. In the 2,4,5-triarylimidazole dimer, the substituents on the aryl groups of the two triarylimidazole moieties may be the same to give a symmetrical compound, or may be different to give an asymmetrical compound. A thioxanthone compound may also be combined with a tertiary amine, such as the combination of diethylthioxanthone and dimethylaminobenzoic acid. Among these, α-hydroxyketones and phosphine oxides are preferred from the viewpoints of curability, transparency, and heat resistance. The content of the polymerization initiator may be, for example, in the range of 0.1 to 5% by mass, with the total amount of the composition being 100% by mass.

[0051] The composition may further contain any amount of known additives that are typically added to compositions containing a photochromic compound, such as surfactants, antioxidants, radical scavengers, light stabilizers, ultraviolet absorbers, color inhibitors, antistatic agents, fluorescent dyes, dyes, pigments, fragrances, plasticizers, and silane coupling agents. Known compounds may be used as these additives.

[0052] The composition can be prepared by mixing the various components described above simultaneously or sequentially in any order.

[0053] [Optical articles] One aspect of the present invention relates to an optical article having a substrate and a photochromic layer formed by curing the above-described composition.

[0054] The optical article will now be described in more detail.

[0055] <Base material> The optical article may have a photochromic layer on a substrate selected depending on the type of optical article. As an example of the substrate, a spectacle lens substrate may be a plastic lens substrate or a glass lens substrate. The glass lens substrate may be, for example, a lens substrate made of inorganic glass. A plastic lens substrate is preferred as the lens substrate because it is lightweight, shatter-resistant, and easy to handle. Examples of plastic lens substrates include (meth)acrylic resins, styrene resins, polycarbonate resins, allyl resins, allyl carbonate resins such as diethylene glycol bisallyl carbonate resin (CR-39), vinyl resins, polyester resins, polyether resins, urethane resins obtained by reacting an isocyanate compound with a hydroxy compound such as diethylene glycol, thiourethane resins obtained by reacting an isocyanate compound with a polythiol compound, and cured products (generally referred to as transparent resins) obtained by curing a curable composition containing a (thio)epoxy compound having one or more disulfide bonds in the molecule. The lens substrate may be either undyed (colorless lenses) or dyed (dyed lenses). The refractive index of the lens substrate can be, for example, about 1.50 to 1.75. However, the refractive index of the lens substrate is not limited to the above range, and may be within the above range or may deviate above or below the above range. In the present invention and this specification, the refractive index refers to the refractive index for light with a wavelength of 500 nm. Furthermore, the lens substrate may be a lens with refractive power (a so-called prescription lens) or a lens without refractive power (a so-called non-prescription lens).

[0056] The spectacle lens can be any of various lenses, such as a single-vision lens, a multifocal lens, or a progressive-power lens. The type of lens is determined by the surface shapes of both sides of the lens substrate. The surface of the lens substrate may be convex, concave, or flat. In typical lens substrates and spectacle lenses, the object-side surface is convex and the eyeball-side surface is concave. However, the present invention is not limited to this. The photochromic layer can usually be provided on the object-side surface of the lens substrate, but it may also be provided on the eyeball-side surface.

[0057] <Photochromic layer> The photochromic layer of the optical article can be formed by applying the composition directly or indirectly via one or more other layers to the surface of a substrate and then curing the applied composition. Examples of such other layers include a primer layer for improving adhesion between the photochromic layer and the substrate. Such primer layers are known. Known coating methods, such as spin coating and dip coating, can be used as the coating method, with spin coating being preferred from the viewpoint of uniformity of the coating. The curing treatment can be light irradiation and / or heat treatment, with light irradiation being preferred from the viewpoint of progressing the curing reaction in a short period of time. The curing treatment conditions can be determined depending on the types of various components (such as the polymerizable compound and polymerization initiator described above) contained in the composition and the composition of the composition. The thickness of the photochromic layer thus formed is preferably in the range of, for example, 5 to 80 μm. From the viewpoint of exhibiting better photochromic properties, the thickness is more preferably in the range of 20 to 60 μm, even more preferably in the range of 20 to 50 μm, and even more preferably in the range of 25 to 45 μm. With regard to the viscosity of the composition, from the viewpoint of forming a photochromic layer having a thickness within a preferred range and excellent thickness uniformity, the viscosity at a temperature of 25°C is preferably 20 mPa·s or more. The viscosity at a temperature of 25°C may be, for example, 50 mPa·s or less or 40 mPa·s or less. However, from the viewpoint of improving the thickness uniformity of the photochromic layer, the viscosity of the composition may be greater than the values ​​exemplified here.

[0058] The optical article having the photochromic layer may or may not have one or more functional layers in addition to the photochromic layer. Examples of the functional layer include layers known as functional layers for optical articles, such as a protective layer for improving the durability of the optical article, an antireflection layer, a water-repellent or hydrophilic antifouling layer, and an antifogging layer.

[0059] One example of the optical article is a spectacle lens. Other examples of the optical article include a goggle lens, a sun visor, and a helmet shield. The composition is applied to a substrate for these optical articles, and the applied composition is cured to form a photochromic layer, thereby providing an optical article with antiglare properties.

[0060] [glasses] One aspect of the present invention relates to eyeglasses equipped with eyeglass lenses, which are one form of the optical article. Details of the eyeglass lenses included in the eyeglasses are as described above. By including such eyeglass lenses, the eyeglasses can, for example, exhibit anti-glare effects similar to sunglasses outdoors, as the photochromic compound included in the photochromic layer changes color when irradiated with sunlight, and regain transparency when the eyeglasses return indoors as the photochromic compound fades. Known technologies can be applied to the construction of the frames and other components of the eyeglasses. [Example]

[0061] The present invention will be further described below with reference to examples, but the present invention is not limited to the embodiments shown in the examples.

[0062] [Examples 1 and 2, Comparative Examples 1 and 2] <Preparation of polymerizable composition for optical article (coating composition for forming photochromic layer)> The ingredients shown in Table 1 were mixed in the amounts shown in Table 1 in a plastic container. The resulting mixture of polymerizable compounds was mixed with the following photochromic compound (an indeno-fused naphthopyran compound represented by the structural formula described in U.S. Pat. No. 6,296,785), a photoradical polymerization initiator (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (Omnirad 819, manufactured by IGM Resin BV)), an antioxidant (bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)]), and a light stabilizer (bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate) and thoroughly stirred. The mixture was then degassed using a rotation-revolution type stirring and degassing device. This produced a polymerizable composition for optical articles (a coating composition for forming a photochromic layer). The contents of the above components, taking the total amount of the composition as 100% by mass, are 94.9% by mass for the mixture of polymerizable compounds, 3% by mass for the photochromic compound, 0.3% by mass for the photoradical polymerization initiator, 0.9% by mass for the antioxidant, and 0.9% by mass for the light stabilizer.

[0063] [ka]

[0064] [Table 1]

[0065] [ka]

[0066] [ka]

[0067] [ka]

[0068] [ka]

[0069] [ka]

[0070] [ka]

[0071] The viscosity of each of the photochromic layer-forming compositions of Examples 1 and 2 and Comparative Examples 1 and 2 was measured by the following method. Using a viscometer (VM-100A manufactured by Sekonic Corporation), the liquid surface of the sample was adjusted and fixed so that it was approximately 2 to 3 mm from the end of the detection terminal, and the viscosity was measured at a liquid temperature of 25°C. The measured viscosities were 34 mPa·s for Example 1, 30 mPa·s for Example 2, 25 mPa·s for Comparative Example 1, and 23 mPa·s for Comparative Example 2.

[0072] <Production of eyeglass lenses> A plastic lens substrate (manufactured by HOYA Corporation under the trade name HI-LUX; center thickness 2.2 mm, radius 70 mm, S 0.00) was washed with pure water and dried. The photochromic layer-forming coating composition prepared above was then applied to the convex surface (object-side surface) of the plastic lens substrate by spin coating. Spin coating was performed according to the method described in JP 2005-218994 A. The composition applied to the plastic lens substrate was then irradiated with ultraviolet light (wavelength 405 nm) in a nitrogen atmosphere (oxygen concentration 500 ppm or less) to cure the composition and form a photochromic layer. The thickness of the formed photochromic layer was 40 μm. Each photochromic layer-forming composition having the above viscosity enabled the formation of a photochromic layer with excellent film thickness uniformity. In this way, a spectacle lens having a photochromic layer was produced.

[0073] [Evaluation method] (1) Evaluation of fading speed For each spectacle lens photochromic layer (a cured layer obtained by curing the polymerizable composition) in the Examples and Comparative Examples, the surface of the photochromic layer was irradiated with light from a xenon lamp through an aeromass filter for 15 minutes (900 seconds), causing the photochromic compound in the photochromic layer to develop a color. The transmittance (measurement wavelength: 550 nm) during this color development was measured using a spectrophotometer manufactured by Otsuka Electronics Co., Ltd. The light irradiation was carried out so that the irradiance and irradiance tolerance, as specified in JIS T7333:2005, were the values ​​shown in Table 2 below. The transmittance measured in this manner is referred to as the "transmittance during color development."

[0074] [Table 2]

[0075] After measuring the transmittance at color development, the transmittance was measured 60 seconds after the light irradiation was stopped (hereinafter referred to as "transmittance at 60 seconds after fading"). The fading rate (unit: % / second) was calculated using the formula: fading rate = [(transmittance at 60 seconds after fading - transmittance at color development) / 60]. The higher the value of the fading rate calculated in this way, the faster the fading rate.

[0076] (2) Weather resistance evaluation The weather resistance of each of the spectacle lenses of the Examples and Comparative Examples was evaluated using the weather resistance test method described in ISO 8980-3: 2013. The evaluation result of weather resistance was obtained as the amount of change in transmittance when colored (hereinafter referred to as ΔDarkness), and if the value of ΔDarkness is 6.0% or less, it can be said that the weather resistance is excellent.

[0077] The results are shown in Table 3. Figure 1 shows a graph in which the ΔDarkness values ​​are plotted against the (meth)acryloyl group content for each of the polymerizable compositions of the Examples and Comparative Examples. Figure 1 also shows an approximate line calculated by the least squares method.

[0078] [Table 3]

[0079] The results shown in Table 3 confirm that the spectacle lenses of Examples 1 and 2 exhibit a fading rate equivalent to that of the spectacle lenses of Comparative Examples 1 and 2, and are also excellent in weather resistance. In other words, it can be confirmed that the spectacle lenses of Examples 1 and 2 were able to achieve both a fast fading rate and excellent weather resistance. The inventors believe that the fast fading rate of the eyeglass lenses of Examples 1 and 2 was due to the polyfunctional (meth)acrylate (trimethylolpropane polyoxyethylene ether trimethacrylate, polypropylene glycol dimethacrylate) corresponding to Component A. Regarding weather resistance, the graph shown in Figure 1 confirms that there is a correlation between the (meth)acryloyl group content of the composition and ΔDarkness, and that ΔDarkness can be reduced to 6.0% or less by increasing the (meth)acryloyl group content of the composition to 3.50 mmol / g or more.

[0080] Finally, the above-mentioned aspects will be summarized.

[0081] [1] A polymerizable composition for optical articles, comprising two or more types of (meth)acrylates and a photochromic compound, wherein the two or more types of (meth)acrylates include at least a polyfunctional (meth)acrylate containing a polyalkylene glycol moiety and having a molecular weight of 500 or more, and the polymerizable composition for optical articles has a (meth)acryloyl group content of 3.50 mmol / g or more. [2] The polymerizable composition for optical articles according to [1], wherein the two or more (meth)acrylates include a monofunctional (meth)acrylate having a molecular weight of 150 or less. [3] The polymerizable composition for an optical article according to [1] or [2], wherein the polyalkylene glycol moiety of Component A is selected from the group consisting of a polyethylene glycol moiety and a polypropylene glycol moiety. [4] The polymerizable composition for optical articles according to any one of [1] to [3], wherein component A is a difunctional or trifunctional (meth)acrylate. [5] The polymerizable composition for an optical article according to any one of [1] to [4], which has a viscosity of 20 mPa·s or more at a temperature of 25°C. [6] An optical article comprising a substrate and a photochromic layer obtained by curing the polymerizable composition for an optical article according to any one of [1] to [5]. [7] The optical article according to [6], which is a spectacle lens. [8] The optical article according to [6], which is a lens for goggles. [9] The optical article according to [6], which is a visor part of a sun visor.

[10] The optical article according to [6], which is a shielding member for a helmet.

[11] Eyeglasses equipped with the eyeglass lenses described in [7].

[0082] Two or more of the various aspects and configurations described herein may be combined in any combination.

[0083] The embodiments disclosed herein should be considered to be illustrative in all respects and not restrictive. The scope of the present invention is defined by the claims, not by the above description, and is intended to include all modifications within the meaning and scope of the claims. [Industrial Applicability]

[0084] The present invention is useful in the technical fields of eyeglasses, goggles, sun visors, helmets, etc.

Claims

1. two or more (meth)acrylates; a photochromic compound; A polymerizable composition for an optical article, comprising: The two or more (meth)acrylates include at least Component A, Component A is a tri(meth)acrylate having a molecular weight of 500 or more and represented by the following formula 4: The polymerizable composition for an optical article has a (meth)acryloyl group content of 3.50 mmol / g or more and 4.00 mmol / g or less, and The polymerizable composition for optical articles contains 50% by mass or more and 80% by mass or less of Component A, where the total amount of polymerizable compounds contained in the polymerizable composition for optical articles is 100% by mass. 【Chemistry 1】 (In formula 4, R ４０ , R ４１ , R ４４ , R ４５ , R ４７ and R ４８ each independently represents an alkylene group; R ４３ represents an alkyl group, and R ４２ , R ４６ and R ４９ each independently represents a hydrogen atom or a methyl group. ４１ n2 represents the number of repeats of the group represented by the formula: ４５ n3 represents the number of repeats of the group represented by the formula: ４８ and is 2 or more.)

2. The polymerizable composition for an optical article according to claim 1 , wherein the two or more (meth)acrylates include a monofunctional (meth)acrylate having a molecular weight of 150 or less.

3. 2. The polymerizable composition for an optical article according to claim 1, wherein the polyalkylene glycol moiety of Component A is selected from the group consisting of a polyethylene glycol moiety and a polypropylene glycol moiety.

4. The polymerizable composition for an optical article according to claim 2 , wherein the polyalkylene glycol moiety of Component A is selected from the group consisting of a polyethylene glycol moiety and a polypropylene glycol moiety.

5. A polymerizable composition for optical articles as described in claim 1, further comprising a polyfunctional (meth)acrylate having a molecular weight of 500 or more and containing a polyalkylene glycol moiety other than the tri(meth)acrylate represented by formula 4.

6. A polymerizable composition for optical articles as described in claim 2, further comprising a polyfunctional (meth)acrylate having a molecular weight of 500 or more and containing a polyalkylene glycol moiety other than the tri(meth)acrylate represented by formula 4.

7. A polymerizable composition for optical articles as described in claim 3, further comprising a polyfunctional (meth)acrylate having a molecular weight of 500 or more and containing a polyalkylene glycol moiety other than the tri(meth)acrylate represented by formula 4.

8. A polymerizable composition for optical articles as described in claim 4, further comprising a polyfunctional (meth)acrylate having a molecular weight of 500 or more and containing a polyalkylene glycol moiety other than the tri(meth)acrylate represented by formula 4.

9. The polymerizable composition for an optical article according to any one of claims 1 to 8, which has a viscosity of 20 mPa·s or more at a temperature of 25°C.

10. A substrate; A photochromic layer obtained by curing the polymerizable composition for an optical article according to any one of claims 1 to 8; An optical article having the following:

11. The optical article according to claim 10, wherein the polymerizable composition for an optical article has a viscosity of 20 mPa·s or more at a temperature of 25°C.

12. The optical article according to claim 10, which is a spectacle lens.

13. The optical article according to claim 10, which is a lens for goggles, a visor portion of a sun visor, or a shield member for a helmet.

14. Eyeglasses comprising the eyeglass lens according to claim 12.

Images