Curable composition, cured body, laminate, optical article, lens, and spectacles

Abstract

The present disclosure provides: a curable composition capable of realizing a cured body that achieves photochromic compound performance and photochromic compound elution resistance; a cured body; a laminate; a lens; spectacles; and a photochromic optical article. A curable composition according to an embodiment includes a photochromic compound and a radically polymerizable monomer. The photochromic compound has a radically polymerizable substituent. The polymerizable monomer includes, in the amount of 50 mass% or more, a first (meth)acrylate that has a number average molecular weight of 600 or more and that comprises a polyalkylene glycol chain structure having a number average molecular weight of 250 or more and two or more (meth)acryloyl groups.

Description

Curable composition, cured product, laminate, optical article, lens, and eyeglasses

[0001] The present invention relates to a curable composition, a cured product, a laminate, an optical article, a lens, and eyeglasses.

[0002] Photochromic compounds, such as naphthopyran compounds, fulgide compounds, and spirooxazine compounds, are compounds that can reversibly convert into two isomers with different absorption spectra upon irradiation with ultraviolet light, such as sunlight or light from a mercury lamp. Photochromic compounds have the property that when a colorless, bleached compound is irradiated with ultraviolet light, it isomerizes to a colored state and returns to its original color when the light irradiation is stopped and the compound is placed in a dark place. Taking advantage of this property, they are used in a variety of applications, particularly optical materials. For example, photochromic eyeglass lenses, which are imparted with photochromic properties by the use of a photochromic compound, quickly color and function as sunglasses outdoors where they are irradiated with ultraviolet light, such as sunlight, and fade and function as transparent, ordinary eyeglasses indoors where they are not irradiated with such light. Demand for such lenses has been increasing in recent years. Photochromic eyeglass lenses can be obtained, for example, by applying a photochromic curable composition to a plastic lens by spin coating or the like, followed by photocuring to form a photochromic coating layer.

[0003] International Publication No. 2020 / 261961 International Publication No. 2021 / 172511

[0004] An object of the present invention is to provide a curable composition capable of realizing a cured product that satisfies both the performance of a photochromic compound and the resistance to elution of the photochromic compound, as well as a cured product, a laminate, a lens, eyeglasses, and a photochromic optical article.

[0005] According to the present disclosure, there is provided a curable composition. The curable composition includes a radically polymerizable photochromic compound represented by the following formula (1) and a radically polymerizable monomer. The radically polymerizable monomer includes a first (meth)acrylate having a number-average molecular weight of 600 or more and including a polyalkylene glycol chain structure having a number-average molecular weight of 250 or more and two or more (meth)acryloyl groups. The proportion of the first (meth)acrylate in the radically polymerizable monomer is 50 mass% or more.

[0006]

[0007] In formula (1), M is a substituted or unsubstituted carbon, nitrogen, silicon, or germanium, and two or more substituents may be bonded to form a ring structure.

[0008] Ring A is a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to any of these rings, and Ring A may not be present.

[0009] Ring B is a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to the above ring.

[0010] R １ and R ２ are each independently a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.

[0011] M, ring A, ring B, R １ and R ２ At least one of the groups has a radically polymerizable substituent.

[0012] According to another embodiment, a cured body is provided. The cured body is obtained by curing the curable composition according to the embodiment.

[0013] According to another embodiment, a laminate is provided, which includes an optical substrate and a cured body according to an embodiment located on a surface of the optical substrate.

[0014] According to another embodiment, an optical article is provided, the optical article including the cured body according to the embodiment.

[0015] According to another embodiment, a lens is provided, the lens comprising a cured body according to an embodiment.

[0016] According to another embodiment, a pair of eyeglasses is provided, the eyeglasses including a lens according to an embodiment.

[0017] According to the present invention, there are provided a curable composition capable of realizing a cured product having excellent photochromic compound performance and appearance, as well as a cured product, a laminate, an optical article, a lens, and eyeglasses.

[0018] The curable composition according to the embodiment includes a photochromic compound and a radically polymerizable monomer. The photochromic compound has a radically polymerizable substituent. The radically polymerizable monomer includes 50% by mass or more of a first (meth)acrylate. The first (meth)acrylate has a polyalkylene glycol chain structure having a number-average molecular weight of 250 or more and two or more (meth)acryloyl groups. The number-average molecular weight of the first (meth)acrylate is 600 or more. Use of such a curable composition enables the realization of a cured product with excellent photochromic performance and appearance. In this specification and claims, "(meth)acrylate" refers to a compound having at least one of an acryloyl group and a methacryloyl group. "(meth)acryloyl group" refers to at least one of an acryloyl group and a methacryloyl group.

[0019] First, photochromic compounds undergo structural changes (isomerization) in response to energy such as light, resulting in color development, fading, or discoloration. For such photochromic compounds to easily undergo structural changes in a polymer solid matrix, it is important that the photochromic compound be located within a soft segment in the polymer solid matrix. Polymer solid soft segments with a high proportion of soft segments can be obtained, for example, by curing a curable composition containing a high proportion of poly(meth)acrylates having polyalkylene glycol chains. However, such curable compositions tend to have lower curability than curable compositions containing a large amount of trifunctional or higher (meth)acrylates due to a low proportion of (meth)acryloyl groups that serve as crosslinking points. In particular, curable compositions containing photochromic compounds tend to have lower curability upon photocuring because the photochromic compound itself absorbs ultraviolet light. Poor curability of a curable composition not only reduces the appearance of the cured product, such as causing cloudiness on the surface of the cured product, but can also reduce photochromic performance.

[0020] Such deterioration in the photochromic performance and appearance of the cured product can occur more significantly when a resin layer having a higher hardness than the cured product is laminated on the surface of the cured product. This is thought to be due to bleed-out of the photochromic compound from the cured product. In the case of a cured product of a curable composition having a high proportion of poly(meth)acrylate having a polyalkylene glycol chain and a low proportion of tri- or higher-functional (meth)acrylate, the crosslink density in the polymer solid matrix is ​​low and the proportion of soft segments is high, resulting in low curability and the tendency for the photochromic compound to easily migrate through the polymer solid matrix. As a result, when a curable composition that forms a resin layer having a higher hardness than the cured product is applied to the surface of the cured product and cured, the photochromic compound near the surface of the cured product migrates to the hard resin layer or to the interface with that resin layer, which is thought to result in deterioration in the photochromic performance and appearance of the cured product. In the case of a cured product of a curable composition containing a large amount of tri- or higher functional (meth)acrylate, the crosslink density in the polymer solid matrix is ​​high and the proportion of soft segments is low, so the photochromic compound tends to be less likely to move in the polymer solid matrix, and it is thought that such problems are unlikely to occur. However, simply increasing the content of tri- or higher functional (meth)acrylate in the polymer solid matrix may restrict the molecular motion of the photochromic compound, making it difficult to fully exhibit the performance of the photochromic compound.

[0021] The curable composition according to the embodiment uses a photochromic compound having a radically polymerizable substituent. Therefore, the photochromic compound can be immobilized in a polymer solid matrix, suppressing bleed-out of the photochromic compound. Furthermore, the soft segment of the polymer solid matrix that immobilizes the photochromic compound uses a first (meth)acrylate having two or more (meth)acryloyl groups and a polyalkylene glycol chain structure with a number-average molecular weight of 250 or more. By setting the content of this first (meth)acrylate to 50% or more, the molecular motion of the photochromic compound is less likely to be restricted even when the photochromic compound is immobilized. Therefore, the cured product obtained by curing this curable composition can fully exhibit the performance of the photochromic compound and achieve minimal appearance defects.

[0022] Each component will be described in detail below.

[0023] <Radical Polymerizable Photochromic Compound> The radically polymerizable photochromic compound is a photochromic compound having at least one radically polymerizable substituent. The structure of the photochromic compound may be at least one selected from the group consisting of chromene compounds, fulgide compounds, fulgimide compounds, and spirooxazine compounds. The chromene compounds include compounds having a 1-benzopyran skeleton, spiropyran compounds containing a spiropyran skeleton, and naphthopyran compounds having a naphthopyran skeleton.

[0024] From the viewpoint of obtaining excellent photochromic properties, it is preferable to use the photochromic compound represented by formula (1).

[0025]

[0026] In formula (1), M, ring A, ring B, R １ and R ２ At least one selected from the group consisting of has a radically polymerizable substituent.

[0027] The photochromic compound represented by formula (1) will be described in detail below.

[0028] <Radical Polymerizable Group> The photochromic compound represented by formula (1) has at least one radically polymerizable group in the molecule. The radically polymerizable group is a functional group that can participate in a reaction by a radical, so that at least one atom of the functional group is covalently bonded to an atom of a radically polymerizable monomer. Examples of the radically polymerizable group include a functional group having an ethylenically unsaturated bond.

[0029] The number of radical polymerizable groups in the photochromic compound may be one or more per molecule. The greater the number of substituents, the easier it is for the photochromic compound to be fixed in the cured product, and the cured product's appearance tends to improve. On the other hand, the greater the number of substituents on the radical polymerizable groups, the easier it is for the photochromic compound to be fixed as a crosslinking agent in the cured product, and the photochromic performance tends to be more easily reduced. From the viewpoint of the appearance and photochromic properties of the resulting cured product, the number of radical polymerizable groups is preferably 1 to 3, more preferably 1 to 2, and most preferably 1.

[0030] The radical polymerizable group is preferably a substituent represented by the following formula (X4).

[0031] L １ -PG (X4) In formula (X4), PG is a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a 1-chlorovinyl group, an allyl group, a styryl group, a (meth)acryloyl group, a 2-(meth)acryloxyethylcarbamyl group, a 2-(meth)acryloxyethoxycarbonyl group, and a crotyl group, and the (meth)acryloyl group, the 2-(meth)acryloxyethylcarbamyl group, and the 2-(meth)acryloxyethoxycarbonyl group are preferred.

[0032] In formula (X4), L １ is a group represented by the following formula (X2).

[0033]

[0034] In formula (X2), J is a divalent group. Each of the plurality of Js independently represents a direct bond, a substituted or unsubstituted methylene group, an oxygen atom, a sulfur atom, or an NR ３０１ It is. ３０１ is a hydrogen atom or an alkyl group. ３０１ is preferably an alkyl group having 1 to 20 carbon atoms. L is an oxygen atom or a sulfur atom.

[0035] R ３００ is an alkylene group or a silylene group having an alkyl group or an aryl group as a substituent. ３００ is preferably an alkylene group having 1 to 6 carbon atoms or a silylene group having an alkyl group having 1 to 6 carbon atoms as a substituent.

[0036] R ３０２ , R ３０３ , and R ３０４ are each independently an alkylene group. ３０２ is preferably an alkylene group having 1 to 6 carbon atoms. ３０３ is preferably an alkylene group having 1 to 6 carbon atoms. ３０４ is preferably an alkylene group having 1 to 6 carbon atoms.

[0037] h, j, k and l each independently represent 0 or 1.

[0038] "i" is an integer of 0 to 200. When "i" is 2 or more, the structures of the groups to which multiple "i"s are attached may be the same or different. "i" is preferably a number in the range of 1 to 100, more preferably 1 to 50, and most preferably 1 to 20.

[0039] The dashed line represents the bond to PG.

[0040] Particularly preferred groups of formula (X2) are represented by the following formula:

[0041]

[0042] <M> In formula (1), M is substituted or unsubstituted carbon, nitrogen, silicon, or germanium.

[0043] When M has two or more substituents, these substituents may be bonded to form a ring structure.

[0044] M is preferably a substituted or unsubstituted carbon atom.

[0045] <Ring A> In formula (1), ring A is a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to the above ring. Ring A is not essential and may not be present. Examples of aromatic hydrocarbon rings include a benzene ring and a cyclotetradecaheptaene ring.

[0046] Examples of the aromatic heterocycle include a furan ring, a thiophene ring, and a pyridine ring.

[0047] Examples of the fused polycyclic ring include a naphthalene ring, a fluorene ring, an anthracene ring, a phenanthrene ring, a tetracene ring, a pentacene ring, a benzopyrene ring, a chrysene ring, a pyrene ring, a triphenylene ring, a perylene ring, a benzofuran ring, a benzothiophene ring, a quinoline ring, an isoquinoline ring, an indole ring, a pyrimidine ring, a quinazoline ring, a pyridazine ring, a cinnoline ring, a phthalazine ring, a 1,2,3-, 1,2,4-, or 1,3,5-triazine ring, a carbazole ring, a benzoxazole ring, and an isothiazole ring.

[0048] Among these, a benzene ring, a naphthalene ring, a fluorene ring, a phenanthrene ring, a pyrene ring, a furan ring, a thiophene ring, and a pyridine ring are preferred, a benzene ring, a naphthalene ring, a fluorene ring, and a phenanthrene ring are more preferred, and a benzene ring is most preferred.

[0049] <Ring B> In formula (1), ring B is a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to the above ring. Suitable ring B has the same meaning as that exemplified for ring A.

[0050] <R １ and R ２ In formula (1), R １ and R２ are each independently an aryl group which may have a substituent, or a heteroaryl group which may have a substituent.

[0051] R １ and R ２ are each independently preferably a phenyl group which may have a substituent, a 1-naphthyl group which may have a substituent, a 2-naphthyl group which may have a substituent, a thienyl group which may have a substituent, a furyl group which may have a substituent, a pyrrolinyl group which may have a substituent, a pyridyl group which may have a substituent, a benzothienyl group which may have a substituent, a benzofuranyl group which may have a substituent, or a benzopyrrolinyl group which may have a substituent. １ and R ２ Preferably, at least one of R is a phenyl group which may have a substituent, １ and R ２ More preferably, both are substituted phenyl groups.

[0052] <Suitable radically polymerizable photochromic compound> The radically polymerizable photochromic compound is preferably a photochromic compound represented by the following formula (2): ３ , R ４ , R ５ , R ６ , R ７ , and R ８ At least one selected from the group consisting of: is a group represented by formula (X4).

[0053]

[0054] (R ３ , R ４ , R ５ , R ６ , R ７ , and R ８ ) R ３ , R ４ , R ５ , R ６ , R ７ , and R ８each independently represents a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted haloalkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a cyano group, a halogen atom, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a nitro group, a formyl group, a hydroxycarbonyl group, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aralkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a thiol group, a substituted or unsubstituted alkoxyalkylthio group, a haloalkylthio group, a substituted or unsubstituted cycloalkylthio group, a substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, a group represented by the following formula (2a), a group represented by the following formula (X), or a group represented by the following formula (X3):

[0055] (Group represented by formula (2a)) -Q １００ - (P １００ Q ２００ ) ａａ -P ２００ Q ３００ (2a)

[0056] In formula (2a), Q １００ is an alkylene group which may contain a halogen atom as a substituent. １００ may be a linear alkylene group or a branched alkylene group. １００ is preferably a linear alkylene group.

[0057] Q １００ The alkylene group preferably has 1 or more and 20 or less carbon atoms, more preferably 1 or more and 15 or less carbon atoms, even more preferably 1 or more and 9 or less carbon atoms, and most preferably 2 or more and 6 or less carbon atoms.

[0058] Q １００The halogen atom contained in may be at least one selected from the group consisting of I, Cl, Br, and F. The halogen atom is preferably at least one of Cl and F, and more preferably F.

[0059] Q ２００ is an alkylene group which may contain a halogen atom as a substituent. ２００ is an alkylene group or a haloalkylene group, and the preferred embodiment of the number of carbon atoms and halogen atoms in the alkylene group is １００ It is the same as: ２００ The number of carbon atoms in the alkylene group is １００ The number of carbon atoms in the alkylene group may be the same as or different from that of the alkylene group in the alkylene group.

[0060] Q ３００ is an alkyl group which may contain a halogen atom as a substituent. ３００ is an alkyl group or a haloalkyl group, and the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 12, even more preferably 1 to 7, and most preferably 1 to 3. ３００ may be a linear alkyl group or a branched alkyl group, and Q ３００ is preferably a linear alkyl group.

[0061] Q ３００ When the halogen atom is a haloalkyl group, the halogen atom can be at least one selected from the group consisting of I, Cl, Br, and F. The halogen atom is preferably at least one of Cl and F, and more preferably F.

[0062] P １００ , and P ２００ are each independently O, S, or NR ７００ , P.R. ７０１ , or P(=O).

[0063] P １００ , and P ２００ is O, S or NR ７００ is preferred, O or S is more preferred, and O is most preferred.

[0064] R ７００ , and R ７０１ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

[0065] R ７００ is preferably a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. Preferred alkyl groups are methyl, ethyl, propyl, butyl, and pentyl. Preferred aryl groups are phenyl and naphthyl.

[0066] R ７０１ R is a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent. ７０１ is preferably a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. Preferred alkyl groups are methyl, ethyl, propyl, butyl, and pentyl. Preferred aryl groups are phenyl and naphthyl.

[0067] aa is 0 or 1 or more and 10 or less, preferably 0 or 1 or more and 5 or less, more preferably 0 or 1 or more and 3 or less, and particularly preferably 0 or 1 or more and 2 or less.

[0068] Specific examples of formula (2a) include -CH ２ OCH ３ , -CH ２ SCH ３ , -CH ２ CH ２ OCH ３ , -CH ２ CH ２ OCH ２ CH ３ , -CH ２ CH ２ SCH ３ , -CH ２ CH ２ CH ２ OCH ３ , -CH ２ CH２ CH ２ SCH ３、 -CH ２ CH ２ OCH ２ CH ２ OCH ３ ,-CH ２ CH ２ OCH ２ CH ２ OCH ２ CH ３ ,-CH ２ CH ２ OCH ２ CH ２ OCH ２ CH ２ OCH[[ID=4​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​

[0072] In formula (X), E is an oxygen atom or NR １０１ It is. １０１ is a hydrogen atom or an alkyl group. １０１ and R １０１ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0073] F is an oxygen atom or a sulfur atom, and preferably an oxygen atom.

[0074] G is an oxygen atom, a sulfur atom, or NR ２０２ It is. ２０２ is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group. ２０２ and R ２０２ is preferably a hydrogen atom, that is, G is preferably NH.

[0075] g is 0 or 1.

[0076] R ２０１ is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group. When G is an oxygen atom or a sulfur atom, R ２０１ is a group other than a hydrogen atom. ２０１ is preferably an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

[0077] Suitable groups of formula (X) are as follows:

[0078]

[0079] <Group represented by formula (X3)> L １ -R ４００ (X3) In formula (X3), L １ has the same meaning as formula (X4).

[0080] R ４００is a hydrogen atom, an alkyl group, an aryl group, a photochromic group, or a silyl group having an alkyl group, an alkoxy group, or an aryl group as a substituent. The photochromic group is a group containing a photochromic moiety. Representative examples of the photochromic group include naphthopyran, spirooxazine, spiropyran, fulgide, fulgimide, and diarylethene. In terms of being able to exhibit excellent photochromic properties, indenonaphthopyran is preferred, and among these, indeno[2,1-f]naphtho[1,2-b]pyran is particularly preferred.

[0081] The indeno[2,1-f]naphtho[1,2-b]pyran is preferably a group represented by the following formula (X5).

[0082]

[0083] In formula (X5), R ４０１ , R ４０２ , R ４０３ and R ４０４ are each independently the R ３ The group may be the same as the group used in

[0084] R ４０５ and R ４０６ are each independently a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. ４０５ and R ４０６ is the above-mentioned R １ and R ２ The substituents on the aryl group or heteroaryl group may be the same as those used in the above-mentioned R ３ The group may be the same as the group used in

[0085] o is an integer of 0 to 4. n is an integer of 0 to 4. When o is 2 to 4, a plurality of R ４０３ may be the same or different. When n is 2 or more and 4 or less, a plurality of R ４０４ may be the same or different from each other.

[0086] R ４０１ , R ４０２ , R４０３ , R ４０４ , and R ４０５ At least one of the substituents on the aryl or heteroaryl group of L １ and combine.

[0087] R ３ and R ４ may together with the carbon atom to which they are bonded form a substituted or unsubstituted aliphatic ring having 3 to 20 ring carbon atoms, a substituted or unsubstituted fused polycyclic ring in which an aromatic hydrocarbon ring or an aromatic heterocycle is fused to the aliphatic ring, a substituted or unsubstituted heterocycle having 3 to 20 ring atoms, or a substituted or unsubstituted fused polycyclic ring in which an aromatic ring or an aromatic heterocycle is fused to a heterocycle.

[0088] It is preferable that the ring be a substituted or unsubstituted aliphatic ring having 3 to 20 ring atoms, a substituted or unsubstituted fused polycyclic ring in which an aromatic hydrocarbon ring or an aromatic heterocycle is fused to an aliphatic ring, or a substituted or unsubstituted heterocyclic ring having 3 to 20 ring atoms. It is more preferable that the ring be formed together with the carbon atom at position 13, into a ring selected from a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cycloundecane ring, a cyclododecane ring, and a spirodicyclohexane ring. Furthermore, the ring may have 1 to 10 substituents, which may be alkyl groups having 1 to 5 carbon atoms or cycloalkyl groups having 5 to 7 carbon atoms, or may be fused with cycloalkyl groups having 5 to 7 carbon atoms. Specifically, it is more preferable that the ring be formed as shown below.

[0089]

[0090] In formula (2), a100 is an integer of 1 or more and 4 or less. When a100 is 2 or more and 4 or less, a plurality of R ５ may be the same or different. a100 is 2 or more and 4 or less, and adjacent R ５ If there is a ５ is R ５and the carbon atom bonded thereto may form a substituted or unsubstituted aliphatic ring, a substituted or unsubstituted aliphatic heterocycle, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to any of these rings. ５ The combinations are the 5th and 6th positions, the 6th and 7th positions, or the 7th and 8th positions of the naphthopyran skeleton.

[0091] a101 is an integer of 1 to 4. When a101 is an integer of 2 to 4, a plurality of R ６ may be the same or different from each other. ６ If there is a ６ is R ６ and the carbon atom bonded thereto may form a substituted or unsubstituted aliphatic ring, a substituted or unsubstituted aliphatic heterocycle, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to any of these rings. ６ The combinations are the 9th and 10th positions, the 10th and 11th positions, or the 11th and 12th positions of the naphthopyran skeleton.

[0092] a102 is an integer of 1 to 5. When a102 is an integer of 2 to 5, a plurality of R ７ may be the same or different from each other. ７ If there is a ７ is R ７ and the carbon atom bonded to the ring may form a substituted or unsubstituted aliphatic ring, a substituted or unsubstituted aliphatic heterocycle, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to any of these rings.

[0093] a103 is an integer of 1 to 5. When a103 is 2 or more and 4 or less, a plurality of R ８ may be the same or different from each other.８ If there is a ８ is R ８ and the carbon atom bonded to the ring may form a substituted or unsubstituted aliphatic ring, a substituted or unsubstituted aliphatic heterocycle, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to any of these rings.

[0094] R ５ , R ６ , R ７ , and R ８ may form a ring having 5 to 8 atoms, including the carbon atom to which is bonded. The ring may have a substituent, and examples of the substituent include a substituent selected from a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an amino group, a substituted amino group, a heterocyclic group having 3 to 8 atoms, a cyano group, a nitro group, and a halogen atom. Specific examples of these substituents that can be suitably used include the substituents described below.

[0095] Suitable rings include those represented by the following formula (X6).

[0096]

[0097] In formula (X6), Q and T each independently represent a sulfur atom, a substituted or unsubstituted methylene group, an oxygen atom, or NR ３０７ R ３０７ represents a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a group represented by formula (2a). N represents a nitrogen atom.

[0098] R ３０５ and R ３０６are each independently a hydroxy group, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, an amino group, a substituted amino group, a substituted or unsubstituted heterocyclic group, a cyano group, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a halogen atom, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aralkoxy group, a substituted or unsubstituted aryl group, a thiol group, an alkylthio group, an alkoxyalkylthio group, a haloalkylthio group, a cycloalkylthio group, or a substituted or unsubstituted arylthio group.

[0099] Also, R ３０５ and R ３０６ may form a substituted or unsubstituted aliphatic ring together with the carbon atom to which they are bonded. Specific examples of the aliphatic ring include a cyclopentane ring and a cyclohexane ring. Furthermore, in the aliphatic ring, 1 to 8 hydrogen atoms, and particularly preferably 1 to 4 hydrogen atoms, may be substituted with at least one group selected from the group consisting of a hydroxyl group, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, an amino group, a substituted amino group, a heterocyclic group, a cyano group, a nitro group, and a halogen atom. Specific examples of these substituents will be described later. In formula (X6), m is an integer of 1 to 4.

[0100] (Suitable R ３ , R ４ , R ５ , R ６ , R ７ , and R ８ Specific example of R ３ , R ４ , R ５ , R ６ , R ７ , and R ８ are the above-mentioned groups, the alkyl group is preferably an unsubstituted alkyl group having 1 to 20 carbon atoms, more preferably an unsubstituted alkyl group having 1 to 10 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.

[0101] The haloalkyl group is preferably a haloalkyl group having 1 to 20 carbon atoms. The number of halogen atoms is preferably 1 to 20, and more preferably 2 to 10. The haloalkyl group having 1 to 20 carbon atoms is preferably an alkyl group substituted with a fluorine atom, a chlorine atom, or a bromine atom. The haloalkyl group preferably has a perfluoromethyl group at the terminal. Suitable examples of the haloalkyl group include a trifluoromethyl group, a trifluoroethyl group, a trifluoropropyl group, a tetrafluoroethyl group, a chloromethyl group, a 2-chloroethyl group, and a bromomethyl group.

[0102] The cycloalkyl group is preferably a cycloalkyl group having 3 to 10 carbon atoms (a cycloalkyl group having 3 to 8 carbon atoms forming a ring). Examples of the cycloalkyl group having 3 to 10 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

[0103] The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms. Examples of suitable alkoxy groups having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a tert-butoxy group.

[0104] The haloalkoxy group is preferably a haloalkoxy group having 1 to 20 carbon atoms. The number of halogen atoms is preferably 1 to 20, and more preferably 2 to 10. The haloalkoxy group having 1 to 20 carbon atoms is preferably an alkoxy group substituted with a fluorine atom, a chlorine atom, or a bromine atom. The haloalkoxy group preferably has a perfluoromethyl group at the terminal. Suitable examples of the haloalkoxy group include a trifluoromethoxy group, a trifluoroethoxy group, a trifluoropropoxy group, and a tetrafluoroethoxy group.

[0105] The amino group is a primary amino group (—NH ２) or a secondary or tertiary amino group in which one or two hydrogen atoms have been substituted. The amino group may be a group represented by the above formula (2a). Examples of the substituent on the substituted amino group include an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, an aryl group having 6 to 14 carbon atoms, and a heteroaryl group having 4 to 14 carbon atoms. Examples of suitable amino groups include an amino group, a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a methylphenylamino group, and a diphenylamino group.

[0106] The heterocyclic group is preferably a heterocyclic group having 3 to 10 atoms. The heteroatom of the heterocyclic group is preferably at least one selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom. The number of heteroatoms is, for example, 1 to 5, preferably 1 or 2. Specific examples include aliphatic heterocyclic groups such as a morpholino group, a piperidino group, a pyrrolidinyl group, a piperazino group, and an N-methylpiperazino group, and aromatic heterocyclic groups such as an indolinyl group. The heterocyclic group may be a 2,6-dimethylmorpholino group, a 2,6-dimethylpiperidino group, or a 2,2,6,6-tetramethylpiperidino group.

[0107] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred.

[0108] The alkylthio group is preferably an alkylthio group having 1 to 6 carbon atoms. Examples of the alkylthio group having 1 to 6 carbon atoms include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, a sec-butylthio group, and a t-butylthio group.

[0109] The arylthio group is preferably an arylthio group having 6 to 10 carbon atoms. Examples of the arylthio group having 6 to 10 carbon atoms include a phenylthio group, a 1-naphthylthio group, and a 2-naphthylthio group.

[0110] The alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 7 carbon atoms. Examples of the alkylcarbonyl group having 2 to 7 carbon atoms include an acetyl group and an ethylcarbonyl group.

[0111] The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 7 carbon atoms. Examples of the alkoxycarbonyl group having 2 to 7 carbon atoms include a methoxycarbonyl group and an ethoxycarbonyl group.

[0112] The aralkyl group is preferably an aralkyl group having a carbon number of 7 to 11. Examples of the aralkyl group having a carbon number of 7 to 11 include a benzyl group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group, and a naphthylmethyl group.

[0113] The aralkoxy group is preferably an aralkoxy group having 7 to 11 carbon atoms. Examples of the aralkoxy group having 7 to 11 carbon atoms include a benzyloxy group and a naphthylmethoxy group.

[0114] The aryloxy group is preferably an aryloxy group having 6 to 12 carbon atoms. Examples of the aryloxy group having 6 to 12 carbon atoms include a phenyloxy group and a naphthyloxy group.

[0115] The aryl group is not particularly limited, but is preferably an aryl group having 5 to 12 carbon atoms. Examples of the aryl group having 5 to 12 carbon atoms include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

[0116] The heteroaryl group is not particularly limited, but is preferably a heteroaryl group having 3 to 12 carbon atoms. Examples of heteroatoms include at least one selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom. The number of heteroatoms in the substituted or unsubstituted heteroaryl group is, for example, 1 to 3, preferably 1 or 2. The number of carbon atoms in the substituted or unsubstituted heteroaryl group is, for example, 4 to 11, preferably 5 to 9. Examples of heteroaryl groups having 3 to 12 carbon atoms include a thienyl group, a furyl group, a pyrrolinyl group, a pyridyl group, a benzothienyl group, a benzofuranyl group, and a benzopyrrolinyl group.

[0117] The alkoxyalkylthio group is preferably an alkoxyalkylthio group having 2 to 9 carbon atoms. Examples of the alkoxyalkylthio group having 2 to 9 carbon atoms include a methoxymethylthio group, a methoxyethylthio group, a methoxy n-propylthio group, a methoxy n-butylthio group, an ethoxyethylthio group, and an n-propoxypropylthio group.

[0118] The haloalkylthio group is preferably a haloalkylthio group having 1 to 6 carbon atoms. Examples of the haloalkylthio group having 1 to 6 carbon atoms include a trifluoromethylthio group, a tetrafluoroethylthio group, a chloromethylthio group, a 2-chloroethylthio group, and a bromomethylthio group.

[0119] The cycloalkylthio group is preferably a cycloalkylthio group having 3 to 8 carbon atoms. Examples of the cycloalkylthio group having 3 to 8 carbon atoms include a cyclopropylthio group, a cyclobutylthio group, a cyclopentylthio group, and a cyclohexylthio group.

[0120] The silyl group may have a substituent. The substituent of the substituted silyl group is not particularly limited, but examples thereof include an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, an aryl group having 6 to 14 carbon atoms, and a heteroaryl group having 4 to 14 carbon atoms.

[0121] The oxysilyl group may have a substituent. The substituent of the substituted oxysilyl group is not particularly limited, and examples thereof include an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, an aryl group having 6 to 14 carbon atoms, and a heteroaryl group having 4 to 14 carbon atoms.

[0122] The cycloalkyl group, the arylthio group, the aralkyl group, the aralkoxy group, the aryloxy group, the aryl group, the heteroaryl group, and the cycloalkylthio group may be unsubstituted. However, when they have a substituent, it is preferred that 1 to 8 hydrogen atoms, particularly preferably 1 to 4 hydrogen atoms, in the group forming the ring are substituted with a substituent selected from a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an amino group, a substituted amino group, a heterocyclic group having 3 to 8 atoms, a cyano group, a nitro group, and a halogen atom.

[0123] <Particularly Suitable Photochromic Compounds> Among the photochromic compounds represented by formula (2), from the viewpoint of excellent performance of the photochromic compound, R ５ , R ６ , R ７ , and R ８ At least one selected from the group consisting of is preferably a group represented by formula (X4), and R ７ is more preferably a group represented by formula (X4).

[0124] The photochromic compound represented by formula (2) is R ７ is a group represented by formula (X4), R ３ , and R ４ are each independently any one of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, and a group represented by formula (2a), or R ３ , and R ４and more preferably form, together with the carbon atom to which they are bonded, any one of a substituted or unsubstituted aliphatic ring having 3 to 20 ring carbon atoms, a substituted or unsubstituted condensed polycyclic ring in which an aromatic hydrocarbon ring or an aromatic heterocycle is condensed to an aliphatic ring, a substituted or unsubstituted heterocycle having 3 to 20 ring atoms, and a substituted or unsubstituted condensed polycyclic ring in which an aromatic ring or an aromatic heterocycle is condensed to a heterocycle. ３ , and R ４ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, or a group represented by formula (2a), and R ３ , and R ４ It is particularly preferable that the structures of the

[0125] Specific examples of suitable photochromic compounds include the following structures:

[0126]

[0127]

[0128] <(A) Radically Polymerizable Monomer> The radically polymerizable monomer (A) includes (A-1) a first (meth)acrylate having a number-average molecular weight of 600 or more and having a polyalkylene glycol chain structure with a number-average molecular weight of 250 or more and two or more (meth)acryloyl groups. Hereinafter, the first (meth)acrylate will also be referred to as component (A-1). The radically polymerizable monomer (A) will also be referred to as component (A). The radically polymerizable monomer (A) may include other radically polymerizable monomers depending on the desired properties of the cured product.

[0129] <(A-1) First (meth)acrylate> The first (meth)acrylate has two or more (meth)acryloyl groups. The number of (meth)acryloyl groups may be 2, 3, 4, 5, 6, 7, or 8. From the viewpoint of enhancing the photochromic properties of the cured body and improving the appearance, the number of (meth)acryloyl groups is preferably 2, 3, 4, 5, or 6, and the number of (meth)acryloyl groups is particularly preferably 2, 3, or 4. The higher the ratio of the number of methacryloyl groups to the number of (meth)acryloyl groups in the first (meth)acrylate, the more likely it is that deterioration of the photochromic compound will be suppressed and the photochromic properties of the cured body will be enhanced. The ratio of the methacryloyl groups in the first (meth)acrylate is preferably 30% or more, more preferably 50% or more, and even more preferably 80% or more, and it is particularly preferred that all of the (meth)acryloyl groups are methacryloyl groups.

[0130] The first (meth)acrylate contains a polyalkylene glycol chain having a number-average molecular weight of 250 or more. The use of such a component (A-1) tends to enhance the photochromic properties of the cured product. The number of carbon atoms in the alkylene glycol chain is preferably 1 or more and 10 or less, and more preferably 2 or more and 5 or less. The proportion N2 / N1 of the number-average molecular weight N1 of the component (A-1) accounted for by the number-average molecular weight N2 of the polyalkylene glycol chain is preferably 50% or more, more preferably 60% or more, and even more preferably 80% or more. This proportion may be 95% or less, or may be 90% or less. The number-average molecular weight N2 of the polyalkylene glycol chain can be measured using an NMR (nuclear magnetic resonance) spectrometer.

[0131] From the viewpoint of enhancing the functionality of the cured product, the number average molecular weight N2 of the polyalkylene glycol chain of the component (A-1) is preferably at least 290, more preferably at least 350, more preferably at least 650, and even more preferably at least 800. From the viewpoint of enhancing the handleability and coatability of the curable composition, the number average molecular weight N2 of the polyalkylene glycol chain of the component (A-1) is preferably at most 3000, more preferably at most 2500, more preferably at most 2000, and even more preferably at most 1650.

[0132] The first (meth)acrylate may contain at least one structure selected from the group consisting of an ester bond, a urethane bond, a urea bond, a carbonate bond, and a carbonyl group. The first (meth)acrylate preferably does not contain at least one structure selected from the group consisting of an ester bond, a urethane bond, a urea bond, a carbonate bond, and a carbonyl group.

[0133] The number-average molecular weight N1 of the first (meth)acrylate is 600 or more. The number-average molecular weight N1 of the component (A-1) can be measured, for example, by gel permeation chromatography (GPC). From the viewpoint of enhancing the functionality of the cured product, the number-average molecular weight of the first (meth)acrylate is preferably 650 or more, more preferably 850 or more, more preferably 1000 or more, and even more preferably 1100 or more. On the other hand, if the number-average molecular weight N1 of the first (meth)acrylate is excessively high, the fluidity of the first (meth)acrylate may decrease, which may result in deterioration in handling and coating properties. Furthermore, reactivity with the radically polymerizable photochromic compound may also tend to decrease. From this viewpoint, the number-average molecular weight N1 of the first (meth)acrylate is preferably 6000 or less, more preferably 3500 or less, and even more preferably 2500 or less. The number-average molecular weight N1 of the component (A-1) may be 650 or more and 3500 or less, or may be 850 or more and 2500 or less.

[0134] In terms of enhancing the photochromic properties of the cured product, the proportion of the first (meth)acrylate in the radical polymerizable monomer (A) is more preferably 60% by mass or more, even more preferably 70% by mass or more, and particularly preferably 75% by mass or more. If the proportion of the first (meth)acrylate in the radical polymerizable monomer (A) is high, the appearance of the cured product may be reduced. Furthermore, the reactivity with the radical polymerizable photochromic compound may also be reduced. From this perspective, the proportion of the first (meth)acrylate is preferably 99% by mass or less, more preferably 96% by mass or less, and even more preferably 90% by mass or less. The proportion of the first (meth)acrylate may be 55% by mass or more and 95% by mass or less, 65% by mass or more and 90% by mass or less, or 70% by mass or more and 80% by mass or less. This proportion can be confirmed, for example, by measuring the mass of the first (meth)acrylate separated by silica gel column chromatography.

[0135] The first (meth)acrylate is preferably an acyclic (meth)acrylate that does not contain a cyclic structure such as an aromatic ring or an aliphatic ring. Use of such a first (meth)acrylate tends to further enhance the photochromic properties of the cured product.

[0136] The first (meth)acrylate preferably includes at least one selected from the group consisting of a di(meth)acrylate represented by the following formula (3) and a (meth)acrylate represented by the following formula (4).

[0137] (First (meth)acrylate represented by formula (3)) When the first (meth)acrylate has two (meth)acryloyl groups, it preferably contains a first (meth)acrylate represented by the following formula (3):

[0138]

[0139] In formula (3), Q ３ and Q ６are each independently a hydrogen atom or a methyl group. That is, the first (meth)acrylate represented by formula (3) may be a diacrylate, a dimethacrylate, or a methacrylate acrylate. ３ and Q ６ is preferably a methyl group. ４ and Q ５ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ４ and Q ５ are each independently preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

[0140] a and b each independently represent 0 or more and 10 or less, preferably 0 or more and 5 or less, more preferably 0 or more and 3 or less, and particularly preferably 0 or more and 2 or less.

[0141] Z 1 and Z ２ are each independently 0 or 1, and Z 1 and Z ２ is preferably 0.

[0142] Q ７ is a divalent group having a number average molecular weight of 600 or more and represented by the following formula (3a):

[0143]

[0144] Q ７ａ , Q ７ｂ , Q ７ｄ , and Q ７ｅ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ７ａ , Q ７ｂ , Q ７ｄ , and Q ７ｅ are each independently preferably a hydrogen atom or a methyl group. ７ａ and Q ７ｂ are different groups. ７ｄ and Q ７ｅ are different groups. ７ａ and Q ７ｅ may be the same group. ７ｂ and Q ７ｄmay be the same group.

[0145] Q ７ｃ represents a linear or branched alkylene group having 2 to 10 carbon atoms which may have a substituent, and f1 is 3 or more and 100 or less.

[0146] Repeating unit -(OQ ７ｃ )- is a first alkylene oxide unit. The polymer portion formed by this repeating unit can form the soft segment of the cured product. ７ｃ is preferably a linear alkylene group. The number of carbon atoms in the alkylene group is preferably 3 to 10, more preferably 3 to 6, and particularly preferably 3 to 4. The greater the number of carbon atoms in the alkylene group, the greater the photochromic properties of the cured product. On the other hand, if the number of carbon atoms in the alkylene group is too large, the amount of soft segments per unit mass decreases, which may result in a decrease in the photochromic properties of the cured product.

[0147] From the viewpoint of achieving both photochromic properties and appearance, f1 is preferably from 6 to 85, more preferably from 7 to 60, even more preferably from 8 to 45, and particularly preferably from 9 to 30. d1 and h1 are from 0 to 10. From the viewpoint of achieving both photochromic properties and appearance, d1 and h1 are preferably from 0 to 5, more preferably from 0 to 2, even more preferably 0 or 1, and most preferably 0.

[0148] e1 and g1 are 0 or more and 20 or less. From the viewpoint of achieving both photochromic properties and appearance, e1 and g1 are preferably 0 or more and 15 or less, more preferably 0 or more and 10 or less, even more preferably 0 or more and 5 or less, and particularly preferably 0.

[0149] In other words, the (meth)acrylate represented by formula (3) may be a monomer further comprising at least one of a second alkylene oxide unit which is a repeating unit having e1 and g1 attached thereto, and a third alkylene oxide unit which is a repeating unit having d1 and h1 attached thereto.

[0150] The (meth)acrylate represented by formula (3) is1 and Z ２ is preferably 0. Such a compound is represented by the following formula (3b).

[0151]

[0152] In the above formula (3b), Q ３ , and Q ６ are each independently a hydrogen atom or a methyl group. ７ａ , Q ７ｂ , Q ７ｃ , Q ７ｄ , Q ７ｅ , d1, e1, f1, g1, and h1 have the same meanings as in formula (3a).

[0153] In the di(meth)acrylate represented by formula (3b), d1, e1, g1, and h1 are preferably 0, i.e., the di(meth)acrylate represented by formula (3b) contains only a first alkylene oxide unit. When such a di(meth)acrylate represented by formula (3b) is used, the appearance of the cured body tends to be improved. In the di(meth)acrylate represented by formula (3b) containing only a first alkylene oxide unit, f1 may be 6 or more and 85 or less, or 9 or more and 30 or less. Such a compound is, for example, represented by the following formula (3c):

[0154]

[0155] In the above formula (3c), Q ３ , Q ６ , Q ７ｃ , and f1 have the same meaning as in formula (3b).

[0156] Specific examples of the compound represented by the above formula (3c) include polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytrimethylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, polypentamethylene glycol di(meth)acrylate, and polyhexamethylene glycol di(meth)acrylate.

[0157] When a di(meth)acrylate represented by formula (3b) in which d1 and h1 are 0 and e1 and g1 are 1 or more is used, i.e., a di(meth)acrylate represented by formula (3b) further containing a second alkylene oxide unit, a cured product with high photochromic properties tends to be obtained. In the di(meth)acrylate represented by formula (3b) further containing a second alkylene oxide unit, b1 and d1 may be 2 or more and 15 or less, or 4 or more and 10 or less.

[0158] Specific examples of such di(meth)acrylates represented by formula (3b) are as follows:

[0159]

[0160]

[0161]

[0162]

[0163] The di(meth)acrylate represented by formula (3b) may be a monomer in which d1, e1, g1, and h1 are 1 or more, i.e., further including both a second alkylene oxide unit and a third alkylene oxide unit, wherein the second alkylene oxide unit and the third alkylene oxide unit have different structures.

[0164] Specific examples of such di(meth)acrylates represented by formula (3b) are as follows:

[0165]

[0166]

[0167] The di(meth)acrylate represented by formula (3) can be produced, for example, by the following method: First, an isocyanate compound represented by the following formula (3e) is prepared. This compound contains one isocyanate group and one (meth)acryloyl group.

[0168]

[0169] In formula (3e), Q５ , Q ６ , and b have the same meanings as in formula (3).

[0170] The di(meth)acrylate represented by formula (3) is obtained by reacting the isocyanate compound represented by formula (3e) with the polyol compound represented by the following formula (3d). The di(meth)acrylate represented by formula (3) obtained by the above reaction has a structure in which Q ６ and Q ３ The structure of Q is the same as ５ and Q ４ The structures of the compounds are the same, and a and b are the same. This reaction may be carried out in the presence of a solvent. Examples of the solvent that can be used include acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, cyclohexanone, dioxane, toluene, hexane, heptane, ethyl acetate, butyl acetate, dimethylformamide, and tetrahydrofuran.

[0171]

[0172] Q of the polyol compound of formula (3d) ７ａ , Q ７ｂ , Q ７ｃ , Q ７ｄ , Q ７ｅ , d1, e1, f1, g1, and h1 have the same meanings as in formula (3b). The polyol compound may be derived from plants or petroleum. In formula (3), Z １ , and Z ２ When is 0, that is, the di(meth)acrylate represented by formula (3b) can be produced, for example, by the following method.

[0173] The diacrylate represented by formula (3b) having an acryloyl group can be synthesized by esterification of a polyol compound represented by formula (3d) with acrylic acid.

[0174] Specifically, the polyol compound and acrylic acid dissolved in a solvent such as toluene are stirred in the presence of a mineral acid such as sulfuric acid or hydrochloric acid, an organic acid such as an aromatic sulfonic acid, or a Lewis acid such as boron fluoride ether, while heating as necessary, and the resulting water is removed by azeotropy to cause the reaction. Examples of methods for removing water in the esterification reaction include a method using a drying agent such as anhydrous magnesium sulfate or molecular sieves, and a method in which water is removed in the presence of a dehydrating agent typified by dicyclohexylcarbodiimide.

[0175] Alternatively, the compound can be synthesized by esterification using an acrylic acid halide. Specifically, the polyol compound and acrylic acid dissolved in an ether solvent such as tetrahydrofuran are stirred in the presence of a base such as pyridine or dimethylaniline, with heating as necessary, and the resulting hydrogen halide is removed.

[0176] Furthermore, it can also be synthesized by a transesterification reaction with an ester compound such as acrylic anhydride or methyl acrylate. Specifically, a method can be employed in which the polyol compound and acrylic acid are dissolved in a solvent such as toluene in the presence of an acidic catalyst such as an aromatic sulfonic acid or a basic catalyst such as sodium acetate or pyridine, and then stirred while heating as necessary.

[0177] The compound represented by formula (3b) having a methacryloyl group can be synthesized in the same manner as above, for example, by using methacrylic acid instead of acrylic acid.

[0178] Among the above polyol compounds, a polyol compound in which d1 and h1 are 0 and e1 and g1 are 1 or more, that is, a polyol having a second alkylene oxide unit, can be synthesized, for example, by the following method.

[0179] H-(OQ ７ｃ ) ｆ１A polyol having a second alkylene oxide unit can be synthesized by reacting —OH with a cyclic ether compound such as ethylene oxide or propylene oxide. The polyol compound having a second alkylene oxide unit can be synthesized, for example, by carrying out the reaction in a nitrogen-substituted autoclave at high temperature and pressure in the presence of a catalyst such as an alkali metal hydroxide, e.g., potassium hydroxide.

[0180] Among the above polyol compounds, a polyol compound in which d1, e1, g1, and h1 are 1 or more, i.e., a di(meth)acrylate represented by formula (3b) further containing second and third alkylene oxide units, can be synthesized, for example, by the following method.

[0181] A polyol compound having a second alkylene oxide unit is reacted with a cyclic ether compound to synthesize a polyol compound having a third alkylene oxide unit, and the resulting polyol compound further having a third alkylene oxide unit is reacted with acrylic acid or methacrylic acid in the same manner as described above to synthesize a di(meth)acrylate represented by formula (3b) further containing second and third alkylene oxide units.

[0182] (First (meth)acrylate represented by formula (4)) When the first (meth)acrylate has three or more (meth)acryloyl groups, it preferably contains a first (meth)acrylate represented by the following formula (4):

[0183]

[0184] In formula (4), Q １０ is a linear or branched alkylene group having 1 to 3 carbon atoms. １０ is preferably a linear alkylene group having 1 to 3 carbon atoms, and particularly preferably a methylene group.

[0185] Q １１ is a linear or branched alkylene group having 1 to 10 carbon atoms. １１is preferably a linear alkylene group having 1 to 10 carbon atoms, more preferably a linear alkylene group having 2 to 6 carbon atoms, and particularly preferably a linear alkylene group having 2 to 4 carbon atoms.

[0186] Q １２ is a hydrogen atom or a methyl group. １２ is preferably a methyl group.

[0187] Q １３ is a trivalent to hexavalent organic group having 1 to 10 carbon atoms. １３ Examples of the organic group represented by the formula Q include a group derived from a polyol, a trivalent to hexavalent hydrocarbon group, and an organic group containing a trivalent to hexavalent urethane bond. １３ is preferably a group derived from a polyol or a trivalent to hexavalent hydrocarbon group, and is preferably a group derived from glycerin, a group derived from trimethylolpropane, a group derived from pentaerythritol, a group derived from ditrimethylolpropane, or a group derived from dipentaerythritol.

[0188] a1 is 0 or 1.

[0189] b1 is a number of 3 or more and 15 or less. If it is desired to improve the photochromic properties and appearance of the resulting cured product, b1 is preferably a number of 4 or more and 15 or less, more preferably a number of 4 or more and 13 or less, even more preferably a number of 5 or more and 12 or less, and particularly preferably a number of 5 or more and 10 or less.

[0190] c1 is 3 or more and 6 or less.

[0191] The polyfunctional (meth)acrylate represented by formula (4) more preferably contains a tri- or tetrafunctional (meth)acrylate represented by the following formula (4a):

[0192]

[0193] In formula (4a), Q ２０ , Q ２１ , Q ２２ , and Q ２３ are each independently an alkylene group having 1 to 3 carbon atoms. ２０ , Q ２１ , Q２２ , and Q ２３ is preferably a methylene group. a4, a5, a6, and a7 each independently represent an integer of 0 or 1.

[0194] Q ２４ , Q ２５ , and Q ２６ are each independently a monovalent group represented by the following formula (4b):

[0195]

[0196] In formula (4b), Q １１ , Q １２ , b1 have the same meaning as in formula (4).

[0197] Q ２４ , Q ２５ , and Q ２６ may have different structures from each other or may have the same structure. ２４ , Q ２５ , and Q ２６ Preferably, the structures of the two compounds are the same.

[0198] Q ２７ Q is a hydrogen atom, a linear or branched alkyl group having from 1 to 5 carbon atoms, a linear or branched alkoxy group having from 1 to 5 carbon atoms, or a monovalent group represented by formula (4b). ２７ is preferably a hydrogen atom, a linear alkyl group having 1 to 3 carbon atoms, or a monovalent group represented by formula (4b).

[0199] Specific examples of the polyfunctional (meth)acrylate represented by the above formula (4) include at least one selected from the group consisting of alkoxylated trimethylolpropane tri(meth)acrylate, alkoxylated glycerin tri(meth)acrylate, alkoxylated pentaerythritol tetra(meth)acrylate, alkoxylated ditrimethylolpropane (meth)acrylate, and alkoxylated dipentaerythritol (meth)acrylate.

[0200] The alkoxylated trimethylolpropane tri(meth)acrylate includes at least one selected from the group consisting of ethoxylated trimethylolpropane trimethacrylate, propoxylated trimethylolpropane trimethacrylate, butoxylated trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, and butoxylated trimethylolpropane triacrylate.

[0201] The alkoxylated glycerin tri(meth)acrylate includes at least one selected from the group consisting of ethoxylated glycerin trimethacrylate, propoxylated glycerin trimethacrylate, butoxylated glycerin trimethacrylate, ethoxylated glycerin triacrylate, propoxylated glycerin triacrylate, and butoxylated glycerin triacrylate.

[0202] The alkoxylated pentaerythritol tetra(meth)acrylate includes at least one selected from the group consisting of ethoxylated pentaerythritol tetramethacrylate, propoxylated pentaerythritol tetramethacrylate, butoxylated pentaerythritol tetramethacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated pentaerythritol tetraacrylate, and butoxylated pentaerythritol tetraacrylate.

[0203] The polyfunctional (meth)acrylate represented by formula (4) more preferably includes at least one selected from the group consisting of ethoxylated trimethylolpropane tri(meth)acrylate, ethoxylated glycerin tri(meth)acrylate, and ethoxylated pentaerythritol tetra(meth)acrylate.

[0204] The radical polymerizable monomer (A) according to this embodiment may consist solely of (A-1) a first (meth)acrylate, or may also contain (A-2) a second (meth)acrylate.

[0205] <(A-2) Second (meth)acrylate> The radical polymerizable monomer (A) may consist solely of (A-1) first (meth)acrylate, but preferably further contains (A-2) second (meth)acrylate having three or more (meth)acryloyl groups and represented by the following formula (5):

[0206]

[0207] In formula (5), Q １０ , Q １１ , Q １２ , Q １３ , a1, and c1 have the same meanings as in formula (4), and b2 is 0, 1, 2, or 3.

[0208] The second (meth)acrylate more preferably contains a tri- or tetrafunctional (meth)acrylate represented by the following formula (5a):

[0209]

[0210] In formula (5a), Q ２０ , Q ２１ , Q ２２ , Q ２３ , a4, a5, a6, and a7 have the same meanings as in formula (4a).

[0211] Q ３０ , Q ３１ , and Q ３２ are each independently a monovalent group represented by the following formula (5b):

[0212]

[0213] In formula (5b), Q １１ , Q １２ , and b2 have the same meanings as in formula (5). ３０ , Q ３１ , and Q ３２ may have different structures from each other or may have the same structure. ３０ , Q ３１ , and Q ３２ Preferably, the structures of the two compounds are the same.

[0214] Q ３３Q is a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a linear or branched alkoxy group having 1 to 5 carbon atoms, or a monovalent group represented by formula (5b). ３３ is preferably a hydrogen atom, a linear alkyl group having 1 to 3 carbon atoms, or a monovalent group represented by formula (5b).

[0215] Specific examples of the polyfunctional (meth)acrylate represented by the above formula (5) include trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetramethacrylate, tetramethylolmethane tetraacrylate, trimethylolpropane triethylene glycol trimethacrylate, trimethylolpropane triethylene glycol triacrylate, ditrimethylolpropane tetramethacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentamethacrylate, etc. When the radical polymerizable monomer (A) contains a second (meth)acrylate, the appearance of the cured body tends to be improved. In the radical polymerizable monomer (A), the proportion of the second (meth)acrylate is preferably 5% by mass or more, more preferably 7% by mass or more, and even more preferably 15% by mass or more, from the viewpoint of improving the appearance of the cured product. In terms of improving the photochromic properties of the cured product, the proportion of the second (meth)acrylate is preferably 49% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and particularly preferably 25% by mass or less. This proportion can be confirmed, for example, by measuring the mass of the second (meth)acrylate separated by silica gel column chromatography. The proportion of the second (meth)acrylate may be 5% by mass or more and 45% by mass or less, 10% by mass or more and 35% by mass or less, or 20% by mass or more and 30% by mass or less.

[0216] The radical polymerizable monomer (A) may contain, in addition to the first and second (meth)acrylates, (A-3) another (meth)acrylate and (A-4) another radical polymerizable monomer (hereinafter, these may be referred to as "component (A-3)" and "component (A-4)", respectively).

[0217] <(A-3) Other (meth)acrylates> Examples of the component (A-3) include (meth)acrylates that can polymerize with a radically polymerizable photochromic compound, have a (meth)acryloyl group in their molecular structure, and are radically polymerizable monomers that do not fall under (A-1) or (A-2). Such radically polymerizable monomers are not particularly limited, and known monomers can be used. The component (A-3) can also include a bifunctional (meth)acrylate having two (meth)acryloyl groups in the molecule, a polyfunctional (meth)acrylate having three (meth)acryloyl groups in the molecule, or a monofunctional (meth)acrylate having only one (meth)acryloyl group.

[0218] <Bifunctional (meth)acrylate having two (meth)acryloyl groups in the molecule> The curable composition according to this embodiment may contain the following bifunctional (meth)acrylate as the component (A-3). When a di(meth)acrylate other than the first (meth)acrylate is contained, the hardness of the cured body may be improved. Specific examples include a bifunctional (meth)acrylate represented by formula (3) and having a number average molecular weight of less than 600, a bifunctional (meth)acrylate represented by formula (6a) or formula (6b) below, a bifunctional (meth)acrylate having a urethane bond, and a bifunctional (meth)acrylate other than the above.

[0219] (Bifunctional (meth)acrylate represented by formula (6a))

[0220]

[0221] In formula (6a), R １４ and R １５ are each a hydrogen atom or a methyl group. １６ and R １７ are each a hydrogen atom or a methyl group. １is a divalent organic group. １ is a linear or branched alkylene group having 1 to 20 carbon atoms, a phenylene group which may have a halogen or an alkyl group having 1 to 5 carbon atoms as a substituent, a cycloalkylene group, a bicycloalkylene group, a tricycloalkylene group, or a group represented by any of the following formulas:

[0222]

[0223]

[0224]

[0225]

[0226]

[0227] In the above formula, R １８Ａ , R １８Ｂ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom. xx and xy represent integers of 0 to 4 or 0 to 10. Ring X represents a benzene ring or a cyclohexane ring. YY represents -O-, -S-, -(SO ２ )-,-CO-,-CH ２ -, -CH=CH-, -C(CH ３ ) ２ -, -C(CH ３ ) (C ６ H ５ )—, or a group represented by any of the following formulae:

[0228]

[0229]

[0230] In the above formula (6a), 11 and mm are each an integer of 1 or more, and 11+mm has an average value of 2 or more and 30 or less.

[0231] Specific examples of the bifunctional (meth)acrylate represented by the above formula (6a) include bisphenol A di(meth)acrylate, 2,2-bis[4-(methacryloyloxyethoxy)phenyl]propane, 2,2-bis[3,5-dibromo-4-(methacryloyloxyethoxy)phenyl]propane, 2,2-bis[4-(methacryloyloxydipropoxy)phenyl]propane, 2,2-bis[4-(acryloyloxydiethoxy)phenyl]propane, 2,2-bis[4-(acryloyloxypolyethoxy)phenyl]propane, 2,2-bis[4-(methacryloyloxypolyethoxy)phenyl]propane, 1,3-adamantanediol dimethacrylate, and ditrimethylolcyclodecane diacrylate.

[0232] (Bifunctional (meth)acrylate represented by formula (6b))

[0233]

[0234] In formula (6b), R １９ and R ２０ are each a hydrogen atom or a methyl group, and nn is a number from 1 to 20 on average.

[0235] B1 and B2 are each independently a linear or branched alkylene group having 2 to 15 carbon atoms. B1 and B2 may be the same or different. When there are multiple B1s, the multiple B1s may be the same or different groups.

[0236] The bifunctional (meth)acrylate represented by the above formula (6b) can be produced by reacting a polycarbonate diol with (meth)acrylic acid.

[0237] Examples of the polycarbonate diol used here include the following: Specifically, polycarbonate diol (average molecular weight 500 to 2000) obtained by phosgenation of trimethylene glycol, polycarbonate diol (average molecular weight 500 to 2000) obtained by phosgenation of tetramethylene glycol, polycarbonate diol (average molecular weight 500 to 2000) obtained by phosgenation of pentamethylene glycol, polycarbonate diol (average molecular weight 500 to 2000) obtained by phosgenation of hexamethylene glycol, polycarbonate diol (average molecular weight 500 to 2000) obtained by phosgenation of octamethylene glycol, polycarbonate diol (average molecular weight 500 to 2000) obtained by phosgenation with nonamethylene glycol, polycarbonate diol (average molecular weight 500 to 2000) obtained by phosgenation with triethylene glycol and tetramethylene glycol, Examples thereof include recarbonate diol (average molecular weight 500 to 2000), polycarbonate diol (average molecular weight 500 to 2000) obtained by phosgenation of tetramethylene glycol and hexamethylene diglycol, polycarbonate diol (average molecular weight 500 to 2000) obtained by phosgenation of pentamethylene glycol and hexamethylene glycol, polycarbonate diol (average molecular weight 500 to 2000) obtained by phosgenation of tetramethylene glycol and octamethylene glycol, polycarbonate diol (average molecular weight 500 to 2000) obtained by phosgenation of hexamethylene glycol and octamethylene glycol, and polycarbonate diol (average molecular weight 500 to 2000) obtained by phosgenation of 1-methyltrimethylene glycol.

[0238] (Bifunctional (meth)acrylate having a urethane bond) Examples of the bifunctional (meth)acrylate having a urethane bond include those obtained by reacting a polyisocyanate compound having two or more isocyanate groups in the molecule, a polyol compound having two or more hydroxyl groups in the molecule, and a hydroxyl group-containing (meth)acrylate.

[0239] Examples of polyols include polyester diols such as polycaprolactone diol, polycarbonate diol, polybutadiene diol, pentaerythritol, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol.

[0240] In addition, a reaction mixture obtained by further reacting a urethane prepolymer obtained by the reaction of such a polyisocyanate and a polyol with 2-hydroxy(meth)acrylate, or a reaction mixture obtained by directly reacting a diisocyanate with 2-hydroxy(meth)acrylate, such as a urethane(meth)acrylate monomer, can also be used.

[0241] Examples of hydroxyl group-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

[0242] The bifunctional (meth)acrylate having a urethane bond may be any commercially available product and can be used without any limitation. Examples of commercially available products include U-2PPA (molecular weight 482), UA-122P (molecular weight 1,100), and U-122P (molecular weight 1,100) manufactured by Shin-Nakamura Chemical Co., Ltd., and EB4858 (molecular weight 454) manufactured by Daicel-UCB Ltd.

[0243] (Bifunctional (meth)acrylates not falling under the above-mentioned conditions) Examples of "bifunctional (meth)acrylates not falling under the above-mentioned conditions" other than the bifunctional (meth)acrylates represented by the above formula (6a) or (6b) and bifunctional (meth)acrylates having a urethane bond include neopentyl glycol di(meth)acrylate and bifunctional (meth)acrylates containing a sulfur atom. The sulfur atom preferably forms a part of the molecular chain as a sulfide group. Specific examples include bis(2-methacryloyloxyethylthioethyl)sulfide, bis(methacryloyloxyethyl)sulfide, bis(acryloyloxyethyl)sulfide, 1,2-bis(methacryloyloxyethylthio)ethane, 1,2-bis(acryloyloxyethyl)ethane, bis(2-methacryloyloxyethylthioethyl)sulfide, bis(2-acryloyloxyethylthioethyl)sulfide, 1,2-bis(methacryloyloxyethylthioethylthio)ethane, 1,2-bis(acryloyloxyethylthioethylthio)ethane, 1,2-bis(methacryloyloxyisopropylthioisopropyl)sulfide, and 1,2-bis(acryloyloxyisopropylthioisopropyl)sulfide.

[0244] The above bifunctional (meth)acrylate compounds can be used as a single component of each of the individually described components, or as a combination of multiple components. Furthermore, the individually described components can also be used in combination. When multiple components or multiple combinations are used, the reference mass is the total amount of the multiple components.

[0245] <Other Polyfunctional (meth)acrylates Having Three (meth)acryloyl Groups in the Molecule> The curable composition according to the embodiment may contain, as the component (A-3), a polyfunctional (meth)acrylate having three or more (meth)acryloyl groups in one molecule, other than the first and second (meth)acrylates. The inclusion of a polyfunctional (meth)acrylate can improve the appearance of the cured product. Specific examples include polyfunctional (meth)acrylates having a urethane bond and polyfunctional (meth)acrylates other than those described above.

[0246] (Polyfunctional (meth)acrylate having a urethane bond) A polyfunctional (meth)acrylate having a urethane bond is obtained by reacting a polyisocyanate compound having three or more isocyanate groups in the molecule with a polyol compound having two or more hydroxyl groups in the molecule and a hydroxyl group-containing (meth)acrylate. Other examples include those obtained by reacting a polyfunctional polyol compound with an isocyanate having a (meth)acryloyl group. A suitable polyfunctional (meth)acrylate having a urethane bond is a polyfunctional (meth)acrylate having 3 to 6 (meth)acryloyl groups in the molecule. Commercially available products include U-4HA (molecular weight 596, number of functional groups 4), U-6HA (molecular weight 1,019, number of functional groups 6), U-6LPA (molecular weight 818, number of functional groups 6), and U-15HA (molecular weight 2,300, number of functional groups 15), all manufactured by Shin-Nakamura Chemical Co., Ltd.

[0247] (Polyfunctional (meth)acrylates other than the above) The first and second (meth)acrylates and the polyfunctional (meth)acrylates having a urethane bond can be exemplified by compounds in which the end of a polyester compound is modified with a (meth)acryloyl group. As such polyester (meth)acrylate compounds, various polyester (meth)acrylate compounds having different molecular weights of raw polyester compounds and different amounts of modification with a (meth)acryloyl group are commercially available, and these can be used. Specific examples include tetrafunctional polyester oligomers (molecular weight 2,500 to 3,500, Daicel-UCB, EB80, etc.), hexafunctional polyester oligomers (molecular weight 6,000 to 8,000, Daicel-UCB, EB450, etc.), hexafunctional polyester oligomers (molecular weight 45,000 to 55,000, Daicel-UCB, EB1830, etc.), and tetrafunctional polyester oligomers (particularly GX8488B, molecular weight 10,000, Dai-ichi Kogyo Seiyaku Co., Ltd., etc.).

[0248] <Monofunctional (meth)acrylate having only one (meth)acrylate group> The curable composition according to this embodiment may also contain, as component (A-3), a monofunctional (meth)acrylate having only one (meth)acryloyl group. The monofunctional (meth)acrylate can reduce the viscosity of the curable composition and improve handleability. Examples of the monofunctional (meth)acrylate include monofunctional (meth)acrylates represented by the following formula (7):

[0249]

[0250] In formula (7), R ２１ is a hydrogen atom, a methyldimethoxysilyl group, a trimethoxysilyl group, a glycidyl group, a pentamethylpiperidino group, a 2,2,6,6-tetramethylpiperidino group, or a piperidino group. ２２ is a hydrogen atom or a methyl group, oo is an integer of 0 or more and 10 or less, and pp is an integer of 0 or more and 20 or less.

[0251] Specific examples of the monofunctional (meth)acrylate represented by the above formula (7) include methoxypolyethylene glycol methacrylate, methoxypolyethylene glycol acrylate, stearyl methacrylate, lauryl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, lauryl acrylate, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, glycidyl methacrylate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, and 2,2,6,6-tetramethyl-4-piperidyl methacrylate.

[0252] <(A-4) Other Radically Polymerizable Monomers> The curable composition according to the embodiment may contain the component (A-4). The component (A-4) is not particularly limited as long as it is a radically polymerizable monomer that can be polymerized with the first (meth)acrylate or the radically polymerizable photochromic compound, and known monomers can be used. For example, radically polymerizable polyrotaxanes, radically polymerizable silsesquioxane compounds, allyl compounds, and vinyl compounds are preferably used.

[0253] <Radically Polymerizable Polyrotaxane> Polyrotaxane has a composite molecular structure consisting of an axis molecule and multiple cyclic molecules that encapsulate the axis molecule. Bulky terminal groups are formed at both ends of the axis molecule, preventing the cyclic molecules from detaching from the axis molecule. Radical-polymerizable polyrotaxane is a polyrotaxane in which radically polymerizable groups are introduced into the side chains of the cyclic molecules. The radically polymerizable groups are introduced, for example, by modifying 1 mol % or more but less than 100 mol % of the hydroxyl groups of the cyclic molecules with radically polymerizable groups. The modification ratio can be calculated by (number of moles of polymerizable groups introduced) / (number of moles of total OH groups in the side chains) × 100. From the viewpoints of adhesion and the mechanical strength and functionality of the resulting cured product, the modification ratio is preferably 10 mol % or more but less than 95 mol %.

[0254] If the weight-average molecular weight of the axial molecule is too large, the compatibility with other polymerizable monomers, etc. tends to decrease, while if it is too small, the mobility of the cyclic molecule tends to decrease. The weight-average molecular weight of the axial molecule is preferably in the range of 1,000 to 10,0000, more preferably in the range of 5,000 to 80,000, and most preferably in the range of 8,000 to 50,000.

[0255] The cyclic molecule is preferably a cyclodextrin ring, a crown ether ring, a benzocrown ring, a dibenzocrown ring, or a dicyclohexanocrown ring, with a cyclodextrin ring and a crown ether ring being particularly preferred, and a cyclodextrin ring being most preferred. Furthermore, among cyclodextrin rings, there are α-cyclodextrin rings (inner ring diameter 0.45 to 0.6 nm), β-cyclodextrin rings (inner ring diameter 0.6 to 0.8 nm), and γ-cyclodextrin rings (inner ring diameter 0.8 to 0.95 nm), with α-cyclodextrin rings and β-cyclodextrin rings being preferred, and an α-cyclodextrin ring being most preferred. When the inclusion number when all cyclic molecules are introduced into the axial molecule is taken as 1, the inclusion number of the cyclic molecules is preferably in the range of 0.001 to 0.6, more preferably in the range of 0.002 to 0.5, and most preferably in the range of 0.003 to 0.4.

[0256] As the radical polymerizable group, a (meth)acryloyl group is preferred in consideration of reactivity with other polymerizable monomers, etc. The number of radical polymerizable groups is not particularly limited, and is preferably 0 to 5,000 per molecule.

[0257] The above-described polyrotaxane having a (meth)acryloyl group is described, for example, in WO 2018 / 030257.

[0258] <Silsesquioxane Radically Polymerizable Compound> Silsesquioxane radically polymerizable compounds have various molecular structures such as cage-like, ladder-like, and random structures, and have a radically polymerizable group such as a (meth)acryloyl group.

[0259] An example of such a silsesquioxane polymerizable compound is one represented by the following formula (8).

[0260]

[0261] In formula (8), q is the degree of polymerization and is an integer of 3 or more and 100 or less.

[0262] Multiple R ２３may be the same or different and are a radical polymerizable group, an organic group containing a radical polymerizable group, a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, or a phenyl group, and at least one R ２３ is a radically polymerizable group or an organic group containing a radically polymerizable group.

[0263] Here, R ２３ Examples of the radical polymerizable group represented by the formula (I) or an organic group containing a radical polymerizable group include a (meth)acryloyl group; organic groups having a (meth)acryloyl group such as a (meth)acryloyloxypropyl group or a (3-(meth)acryloyloxypropyl)dimethylsiloxy group; an allyl group; organic groups having an allyl group such as an allylpropyl group or an allylpropyldimethylsiloxy group; a vinyl group; and organic groups having a vinyl group such as a vinylpropyl group or a vinyldimethylsiloxy group.

[0264] <Allyl-Based Polymerizable Compound> Examples of allyl-based polymerizable compounds having an allyl group include the following: diethylene glycol bisallyl carbonate, methoxypolyethylene glycol allyl ether, methoxypolyethylene glycol-polypropylene glycol allyl ether, butoxypolyethylene glycol-polypropylene glycol allyl ether, phenoxypolyethylene glycol allyl ether, vinyloxypolyethylene glycol allyl ether, styryloxypolyethylene glycol allyl ether, and methoxypolyethylene thioglycol allyl thioether.

[0265] <Vinyl-Based Polymerizable Compounds> Examples of vinyl-based polymerizable compounds having a vinyl group include methyl vinyl ketone, ethyl vinyl ketone, ethyl vinyl ether, styrene, vinylcyclohexane, butadiene, 1,4-pentadiene, divinyl sulfide, divinyl sulfone, 1,2-divinylbenzene, 1,3-divinyl-1,1,3,3-tetramethylpropanedisiloxane, diethylene glycol divinyl ether, divinyl adipate, divinyl sebacate, ethylene glycol divinyl ether, divinyl sulfoxide, divinyl persulfide, dimethyldivinylsilane, 1,2,4-trivinylcyclohexane, methyltrivinylsilane, α-methylstyrene, and α-methylstyrene dimer.

[0266] <Proportions of Each Component of the Radical Polymerizable Monomer> In consideration of the photochromic properties and appearance of the resulting photochromic cured product, the components (A-1), (A-2), (A-3), and (A-4) in the component (A) are preferably 51 to 100 parts by mass of the component (A-1), 0 to 49 parts by mass of the component (A-2), 0 to 20 parts by mass of the component (A-3), and 0 to 5 parts by mass of the component (A-4), relative to 100 parts by mass of the component (A), and more preferably 60 to 95 parts by mass of the component (A-1), 5 to 40 parts by mass of the component (A-2). It is more preferable that the (A-1) component be 70 to 95 parts by mass, the (A-2) component be 5 to 30 parts by mass, the (A-3) component be 0 to 15 parts by mass, and the (A-4) component be 0 to 5 parts by mass, and it is particularly preferable that the (A-1) component be 80 to 95 parts by mass, the (A-2) component be 5 to 20 parts by mass, the (A-3) component be 0 to 10 parts by mass, and the (A-4) component be 0 to 5 parts by mass.

[0267] When the radical polymerizable monomer consists only of the first and second (meth)acrylates, the proportion of the first (meth)acrylate in the (meth)acrylate component is, for example, 50% by mass or more and 99% by mass or less, preferably 60% by mass or more and 97% by mass or less, 65% by mass or more and 95% by mass or less, or 70% by mass or more and 93% by mass or less.

[0268] <(Meth)acryloyl Group Content of Radically Polymerizable Monomer> In consideration of the photochromic properties and appearance of the resulting cured product, the (meth)acryloyl group content in the component (A) is preferably less than 5.50 mmol / g, and more preferably 0.50 mmol / g or more but less than 5.50 mmol / g.

[0269] The "(meth)acryloyl group content" of a polymerizable composition containing a (meth)acrylate can be calculated as follows: First, the content ratio of each (meth)acrylate contained in the polymerizable monomer is calculated on a mass basis. For each (meth)acrylate, "(meth)acryloyl group content x the above content ratio" is calculated, and the sum of the calculated values ​​for all (meth)acrylates contained in the polymerizable monomer is taken as the (meth)acryloyl group content of that polymerizable monomer.

[0270] If the (meth)acryloyl group content is too low, the crosslinking density of the cured product will be extremely low, resulting in excellent photochromic properties but poor appearance. On the other hand, if the (meth)acryloyl group content is too high, the crosslinking density of the cured product will be high, resulting in good appearance but poor photochromic properties. In order to obtain a cured product that is excellent in both appearance and photochromic properties, the (meth)acryloyl group content is preferably 0.75 mmol / g or more and less than 4.65 mmol / g, more preferably 1.25 mmol / g or more and less than 4.00 mmol / g, even more preferably 1.50 mmol / g or more and less than 3.75 mmol / g, and particularly preferably 1.75 mmol / g or more and less than 3.50 mmol / g.

[0271] <Amount of Radical Polymerizable Photochromic Compound> The radical polymerizable photochromic compound is used in an amount sufficient to obtain the desired photochromic properties. The ratio M1 / M2, the mass M1 of the radical polymerizable photochromic compound to the mass M2 of the radical polymerizable monomer, is preferably 0.001 or more and 0.1 or less. It is preferable to adjust the optimal amount depending on the intended use. Specifically, when a curable composition containing a photochromic compound is used to form a thin film such as a coating, for example, a thin film of about 100 μm (a polymer film formed by polymerization of the photochromic curable composition), it is preferable to adjust the color tone by incorporating a photochromic compound with a ratio M1 / M2 of 0.005 or more and 0.075 or less. The ratio M1 / M2 is more preferably 0.010 or more and 0.065 or less, and particularly preferably 0.015 or more and 0.060 or less. Furthermore, when a thick cured body (a polymer molded body obtained by polymerizing a photochromic curable composition) is to be produced, for example, a cured body having a thickness of 1 mm or more, it is preferable to adjust the color tone by blending a photochromic compound in which the ratio M1 / M2 is 0.001 or more and 0.05 or less.

[0272] The photochromic compounds other than the radical polymerizable photochromic compounds are also not limited to any particular compounds, and known compounds can be used, and these compounds can be used alone or in combination of two or more. In consideration of the appearance and photochromic properties of the resulting cured product, the content of the photochromic compounds other than the radical polymerizable photochromic compounds relative to the radical polymerizable photochromic compounds is preferably 50% or less, more preferably 35% or less, even more preferably 15% or less, and particularly preferably 0%.

[0273] <Other Additives> Various known additives can be blended into the curable composition as long as the effects are not impaired. Examples of additives include release agents, ultraviolet absorbers, infrared absorbers, ultraviolet stabilizers, antioxidants, coloring inhibitors, antistatic agents, fluorescent dyes, dyes, pigments, fragrances, and other additives. Solvents and leveling agents can also be blended. Thiols such as t-dodecyl mercaptan can also be blended as polymerization regulators.

[0274] <UV Stabilizer> The curable composition preferably contains an UV stabilizer. This is because the durability of the photochromic compound can be further improved. Examples of suitable UV stabilizers include hindered amine light stabilizers, hindered phenol antioxidants, and sulfur-based antioxidants. The hindered amine light stabilizer is not particularly limited, but bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate is preferred, particularly in terms of preventing deterioration of the photochromic compound. Furthermore, hindered amine light stabilizers commercially available from ADEKA Corporation under the trade names Adekastab LA-52, LA-57, LA-62, LA-63, LA-67, LA-77, LA-87, and the like can also be suitably used.

[0275] In terms of preventing deterioration of the photochromic compound, it is preferable to incorporate a hindered phenol antioxidant into the curable composition. Examples of the hindered phenol antioxidant include 2,6-di-t-butyl-4-methyl-phenol, IRGANOX 245 (ethylene bis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-toluyl)propionate] manufactured by BASF Japan Ltd., and IRGANOX 1076 (octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) manufactured by BASF Japan Ltd. IRGANOX 1010: pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] manufactured by BASF Japan Ltd., and other products such as IRGANOX 1035, 1075, 1098, 1135, 1141, 1222, 1330, 1425, 1520, 259, 3114, 3790, 5057, and 565 manufactured by BASF Japan Ltd.

[0276] The amount of such an ultraviolet stabilizer used is not particularly limited as long as the effect is not impaired, but is usually in the range of 0.001 to 10 parts by mass, particularly 0.01 to 1 part by mass, per 100 parts by mass of the curable composition. From the viewpoint of enhancing the effect of preventing deterioration of the photochromic compound in the obtained cured product and further improving the appearance, it is preferable that the ultraviolet stabilizer also has a radically polymerizable substituent, like the photochromic compound.

[0277] <UV Absorber> As the UV absorber, known UV absorbers such as benzophenone compounds, benzotriazole compounds, cyanoacrylate compounds, triazine compounds, benzoate compounds, cinnamate ester compounds, and oxanilide compounds can be used, with cyanoacrylate compounds, benzophenone compounds, benzotriazole compounds, and cinnamate ester compounds being particularly preferred. The UV stabilizer is preferably used in an amount of 0.001 to 5 parts by mass per 100 parts by mass of the curable composition containing the photochromic compound and the polymerizable compound. From the viewpoint of further improving the appearance of the resulting cured product, a UV absorber that is polymerizable with component (A) is preferred.

[0278] <Surfactant> Addition of a surfactant can improve the wettability of the optical substrate and the primer layer and prevent the occurrence of poor appearance. Examples of the surfactant include known surfactants such as silicone surfactants having a silicone chain (polyalkylsiloxane unit) as a hydrophobic group and fluorine surfactants having a fluorocarbon chain. When using surfactants, two or more types may be mixed and used.

[0279] Specific examples of silicone surfactants and fluorosurfactants that can be suitably used include L-7001, L-7002, L-7604, FZ-2123, and FZ-2110 manufactured by Dow Toray Co., Ltd.; Megafac F-470, Megafac F-1405, and Megafac F-479 manufactured by DIC Corporation; FLORAD FC-430 manufactured by Sumitomo 3M Limited; TEGORAD 2100 and TEGORAD 2300 manufactured by Evonik Japan Co., Ltd.; and BYK-UV3505 and BYK-UV4505 manufactured by BYK Japan Co., Ltd. Examples of such a resin include K-UV3505, BYK-UV3510, BYK-UV3530, BYK-3550, BYK-3560, BYK-UV3565, BYK-3566, BYK-UV3500, BYK-UV3535, BYK-UV3570, BYK-UV3575, BYK-UV3576, and KR-513, X-22-2445, X-40-9296, X-22-164, X-22-164A, X-22-164B, X-22-164C, and X-22-164E manufactured by Shin-Etsu Chemical Co., Ltd.

[0280] From the viewpoint of further improving the appearance of the resulting cured product, a surfactant that is polymerizable with component (A) is preferred.

[0281] <Polymerization Initiator> Polymerization initiators include thermal polymerization initiators and photopolymerization initiators, and specific examples thereof are as follows.

[0282] Examples of the thermal polymerization initiator include diacyl peroxides; benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide, acetyl peroxide, peroxy esters; t-butylperoxy-2-ethylhexanate, t-butylperoxyneodecanate, cumylperoxyneodecanate, t-butylperoxybenzoate, percarbonates; diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, azo compounds; and azobisisobutyronitrile.

[0283] Examples of the photopolymerization initiator include acetophenone-based compounds such as 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, α-dicarbonyl-based compounds such as 1,2-diphenylethanedione, methylphenylglycoxylate, and acylphosphine oxide-based compounds such as 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine acid methyl ester, 2,6-dichlorobenzoyldiphenylphosphine oxide, and 2,6-dimethoxybenzoyldiphenylphosphine oxide.

[0284] When a photopolymerization initiator is used, a known polymerization curing accelerator such as a tertiary amine may be used in combination.

[0285] <Cured Product> A cured product is obtained by curing a curable composition. The curable composition is cured by inducing a radical polymerization reaction by irradiation with active energy rays such as ultraviolet rays, α-rays, β-rays, γ-rays, or LED, heat, or a combination of both. That is, an appropriate curing method may be adopted depending on the type of polymerizable monomer and polymerization curing accelerator used and the form of the cured product to be formed. When forming a laminate by the coating method described below, it is preferable to adopt photopolymerization because a uniform film thickness can be obtained.

[0286] When thermally polymerizing a curable composition containing a polymerizable compound, the thermal polymerization temperature affects the properties of the resulting cured product. While temperature conditions cannot be generally defined because they are influenced by the type and amount of thermal polymerization initiator and the type of polymerizable compound, a generally preferred method is to initiate polymerization at a relatively low temperature and slowly increase the temperature. Like temperature, polymerization time also varies depending on various factors, so it is best to determine the optimal time based on these conditions in advance. Generally, however, it is preferable to select conditions so that polymerization is complete within 2 to 48 hours. When obtaining a photochromic laminate sheet, polymerization is preferably carried out at a temperature at which the reaction between polymerizable functional groups proceeds, and the optimal temperature and time are determined to achieve the desired molecular weight.

[0287] Furthermore, when photopolymerizing a curable composition, among the polymerization conditions, UV intensity in particular affects the properties of the resulting photochromic cured product. The illuminance conditions cannot be generally limited because they are affected by the type and amount of the photopolymerization initiator and the type of polymerizable monomer. However, as an example, it is 50 to 500 mW / cm at a wavelength of 365 nm. ２ In another example, the conditions are such that the UV light is irradiated at a wavelength of 405 nm and at a power of 50 to 500 mW / cm for a time of 0.5 to 5 minutes. ２ The conditions are such that the UV light is irradiated for 0.5 to 5 minutes.

[0288] The biomass plastic degree of the cured body is, for example, 10% by mass or more. The biomass plastic degree can be calculated by a method in accordance with ISO standard 16620-3. The biomass plastic degree of the cured body is preferably 25% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more. There is no particular upper limit to this biomass plastic degree, but in one example it is 100% by mass or less, and in another example it is 80% by mass or less.

[0289] <Laminate> According to another embodiment, there is provided a laminate, which includes an optical substrate and a resin layer that is a cured product according to an embodiment and is located on a surface of the optical substrate.

[0290] The optical substrate may have any shape, such as a flat plate, a circle, a prism, or a cylinder. The optical substrate is preferably lenticular. The optical substrate may be a spherical lens or an aspherical lens. The optical substrate may be a convex lens or a concave lens.

[0291] The optical substrate may be made of an organic material such as a resin, or may be made of an inorganic material such as glass.

[0292] The optical substrate preferably contains a resin. The resin preferably contains at least one selected from the group consisting of allyl resin, cellulose resin, acrylic resin, methacrylic resin, polyurethane resin, polyurethane urea resin, polythiourethane resin, polythioepoxy resin, polyamide resin, polyester resin, polyimide resin, epoxy resin, polyolefin resin, polyvinyl alcohol resin, and polycarbonate resin. The resin preferably contains at least one selected from the group consisting of allyl resin, acrylic resin, methacrylic resin, polyurethane resin, polyurethane urea resin, polythiourethane resin, and polycarbonate resin. The optical substrate may be, for example, a cured product of an eyeglass lens material such as CR-39 (registered trademark) or the MR series. The resin may be derived from plant materials or petroleum materials.

[0293] The biomass plastic content of the optical substrate is preferably 25% by mass or more. The biomass plastic content can be calculated using a method in accordance with ISO standard 16620-3. The biomass plastic content of the optical substrate is preferably 30% by mass or more, and more preferably 40% by mass or more. There is no particular upper limit to this biomass plastic content, but in one example, it is 100% by mass or less.

[0294] A primer layer may be provided between the optical substrate and the cured body (resin layer). The primer layer contains a urethane resin.

[0295] The thickness of the resin layer in the laminate according to the embodiment is preferably, for example, 1.0 μm or more and 100 μm or less, for example, 10.0 μm or more and 100.0 μm or less, and more preferably 20.0 μm or more and 60.0 μm or less.

[0296] The Vickers hardness of the laminate according to the embodiment is measured by a method conforming to Japanese Industrial Standards (JIS) Z 2244-2009: Micro Vickers Hardness Test. To measure the Vickers hardness of the laminate, a primer layer is laminated on an optical substrate, and a laminate in which only the cured product is laminated on this primer layer is used as a sample.

[0297] From the viewpoint of obtaining a resin layer with excellent photochromic properties, the Vickers hardness of the laminate is preferably 0.5 or more and less than 5.0, more preferably 0.8 or more and less than 4.5, even more preferably 1.0 or more and less than 3.0, and most preferably 1.2 or more and less than 2.5.

[0298] <Optical Articles> The cured product according to the embodiment can be used in a wide range of applications as an optical article, including, for example, various memory materials such as various memory materials replacing silver halide photosensitive materials, copying materials, printing photosensitive materials, memory materials for cathode ray tubes, photosensitive materials for lasers, and photosensitive materials for holography, as well as lenses. Lenses are suitable for eyeglasses. Photochromic cured products containing a photochromic compound can also be used as photochromic lens materials, optical filter materials, display materials, actinometers, decorative materials, and the like.

[0299] The cured product according to the embodiment is particularly suitable for use in photochromic lenses. Photochromic lenses are suitable as lenses for spectacles such as sunglasses. Any known method can be used to manufacture photochromic lenses, as long as it can provide uniform photochromic performance.

[0300] When photochromic properties are expressed by the kneading method, the above-mentioned curable composition is injected between glass molds held by elastomer gaskets or spacers, and depending on the types of polymerizable compound and polymerization curing accelerator, a photochromic cured product molded into the shape of an optical material such as a lens can be obtained by casting polymerization using heating in an air oven or irradiation with active energy rays such as ultraviolet rays.

[0301] When photochromic properties are expressed by a lamination method, a coating liquid is prepared by dissolving a curable composition in an appropriate organic solvent, and the coating liquid is applied to the surface of an optical substrate such as a lens substrate by spin coating, dipping, or the like, and then dried to remove the organic solvent. Subsequently, polymerization and curing are carried out by UV irradiation or heating in an inert gas such as nitrogen, thereby forming a resin layer consisting of a photochromic cured product on the surface of the optical substrate (coating method).

[0302] Alternatively, a resin layer made of a photochromic cured body can be formed on the surface of an optical substrate by cast polymerization using an inner mold in which an optical substrate such as a lens substrate is placed facing a glass mold so that a predetermined gap is formed, a curable composition is injected into this gap, and polymerization and curing are carried out in this state by UV irradiation, heating, or the like (cast polymerization method).

[0303] When a photochromic layer is formed on the surface of an optical substrate by the above-mentioned lamination methods (coating method and cast polymerization method), the adhesion between the resin layer and the optical substrate can be improved by previously subjecting the surface of the optical substrate to a chemical treatment using an alkaline solution, an acid solution, etc., or a physical treatment using corona discharge, plasma discharge, polishing, etc. Of course, it is also possible to provide a transparent adhesive resin layer on the surface of the optical substrate.

[0304] Furthermore, the cured product or resin layer formed from the curable composition may be subjected to post-processing depending on its intended use, such as dyeing with a dye such as a disperse dye, laminating a protective layer (described later), laminating a hard coat film (described later), laminating an anti-reflection film (described later), or antistatic treatment.

[0305] <Protective Layer> The protective layer is located on the resin layer formed from the curable composition. The protective layer is in direct contact with at least a portion of the resin layer. The portion of the protective layer that is not in contact with the resin layer may be covered with a hard coat layer, an anti-reflection film, or the like.

[0306] The protective layer contains at least one resin selected from the group consisting of an acrylic resin, a urethane resin, and an epoxy resin. The protective layer preferably contains a urethane resin from the viewpoint of high adhesion.

[0307] <Hard Coat Layer> The hard coat layer covers, for example, at least a part of the surface of the resin layer or protective layer formed from the curable composition, and preferably covers the entire surface.

[0308] The hard coat layer contains, for example, a silicon-containing compound such as an organic silane or an inorganic silane, and an inorganic oxide. Examples of the inorganic oxide include titanium oxide (TiO ２ ), zirconium oxide (ZrO ２ ), cerium oxide (CeO ２ Materials with high refractive indexes, such as titanium oxide and cerium oxide, are used. These inorganic oxides have ultraviolet absorbing properties. Therefore, lenses provided with a hard coat layer containing these inorganic oxides are less likely to discolor. In terms of high ultraviolet absorbing properties, it is preferable that the hard coat layer contains at least one inorganic oxide selected from the group consisting of titanium oxide and cerium oxide.

[0309] <Anti-Reflection Film> The anti-reflection film is a film that prevents reflection of light by interference. For example, the anti-reflection film covers at least a part of the surface of the hard coat layer, and preferably covers the entire surface.

[0310] The anti-reflection film has a multi-layer structure in which a relatively high refractive index film and a low refractive index film are laminated. The low refractive index film is, for example, silicon dioxide (SiO ２ The high refractive index film is made of a material having a higher refractive index than the low refractive index layer. Examples of such materials include zirconium oxide (ZrO ２ ), tin oxide (SnO ２ ), niobium oxide (Nb ２ O ５), tantalum oxide (Ta ２ O ５ ), titanium oxide (TiO ２ ), yttrium oxide (Y ２ O ３ ), aluminum oxide (Al ２ O ３ ), a mixture thereof (for example, indium tin oxide (ITO)), or the like is used.

[0311] EXAMPLES Next, the present invention will be described in detail using examples and comparative examples, but the present invention is not limited to these examples. The notation of each component and the evaluation methods are as follows.

[0312] (Component A) (Component A-1) 14G: polyethylene glycol dimethacrylate (number average molecular weight 752, number average molecular weight of polyalkylene glycol chain structure 616) A-PTMG65: polytetramethylene glycol dimethacrylate (number average molecular weight 778, number average molecular weight of polyalkylene glycol chain structure 670) M-PTMG65: polytetramethylene glycol dimethacrylate (number average molecular weight 786, number average molecular weight of polyalkylene glycol chain structure 650) M-PTMG100: polytetramethylene glycol dimethacrylate (number average molecular weight 1148, number average molecular weight of polyalkylene glycol chain structure 1012) M-PTMG130: polytetramethylene glycol dimethacrylate (number average molecular weight 1436, number average molecular weight of polyalkylene glycol chain structure 1300) M-PTMG150: Polytetramethylene glycol dimethacrylate (number average molecular weight 1636, number average molecular weight of polyalkylene glycol chain structure 1500) M-PTMG300: Polytetramethylene glycol dimethacrylate (number average molecular weight 3136, number average molecular weight of polyalkylene glycol chain structure 3000) UMA-PTMG100: Urethane methacrylate of the following formula (number average molecular weight 1311, number average molecular weight of polyalkylene glycol chain structure 966)

[0313]

[0314] (Synthesis of UMA-PTMG100) 550 mL of dehydrated toluene was added to 100.0 g of polytetramethylene ether glycol having a molecular weight of 1001 calculated from the hydroxyl value, and azeotropic dehydration was carried out. 50 mL of toluene was distilled off from the toluene solution after azeotropic dehydration, and the solution was cooled to 60°C. 19.5 mg of p-methoxyphenol and 6.5 mg of dibutyltin dilaurate were added to the cooled solution. 15.3 g of 2-methacryloyloxyethyl isocyanate was slowly added dropwise to the solution. After the dropwise addition, the mixture was reacted at 60-65°C for 10 hours to obtain a reaction solution. 100 mL of water was added to the reaction solution, and the mixture was separated. Celite was added to the obtained organic layer, and the mixture was stirred and then filtered. The obtained organic layer was concentrated to obtain UMA-PTMG100. Measurement of the proton nuclear magnetic resonance spectrum of the obtained UMA-PTMG100 showed a peak of approximately 61H due to tetramethyleneoxy groups and methyl groups at around δ 1.0 to 2.0 ppm, a peak of approximately 63H due to tetramethyleneoxy groups and ethyleneoxy groups at around δ 3.0 to 4.5 ppm, and a 4H peak due to methacryloyl group protons at around δ 5.5 to 6.5 ppm. The number average molecular weight of UMA-PTMG100 was 1,311, and the number average molecular weight of the polyalkylene glycol chain structure in UMA-PTMG100 was 966.

[0315] PTG25CD100: methacrylate of the following formula (number average molecular weight 1,136, number average molecular weight of polyalkylene glycol chain structure 255)

[0316]

[0317] (Synthesis of PTG25CD100) 330 mL of dehydrated toluene, 1.0 mg of p-methoxyphenol, and 2.86 g of p-toluenesulfonic acid hydrate were added to 100 g of NT1002 (manufactured by Mitsubishi Chemical Corporation) with a molecular weight of 1000 calculated from the hydroxyl value, and the mixture was stirred. 18.9 g of methacrylic acid was added thereto, and the mixture was reacted for 20 hours under azeotropic conditions. After the reaction was completed, 1000 mL of 5% aqueous sodium bicarbonate was added, and the mixture was separated. Celite was added to the obtained organic layer, and the mixture was stirred and then filtered. 20 g of Wakogel 60N was added to the obtained organic layer, and the mixture was stirred and then filtered. 1 mL of a 0.1 mg / mL p-methoxyphenol toluene solution was added to the obtained organic layer, and the mixture was concentrated to synthesize PTG25CD100.

[0318] Measurement of the proton nuclear magnetic resonance spectrum showed a peak of approximately 55H due to the tetramethyleneoxy group and methacryloyl group at around δ 1.0 to 2.5 ppm, a peak of approximately 49H due to the tetramethyleneoxy group at around δ 3.0 to 4.5 ppm, and a peak of 4H due to the protons of the acryloyl group at around δ 5.5 to 6.5 ppm. The number average molecular weight of PTG25CD100 was 1136, and the number average molecular weight of the polyalkylene glycol chain structure in PTG25CD100 was 255.

[0319] TMPT-20E: Ethoxylated trimethylolpropane trimethacrylate (number average molecular weight 1218, number average molecular weight of polyalkylene glycol chain structure 294) Gly-20E: Ethoxylated glycerin trimethacrylate (number average molecular weight 1176, number average molecular weight of polyalkylene glycol chain structure 294)

[0320] (Component A-2) TMPT: trimethylolpropane trimethacrylate GTMA: glycerin trimethacrylate

[0321] (Component A-3) LA82: 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate TSL: γ-methacryloyloxypropyltrimethoxysilane MPC100: polycarbonatediol dimethacrylate obtained by phosgenation of pentamethylene glycol and hexamethylene glycol (number average molecular weight 1156, number average molecular weight of polyalkylene glycol chain structure 0) 9G: polyethylene glycol dimethacrylate (number average molecular weight 536, number average molecular weight of polyalkylene glycol chain structure 400) GMA: glycidyl methacrylate

[0322] (Photochromic Compound) PC1: Compound represented by the following formula: In each of the following formulas, "Me" represents a methyl group.

[0323]

[0324] (Synthesis of PC1) With reference to the method described in Patent Document 1, a naphthol compound of the following formula (9) was reacted with a propargyl alcohol of the following formula (10) to synthesize a photochromic compound of the following formula (11).

[0325]

[0326]

[0327]

[0328] The obtained photochromic compound of formula (11) was deprotected by referring to the method described in Patent Document 1, and then reacted with acryloyl chloride to synthesize PC1.

[0329] PC2: A compound represented by the following formula:

[0330]

[0331] (Synthesis of PC2) PC2 was synthesized by carrying out a reaction in the same manner as in PC1, except that the naphthol compound of the formula (9) above was replaced with a naphthol compound of the following formula (12).

[0332]

[0333] PC3: A compound represented by the following formula:

[0334]

[0335] (Synthesis of PC3) With reference to the method described in WO 2013 / 042800, an iodine compound of the following formula (13) was lithiated with butyllithium, and then reacted with methyl ethyl ketone to synthesize a compound of the following formula (14).

[0336]

[0337]

[0338] A naphthol compound of the following formula (15) was synthesized from the compound of the above formula (14) with reference to the method described in WO 2013 / 042800. PC3 was synthesized by carrying out a reaction in the same manner as in PC1, except that the naphthol compound of the above formula (9) was replaced with the naphthol compound of the following formula (15).

[0339]

[0340] PC4: A compound represented by the following formula:

[0341]

[0342] (Synthesis of PC4) With reference to the method described in Patent Document 1, 4-chloro-4'-hydroxybenzophenone was reacted with 16-chloro-2,5,8,11,14-pentaoxyhexadecane to synthesize a benzophenone compound of the following formula (16).

[0343]

[0344] Using the obtained benzophenone of formula (16), a propargyl alcohol represented by formula (17) was synthesized with reference to the method described in Patent Document 1. PC4 was synthesized by carrying out a reaction using the propargyl alcohol compound of formula (17) instead of formula (10).

[0345]

[0346] (Photopolymerization initiator) PI: phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide (manufactured by IGM, Omnirad 819)

[0347] Example 1 (Production of Photochromic Curable Composition) First, the components were prepared according to the following formulation.

[0348] (A) Component (A-1) Component: 14G 90.0 parts by mass. (A-2) Component: TMPT 10.0 parts by mass. (A-3) Component: TSL 3.0 parts by mass. LA82 2.0 parts by mass.

[0349] (Photochromic compound): PC1 2.0 parts by mass. (Photopolymerization initiator): PI 0.3 parts by mass.

[0350] Next, all of the compounds corresponding to component (A) were mixed together, and then the photochromic compound and other additives were added thereto to obtain a photochromic curable composition. The (meth)acryloyl group content was calculated as follows.

[0351] (Calculation of (meth)acryloyl group content of each component) (meth)acryloyl group content of 14G (mmol / g) = (1 / (weight average molecular weight of 14G)) × methacryloyl groups per molecule × 1000 = 1 / (752) × 2 × 1000 = 2.66 mmol / g

[0352] The (meth)acryloyl group content of each component was calculated in the same manner as in Example 14G, and the results are as follows: (meth)acryloyl group content of TMPT (mmol / g): 8.87 mmol / g (meth)acryloyl group content of TSL (mmol / g): 4.03 mmol / g (meth)acryloyl group content of LA-82 (mmol / g): 4.18 mmol / g From the calculated (meth)acryloyl group content of each component and the content ratio of each component, the (meth)acryloyl group content of the polymerizable monomer was calculated as follows: 2.66 x (90.0 / 105.0) + 8.87 x (10.0 / 105.0) + 4.03 x (3.0 / 105.0) + 4.18 x (2.0 / 105.0) = 3.32 (mmol / g)

[0353] (Production of Optical Article) Using this photochromic curable composition, a photochromic laminate was obtained by a lamination method in which polymerization was carried out as follows.

[0354] First, a thiourethane-based plastic lens with a center thickness of 2 mm and a refractive index of 1.60 was prepared as an optical substrate. This thiourethane-based plastic lens was previously subjected to alkaline etching using a 5% aqueous solution of sodium hydroxide at 50°C for 5 minutes, and then thoroughly washed with distilled water.

[0355] Using a spin coater (1H-DX2, manufactured by MIKASA), the surface of the above plastic lens was coated with a moisture-curable primer (product name: TR-SC-P, manufactured by Tokuyama Corporation) at a rotation speed of 70 rpm for 15 seconds, followed by 10 seconds at 700 rpm. Thereafter, approximately 1 g of the above obtained photochromic curable composition was spin coated to form a photochromic coating layer with a thickness of 40 μm.

[0356] The lens having the photochromic curable composition (photochromic coating layer) applied to its surface was heated in a nitrogen gas atmosphere at an output of 200 mW / cm ２ The coating was cured by irradiating it with light for 90 seconds using a metal halide lamp, and then heated at 90°C for 1 hour to prepare a photochromic laminate having a photochromic layer.

[0357] Examples 2 to 17 and Comparative Examples 1 to 3 Photochromic cured products were prepared in the same manner as in Example 1, except that the photochromic curable compositions shown in Table 1 were used. In Examples 16, 17, and Comparative Example 1, photochromic cured products were prepared in the same manner as in Example 1, except that PC2, PC3, and PC4, respectively, were used as the photochromic compounds.

[0358] <Evaluation Method> The photochromic laminates obtained in the examples and comparative examples were evaluated by the methods described below. The results are shown in Table 2. (1) Photochromic Properties [1] Maximum absorption wavelength (λmax (nm)): This is the maximum absorption wavelength after color development measured using a spectrophotometer (instant multichannel photodetector MCPD3000) manufactured by Otsuka Electronics Co., Ltd., and was used as an index of the color tone during color development. [2] Color density at 23°C (A ２３ ) is the difference between the absorbance {ε(240)} at the maximum absorption wavelength after 300 seconds of light irradiation at 23°C and the absorbance ε(0) without light irradiation, and is used as an index of color density. The higher this value, the better the photochromic properties. [3] 23°C fading half-life [τ1 / 2 (sec.)] is the time required for the absorbance of the sample at the maximum absorption wavelength to decrease to 1 / 2 of {ε(300) - ε(0)} when the light irradiation is stopped after 300 seconds of light irradiation at 23°C, and is used as an index of the fading rate. The shorter this time, the faster the fading rate.

[0359] (2) Vickers hardness Vickers hardness was measured using a micro Vickers hardness tester PMT-X7A (manufactured by Matsuzawa Co., Ltd.). A square pyramidal diamond indenter was used as the indenter, and the measurement was performed under the conditions of a load of 10 gf and a holding time of the indenter of 30 seconds. A total of four measurements were performed, and the measurement results were shown as the average value of three measurements, excluding the value of the first measurement, which had a large measurement error.

[0360] (3) Elution Property In order to evaluate the ease of bleeding out of the photochromic compound, 20 sheets of the photochromic laminate were crushed into small pieces and immersed in 200 mL of 1-methoxy-2-propanol at 25°C for 12 hours. The 1-methoxy-2-propanol after immersion was filtered through a 0.45 μm PTFE filter, and the filtrate was exposed to sunlight to develop color. The elution property was evaluated visually from the intensity of the color development according to the following criteria A to D. The greater the degree of color development (closer to criterion D), the more likely the photochromic compound is to bleed out. A: No color development is observed. B: Slight color development. C: Light color development. D: Color development.

[0361] (4) Appearance In order to promote clouding due to bleeding out of the photochromic compound, the photochromic laminate was placed in a constant temperature and humidity chamber at 70°C and 98% Rh for 3 days. Thereafter, the photochromic laminate was exposed to fluorescent light in a black box, and the appearance was evaluated visually according to the following criteria A to D. A: No clouding at all. B: Very slight clouding is observed upon closer inspection. C: Cloudy upon closer inspection. D: Cloudy.

[0362] (5) Appearance after hard coating A hard coating layer was further laminated on the photochromic laminate using a hard coating composition prepared under the conditions shown below. The appearance was evaluated in the same manner as in (4) Appearance.

[0363] (Formation of Hard Coat Layer) t-Butanol (12.2 g), ethylene glycol monobutyl ether (7.0 g), acetylacetone (3.7 g), methyltriethoxysilane (0.41 g), γ-glycidoxypropyltrimethoxysilane (18.9 g), and a silicone surfactant (Dow-Toray Industries, Inc., trade name: L-7001) (0.06 g) were mixed and stirred at room temperature for 30 minutes. 9.0 g of 0.05 N hydrochloric acid was then added and stirred for 1 hour. Next, a 0.1 N solution of trimethylammonium chloride in methanol (3.2 g) was added and stirred at room temperature for 1 hour. Subsequently, methanol silica sol (solid content concentration: 30% by mass) (44.3 g) and aluminum acetylacetonate (0.51 g) were added and the mixture was aged overnight to obtain a hard coat composition.

[0364] The photochromic laminate was immersed in the hard coat composition and pulled up at a rate of 30 cm / min to coat both surfaces of the photochromic laminate with the hard coat composition. After coating, the composition was dried at 90°C for 20 minutes and then cured at 120°C for 4 hours to form a hard coat layer.

[0365]

[0366]

[0367] Examples 18 to 29 and Comparative Examples 4 to 10 Photochromic cured products were prepared in the same manner as in Example 1, except that the photochromic curable compositions shown in Table 3 were used. Note that photochromic cured products were prepared in the same manner as in Example 1, except that PC5 or PC6 was used as the photochromic compound. The evaluation results are shown in Table 4.

[0368] (Synthesis of PC5) 5.49 g (10.0 mmol) of a photochromic compound represented by the following formula (18) was added to 350 mL of tetrahydrofuran and cooled to -70°C. 7.5 mL of n-BuLi (1.6 mol / L hexane solution) was slowly added dropwise thereto while maintaining the temperature at -70°C or below. After the dropwise addition, the temperature was raised to room temperature over 5 hours. After stirring at room temperature for 2 hours, the mixture was ice-cooled, and 50 mL of water was added while maintaining the temperature at 5°C or below. 200 mL of toluene was added, and the mixture was separated. 50 mL of water was added, and the mixture was separated. The separation was repeated until the pH of the aqueous layer reached 7. The solvent from the resulting organic layer was removed, and the resulting mixture was purified by silica gel chromatography to obtain a compound represented by the following formula (19) in an 82% yield.

[0369] 100 mL of hexaethylene glycol and 190 mL of toluene were added to the compound represented by formula (19) obtained above, and 0.16 g of paratoluenesulfonic acid was added. The mixture was allowed to react while azeotropically dehydrating. After the reaction, the mixture was cooled to room temperature, and the reaction solution was slowly added to 50 mL of 5% aqueous sodium bicarbonate solution and stirred. After stirring, 100 mL of tetrahydrofuran and 150 mL of toluene were added, and the mixture was separated. 50 mL of water was added, and the mixture was washed with water. The solvent from the resulting organic layer was removed, and the mixture was purified by silica gel chromatography to obtain a compound represented by formula (20) below in a 71% yield. 100 mL of toluene was added to the obtained compound, and azeotropically dehydrating was performed while distilling off 20 mL of toluene. This solution was cooled to 50°C. Two drops of dibutyltin dilaurate were added to the cooled solution. 0.9 g of 2-methacryloyloxyethyl isocyanate was slowly added dropwise to this solution, and the mixture was allowed to react. After the reaction, 70 mL of water was added, and the mixture was separated. The solvent in the resulting organic layer was removed, and the residue was purified by silica gel chromatography to obtain PC5 represented by the following formula (21) in a yield of 89%.

[0370]

[0371]

[0372]

[0373]

[0374] (Synthesis of PC6) The same reaction as in the synthesis of PC5 was carried out except that hexaethylene glycol monomethyl ether was used in place of hexaethylene glycol, to obtain PC6 represented by the following formula (22) in a yield of 84%.

[0375]

[0376]

[0377]

[0378] Example 31 A protective layer was further laminated on the photochromic laminate obtained in the same manner as in Example 26, using a protective layer curable composition prepared under the conditions shown below.

[0379] (Preparation of Curable Composition for Protective Layer) TMPT (95.0 parts by mass), LA82 (5.0 parts by mass), PI (2.0 parts by mass), and FZ-2110 (0.03 parts by mass) were mixed to obtain a curable composition for protective layer.

[0380] (Production of Optical Article) 2 g of this curable composition for protective layer was spin-coated onto the surface of a photochromic laminate obtained in the same manner as in Example 26 at a rotation speed of 100 rpm for 10 to 60 seconds, and then at 800 rpm for 10 to 60 seconds. Thereafter, the curable composition for protective layer was spin-coated in a nitrogen gas atmosphere at an output of 200 mW / cm. ２ The coating was cured by irradiating the coating with light for 10 seconds using a metal halide lamp. The thickness of the cured protective layer was 20 μm. In this way, a laminate was obtained in which a protective layer was formed on a photochromic cured product. The photochromic properties of the obtained laminate with the protective layer laminated thereon were evaluated in the same manner as in Example 1, except for the evaluation of elution resistance as described below.

[0381] As an index of elution resistance, the average value obtained by subtracting the 23°C color development half-life of each peak of the photochromic laminate obtained in Example 31 from the 23°C color development half-life of each peak of the photochromic laminate obtained in Example 26, which did not have a protective layer, was calculated as the "decrease in color development rate (sec)." In other words, a large value is considered to indicate that the color development rate of the photochromic laminate was decreased as the photochromic compound in the photochromic layer migrated to the protective layer. The evaluation results are shown in Table 5.

[0382] Examples 32 to 34 and Comparative Examples 12 to 15 The protective layer curable composition was applied and cured in the same manner as in Example 31, except that the photochromic laminates obtained in Examples 27 to 29 and Comparative Examples 7 to 10 were used instead of the photochromic laminate obtained in Example 26 in Example 31, and laminates of Examples 32 to 34 and Comparative Examples 12 to 15 in which a protective layer was further laminated were obtained. The photochromic properties of the above laminates were evaluated in the same manner as in Example 31.

[0383]

[0384]

[0013] The following is a preferred embodiment of the present invention: [1] A curable composition comprising a radically polymerizable photochromic compound represented by the following formula (1) and a radically polymerizable monomer, wherein the radically polymerizable monomer comprises a first (meth)acrylate having a number average molecular weight of 600 or more, the first (meth)acrylate having a polyalkylene glycol chain structure having a number average molecular weight of 250 or more and two or more (meth)acryloyl groups, and the first (meth)acrylate accounts for 50 mass% or more of the radically polymerizable monomer:

[0385]

[0386] In the formula (1), M is a substituted or unsubstituted carbon, nitrogen, silicon, or germanium, and when it has two or more substituents, these substituents may be bonded to form a ring structure, ring A is a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to any of the above rings, and ring A may be absent, ring B is a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to any of the above rings, and R １ and R ２ are each independently a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, and M, ring A, ring B, R １ and R ２[2] The curable composition according to [1], wherein the ratio M1 / M2 of the mass M1 of the radical polymerizable photochromic compound to the mass M2 of the radical polymerizable monomer is 0.001 or more and 0.1 or less. [3] The curable composition according to [1] or [2], wherein the radical polymerizable substituent is represented by the following formula (X4): L １ -PG (X4) PG is a group having an ethylenically unsaturated bond, and L １ is a group represented by the following formula (X2):

[0387]

[0388] In the formula (X2), J represents a divalent group, each independently representing a direct bond, a substituted or unsubstituted methylene group, an oxygen atom, a sulfur atom, or NR ３０１ and R ３０１ is a hydrogen atom or an alkyl group, L is an oxygen atom or a sulfur atom, R ３００ is an alkylene group or a silylene group having an alkyl group or an aryl group as a substituent, and R ３０２ , R ３０３ , and R ３０４ are each independently an alkylene group, h, j, k and l are each independently 0 or 1, i is an integer of 0 to 200, and when i is 2 or more, the structures of the groups to which multiple i's are attached may be the same or different, and the dashed line represents a bond to PG. [4] The radical polymerizable photochromic compound represented by formula (1) contains a compound represented by the following formula (2),

[0389]

[0390] In the formula (2), R ３ , R ４ , R ５ , R ６ , R ７ , and R ８ At least one selected from the group consisting of is a group represented by formula (X4), ３ , R４ , R ５ , R ６ , R ７ , and R ８ each independently represents a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted haloalkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a cyano group, a halogen atom, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a nitro group, a formyl group, a hydroxycarbonyl group, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted alkoxy ... R is an alkoxycarbonyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aralkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a thiol group, a substituted or unsubstituted alkoxyalkylthio group, a substituted or unsubstituted haloalkylthio group, a substituted or unsubstituted cycloalkylthio group, a substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, a group represented by the following formula (2a), a group represented by the following formula (X), or a group represented by the following formula (X3), ３ and R ４ may together with the carbon atom to which they are bonded form a substituted or unsubstituted aliphatic ring having 3 to 20 ring carbon atoms, a substituted or unsubstituted fused polycyclic ring in which an aromatic hydrocarbon ring or an aromatic heterocycle is fused to the aliphatic ring, a substituted or unsubstituted heterocycle having 3 to 20 ring atoms, or a substituted or unsubstituted fused polycyclic ring in which an aromatic ring or an aromatic heterocycle is fused to the heterocycle, a100 is an integer of 1 or more and 4 or less, a101 is an integer of 1 or more and 4 or less, a102 is an integer of 1 or more and 5 or less, and a103 is an integer of 1 or more and 5 or less, when a100 is 2 or more and 4 or less, a plurality of R ５ may be the same or different, and when a101 is 2 or more and 4 or less, a plurality of R ６ may be the same or different, and when a102 is 2 or more and 5 or less, a plurality of R ７may be the same or different, and when a103 is 2 or more and 4 or less, a plurality of R ８ may be the same or different, a100 is 2 or more and 4 or less, and adjacent R ５ If there is a ５ is R ５ and a101 may form, together with the carbon atom bonded to it, a substituted or unsubstituted aliphatic ring, a substituted or unsubstituted aliphatic heterocycle, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to any of these rings, ６ If there is a ６ is R ６ and a102 may form, together with the carbon atom bonded to it, a substituted or unsubstituted aliphatic ring, a substituted or unsubstituted aliphatic heterocycle, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to any of these rings, ７ If there is a ７ is R ７ and a103 may form a substituted or unsubstituted aliphatic ring, a substituted or unsubstituted aliphatic heterocycle, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to any of these rings, together with the carbon atom bonded to the ８ If there is a ８ is R ８ and -Q may together with the carbon atom bonded to form a substituted or unsubstituted aliphatic ring, a substituted or unsubstituted aliphatic heterocycle, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to any of these rings, １００ - (P １００ Q ２００ ) ａａ -P ２００ Q３００ (2a) In the formula (2a), Q １００ is an alkylene group which may contain a halogen atom as a substituent, and Q ２００ is an alkylene group which may contain a halogen atom as a substituent, and Q ３００ is an alkyl group which may contain a halogen atom as a substituent, １００ , and P ２００ are each independently O, S, or NR ７００ , P.R. ７０１ , or P(=O), R ７００ , and R ７０１ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group; aa represents 0 or 1 to 10;

[0391]

[0392] In the formula (X), E is an oxygen atom or NR １０１ and R １０１ is a hydrogen atom or an alkyl group, F is an oxygen atom or a sulfur atom, G is an oxygen atom, a sulfur atom or NR ２０２ and R ２０２ is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group; g is 0 or 1; R ２０１ is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group, and when G is an oxygen atom or a sulfur atom, R ２０１ is a group other than a hydrogen atom, and L １ -R ４００ (X3) In the formula (X3), L １ has the same meaning as in formula (X4), ４００ is a hydrogen atom, an alkyl group, an aryl group, a photochromic group, or a silyl group having an alkyl group, an alkoxy group, or an aryl group as a substituent. [5] The R ３ , and the R ４are each independently any one of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, and a group represented by the formula (2a), or ３ , and the R ４ and form, together with the carbon atom to which they are bonded, any one of a substituted or unsubstituted aliphatic ring having 3 to 20 ring carbon atoms, a substituted or unsubstituted fused polycyclic ring in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is fused to the aliphatic ring, a substituted or unsubstituted heterocyclic ring having 3 to 20 ring atoms, and a substituted or unsubstituted fused polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is fused to the heterocyclic ring. [6] The curable composition according to [4], ３ , and the R ４ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, or a group represented by the formula (2a), ７ [7] The curable composition according to [4] or [5], wherein R is a group represented by formula (X4): ３ , and R ４ [8] The curable composition according to any one of [1] to [7], wherein the first (meth)acrylate is a (meth)acrylate not containing a cyclic structure. [9] The curable composition according to any one of [1] to [8], wherein the first (meth)acrylate contains at least one selected from the group consisting of (meth)acrylates represented by the following formula (3) and (meth)acrylates represented by the following formula (4):

[0393]

[0394] In the formula (3), Q ３ and Q ６ are each independently a hydrogen atom or a methyl group, and Q ４ and Q ５ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and Q ７ is a divalent group having a number average molecular weight of 600 or more and represented by the following formula (3a), a and b each independently represent 0 or more and 10 or less, and Z1 and Z ２ are each independently 0 or 1,

[0395]

[0396] In the formula (3a), Q ７ａ , Q ７ｂ , Q ７ｄ , and Q ７ｅ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and Q ７ａ and Q ７ｂ are different groups, and Q ７ｄ and Q ７ｅ are different groups, and Q ７ｃ represents a linear or branched alkylene group having 2 to 10 carbon atoms which may have a substituent, d1 and h1 are 0 or more and 10 or less, e1 and g1 are 0 or more and 20 or less, and f1 is 3 or more and 100 or less,

[0397]

[0398] In the formula (4), Q １０ is a linear or branched alkylene group having 1 to 3 carbon atoms, and Q １１ is a linear or branched alkylene group having 1 to 10 carbon atoms; １２ is a hydrogen atom or a methyl group, and Q １３ represents a trivalent to hexavalent organic group having 1 to 10 carbon atoms, a1 is 0 or 1, b1 is 3 or more and 15 or less, and c1 is 3, 4, 5, or 6.

[10] The curable composition according to any one of [1] to [9], wherein the radical polymerizable monomer further contains a second (meth)acrylate having three or more (meth)acryloyl groups and represented by the following formula (5):

[0399]

[0400] In the formula (5), Q １０ , Q １１ , Q １２ , Q １３, a1, and c1 are defined as in formula (4), and b2 is 0, 1, 2, or 3.

[11] The curable composition according to any one of [1] to

[10] , wherein the radically polymerizable monomer has a (meth)acryloyl group content of less than 5.50 mmol / g.

[12] A cured product obtained by curing the curable composition according to any one of [1] to

[11] .

[13] A laminate comprising an optical substrate and a resin layer comprising the cured product according to

[12] .

[14] A laminate comprising an optical substrate, a primer layer comprising a urethane resin, and a resin layer comprising the cured product according to

[12] laminated on the primer layer.

[15] The laminate according to

[14] , wherein the Vickers hardness of the laminate measured according to Japanese Industrial Standards Z 2244-2009: Micro Vickers Hardness Test is less than 5.0.

[16] The laminate according to

[14] or

[15] , further comprising a hard coat layer covering at least a portion of the resin layer and containing an inorganic oxide.

[17] The laminate according to any one of

[14] to

[16] , further comprising a protective layer covering at least a portion of the resin layer and containing at least one resin selected from the group consisting of acrylic resins, urethane resins, and epoxy resins.

[18] An optical article comprising the cured product according to

[12] .

[19] A lens comprising the cured product according to

[12] .

[20] Eyeglasses comprising the lens according to

[19] .

Claims

1. A curable composition comprising a radically polymerizable photochromic compound represented by the following formula (1) and a radically polymerizable monomer, wherein the radically polymerizable monomer comprises a first (meth)acrylate having a number average molecular weight of 600 or more, the first (meth)acrylate having a polyalkylene glycol chain structure having a number average molecular weight of 250 or more and two or more (meth)acryloyl groups, and the proportion of the first (meth)acrylate in the radically polymerizable monomer is 50 mass% or more: In the formula (1), M is a substituted or unsubstituted carbon, nitrogen, silicon, or germanium, and when it has two or more substituents, these substituents may be bonded to form a ring structure, ring A is a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to any of the above rings, and ring A may be absent, ring B is a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to any of the above rings, and R １ and R ２ are each independently a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, and M, ring A, ring B, R １ and R ２ At least one selected from the group consisting of has a radically polymerizable substituent.

2. The curable composition according to claim 1, wherein the ratio M1 / M2 of the mass M1 of the radical polymerizable photochromic compound to the mass M2 of the radical polymerizable monomer is 0.001 or more and 0.1 or less.

3. The curable composition according to claim 1, wherein the radical polymerizable substituent is represented by the following formula (X4): L １ -PG (X4) PG is a group having an ethylenically unsaturated bond, and L １ is a group represented by the following formula (X2): In the formula (X2), J represents a divalent group, each independently representing a direct bond, a substituted or unsubstituted methylene group, an oxygen atom, a sulfur atom, or NR ３０１ and R ３０１ is a hydrogen atom or an alkyl group, L is an oxygen atom or a sulfur atom, R ３００ is an alkylene group or a silylene group having an alkyl group or an aryl group as a substituent, and R ３０２ , R ３０３ , and R ３０４ are each independently an alkylene group; h, j, k, and l are each independently 0 or 1; i is an integer of 0 or more and 200 or less, and when i is 2 or more, the structures of the groups to which multiple i's are attached may be the same or different, and the dashed line represents a bond to PG.

4. The curable composition according to claim 3, wherein the radically polymerizable photochromic compound represented by formula (1) includes a compound represented by the following formula (2): In the formula (2), R ３ , R ４ , R ５ , R ６ , R ７ , and R ８ At least one selected from the group consisting of is a group represented by formula (X4), ３ , R ４ , R ５ , R ６ , R ７ , and R ８ each independently represents a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted haloalkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a cyano group, a halogen atom, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a nitro group, a formyl group, a hydroxycarbonyl group, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted alkoxy ... R is an alkoxycarbonyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aralkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a thiol group, a substituted or unsubstituted alkoxyalkylthio group, a substituted or unsubstituted haloalkylthio group, a substituted or unsubstituted cycloalkylthio group, a substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, a group represented by the following formula (2a), a group represented by the following formula (X), or a group represented by the following formula (X3), ３ and R ４ may together with the carbon atom to which they are bonded form a substituted or unsubstituted aliphatic ring having 3 to 20 ring carbon atoms, a substituted or unsubstituted fused polycyclic ring in which an aromatic hydrocarbon ring or an aromatic heterocycle is fused to the aliphatic ring, a substituted or unsubstituted heterocycle having 3 to 20 ring atoms, or a substituted or unsubstituted fused polycyclic ring in which an aromatic ring or an aromatic heterocycle is fused to the heterocycle, a100 is an integer of 1 or more and 4 or less, a101 is an integer of 1 or more and 4 or less, a102 is an integer of 1 or more and 5 or less, and a103 is an integer of 1 or more and 5 or less, when a100 is 2 or more and 4 or less, a plurality of R ５ may be the same or different, and when a101 is 2 or more and 4 or less, a plurality of R ６ may be the same or different, and when a102 is 2 or more and 5 or less, a plurality of R ７ may be the same or different, and when a103 is 2 or more and 4 or less, a plurality of R ８ may be the same or different, a100 is 2 or more and 4 or less, and adjacent R ５ If there is a ５ is R ５ and a101 may form, together with the carbon atom bonded to it, a substituted or unsubstituted aliphatic ring, a substituted or unsubstituted aliphatic heterocycle, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to any of these rings, ６ If there is a ６ is R ６ and a102 may form, together with the carbon atom bonded to it, a substituted or unsubstituted aliphatic ring, a substituted or unsubstituted aliphatic heterocycle, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to any of these rings, ７ If there is a ７ is R ７ and a103 may form a substituted or unsubstituted aliphatic ring, a substituted or unsubstituted aliphatic heterocycle, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to any of these rings, together with the carbon atom bonded to the ８ If there is a ８ is R ８ and -Q may together with the carbon atom bonded to form a substituted or unsubstituted aliphatic ring, a substituted or unsubstituted aliphatic heterocycle, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to any of these rings, １００ - (P １００ Q ２００ ) ａａ -P ２００ Q ３００ (2a) In the formula (2a), Q １００ is an alkylene group which may contain a halogen atom as a substituent, and Q ２００ is an alkylene group which may contain a halogen atom as a substituent, and Q ３００ is an alkyl group which may contain a halogen atom as a substituent, １００ , and P ２００ are each independently O, S, or NR ７００ , P.R. ７０１ , or P(=O), R ７００ , and R ７０１ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, aa is 0 or 1 to 10, In the formula (X), E is an oxygen atom or NR １０１ and R １０１ is a hydrogen atom or an alkyl group, F is an oxygen atom or a sulfur atom, G is an oxygen atom, a sulfur atom or NR ２０２ and R ２０２ is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group; g is 0 or 1; R ２０１ is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group, and when G is an oxygen atom or a sulfur atom, R ２０１ is a group other than a hydrogen atom, and L １ -R ４００ (X3) In the formula (X3), L １ has the same meaning as in formula (X4), ４００ is a hydrogen atom, an alkyl group, an aryl group, a photochromic group, or a silyl group having an alkyl group, an alkoxy group, or an aryl group as a substituent.

5. The above R ３ , and the R ４ are each independently any one of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, and a group represented by the formula (2a), or ３ , and the R ４ and form, together with the carbon atom to which they are bonded, any one of a substituted or unsubstituted aliphatic ring having 3 to 20 ring carbon atoms, a substituted or unsubstituted fused polycyclic ring in which an aromatic hydrocarbon ring or an aromatic heterocycle is fused to the aliphatic ring, a substituted or unsubstituted heterocycle having 3 to 20 ring atoms, and a substituted or unsubstituted fused polycyclic ring in which an aromatic ring or an aromatic heterocycle is fused to the heterocycle.

6. The above R ３ , and the R ４ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, or a group represented by the formula (2a), ７ The curable composition according to claim 4, wherein: is a group represented by formula (X4).

7. The above R ３ , and R ４ The curable composition according to claim 6, wherein the structures of are different from each other.

8. The curable composition according to claim 1, wherein the first (meth)acrylate is a (meth)acrylate that does not contain a cyclic structure.

9. The curable composition according to claim 1, wherein the first (meth)acrylate comprises at least one selected from the group consisting of (meth)acrylates represented by the following formula (3) and (meth)acrylates represented by the following formula (4): In the formula (3), Q ３ and Q ６ are each independently a hydrogen atom or a methyl group, and Q ４ and Q ５ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and Q ７ is a divalent group having a number average molecular weight of 600 or more and represented by the following formula (3a), a and b each independently represent 0 or more and 10 or less, and Z 1 and Z ２ are each independently 0 or 1, In the formula (3a), Q ７ａ , Q ７ｂ , Q ７ｄ , and Q ７ｅ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and Q ７ａ and Q ７ｂ are different groups, and Q ７ｄ and Q ７ｅ are different groups, and Q ７ｃ represents a linear or branched alkylene group having 2 to 10 carbon atoms which may have a substituent, d1 and h1 are 0 or more and 10 or less, e1 and g1 are 0 or more and 20 or less, and f1 is 3 or more and 100 or less, In the formula (4), Q １０ is a linear or branched alkylene group having 1 to 3 carbon atoms, and Q １１ is a linear or branched alkylene group having 1 to 10 carbon atoms; １２ is a hydrogen atom or a methyl group, and Q １３ represents a trivalent to hexavalent organic group having 1 to 10 carbon atoms; a1 is 0 or 1; b1 is 3 or more and 15 or less; and c1 is 3, 4, 5, or 6.

10. The curable composition according to claim 9, wherein the radical polymerizable monomer further comprises a second (meth)acrylate having three or more (meth)acryloyl groups and represented by the following formula (5): In the formula (5), Q １０ , Q １１ , Q １２ , Q １３ , a1, and c1 have the same meanings as in the formula (4), and b2 is 0, 1, 2, or 3.

11. The curable composition according to claim 1, wherein the radically polymerizable monomer has a (meth)acryloyl group content of less than 5.50 mmol / g.

12. A cured product obtained by curing the curable composition according to claim 1.

13. A laminate comprising an optical substrate and a resin layer containing the cured product according to claim 12.

14. A laminate comprising: an optical substrate; a primer layer containing a urethane resin; and a resin layer containing the cured product according to claim 12 laminated on the primer layer.

15. The laminate according to claim 14, wherein the laminate has a Vickers hardness of less than 5.0 as measured by the Micro Vickers Hardness Test according to Japanese Industrial Standards Z 2244-2009.

16. The laminate according to claim 14, further comprising a hard coat layer containing an inorganic oxide and covering at least a portion of the resin layer.

17. The laminate according to claim 14, further comprising a protective layer covering at least a portion of the resin layer and containing at least one resin selected from the group consisting of acrylic resins, urethane resins, and epoxy resins.

18. An optical article comprising the cured product according to claim 12.

19. A lens comprising the cured product of claim 12.

20. Eyeglasses comprising a lens according to claim 19.

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