Photochromic compound, photochromic curable composition, cured product, lens, and eyeglasses

Abstract

The present invention aims to provide a photochromic compound which can exhibit photochromic properties independently of a matrix, stably exist in dispersion without aggregation during optical substrate formation (curing process). According to the present invention, by a macromolecular photochromic compound having a block polymer-like group of a low polymer chain group having superior compatibility with a solid matrix and a low polymer chain group having poor compatibility with a solid matrix, a nano- to micro-sized phase separation structure is formed in the solid matrix, and the dispersion can be improved and aggregation can be inhibited independently of the solid matrix, and as a result, a high degree of photochromic properties can be exhibited.

Description

Technical Field

[0001] This invention relates to photochromic compounds, photochromic curable compositions, cured products, lenses, and eyeglasses. Background Technology

[0002] Photochromic compounds, such as chromene compounds, succinic anhydride compounds, and spiroxazine compounds, have the property of rapidly changing color when exposed to ultraviolet light, such as sunlight or mercury lamp light, and returning to their original color when the light exposure is stopped and they are placed in the dark (photochromism). This property is used for various applications, especially for optical materials.

[0003] For example, eyeglass lenses containing photochromic compounds rapidly color outdoors under ultraviolet light, such as sunlight, functioning as sunglasses, while fading indoors in the absence of such light, functioning as clear eyeglasses. In recent years, the demand for photochromic optical products with such photochromic properties has been expanding.

[0004] As a method for manufacturing such photochromic optical articles, one example is using a photochromic composition containing a polymeric compound and a photochromic compound.

[0005] (a) A method of dissolving a photochromic compound in a polymerizable compound, causing it to polymerize and form a solidified product, which can then be directly used as an optical item such as a lens. This method is called the mixing method.

[0006] (b) A method of applying a cured layer of photochromic compound dispersed on the surface of a plastic molded article such as a lens by coating or casting polymerization. This method is called the lamination method.

[0007] (c) A method for curing and bonding two optical sheets together an adhesive layer formed from an adhesive resin in which a photochromic compound is dispersed. This method is called the adhesive method.

[0008] For optical articles that are endowed with photochromic properties, the following characteristics are also required.

[0009] (I) The chromaticity (initial chromaticity) of the visible light region before ultraviolet irradiation is low.

[0010] (II) High color intensity (color concentration) when irradiated with ultraviolet light.

[0011] (III) The speed at which the color returns to its original state after the UV radiation stops (fading speed) is fast.

[0012] (IV) Good repeatability of the reversible effects of color development and fading.

[0013] (V) High storage stability.

[0014] (VI) It can be easily shaped into various forms.

[0015] To date, various photochromic compounds have been reported, but even those with good photoresponsiveness in liquid matrices tend to exhibit poor photoresponsiveness and longer fading half-lives in solid matrices. This can be attributed to the fact that the free space in solid matrices is much smaller than in liquid matrices, thus limiting structural variations in the photochromic compounds. As a solution to this problem, photochromic compounds (hereinafter also referred to as "polymeric photochromic compounds") with oligomer groups such as polyalkylene oxide oligomer groups and polysiloxane oligomer groups have been disclosed in recent years. These polymeric photochromic compounds have been reported to exhibit low matrix dependence and excellent photoresponsiveness even in solid matrices because the oligomer groups can form free space. (See Patent Documents 1-6).

[0016] Existing technical documents

[0017] Patent documents

[0018] Patent Document 1: International Publication No. 2004 / 041961

[0019] Patent Document 2: International Publication No. 2000 / 015630

[0020] Patent Document 3: International Publication No. 2009 / 146509

[0021] Patent Document 4: International Publication No. 2012 / 149599

[0022] Patent Document 5: International Publication No. 2012 / 162725

[0023] Patent Document 6: Japanese Patent Application Publication No. 2019-182866 Summary of the Invention

[0024] The problem the invention aims to solve

[0025] As mentioned earlier, photochromic polymers exhibit high photochromic properties in solid matrices. However, cured products of photochromic compositions containing photochromic polymers sometimes exhibit cloudiness. That is, it can be assumed that if the solid matrix and the photochromic polymer have low compatibility, the photochromic polymer will aggregate in the cured product, leading to cloudiness.

[0026] On the other hand, since low-molecular-weight photochromic compounds without oligomer chain groups do not aggregate in a solid matrix, transparent photochromic cured products can be obtained when using compositions containing only low-molecular-weight photochromic compounds. However, low-molecular-weight photochromic compounds are highly matrix-dependent, and sometimes the fading rate in a solid matrix can become a problem.

[0027] The object of the present invention is to provide a photochromic compound that exhibits photochromic properties independently of a matrix and is stably dispersed in a cured product without aggregation; a photochromic curable composition containing the photochromic compound; a cured product; a lens; and eyeglasses.

[0028] Solution for solving the problem

[0029] In order to solve the above-mentioned technical problems, the inventors conducted research on ensuring free space and compatibility between the polymeric photochromic compound and the solid matrix. As a result, they found that if the following steps are taken, free space can be ensured and compatibility with the solid matrix can be improved.

[0030] In other words, by manufacturing a polymeric photochromic compound having block polymer-like groups with oligomer chain groups that have excellent compatibility with the solid matrix and oligomer chain groups that have poor compatibility with the solid matrix, the oligomer chain group portion with excellent compatibility is compatible with the solid matrix, while the oligomer chain group portion with poor compatibility forms free space in the solid matrix, forming a phase-separated structure at the nanometer to micrometer scale. As a result, the polymeric photochromic compound does not aggregate in the solid matrix, thereby improving dispersibility. To this end, various block polymer-like groups serving as oligomer chain groups were studied, and it was found that using a specific combination of block polymer-like groups resulted in excellent dispersibility in the solid matrix and the ability to exhibit high photochromic properties, thus completing this invention.

[0031] That is, the first embodiment is a photochromic compound, which is represented by the following formula (1) or (2).

[0032]

[0033] (In the formula, PC is a group having at least one photochromic site,)

[0034] X1 and X3 are each independently a straight-chain or branched alkylene group with 12 to 30 carbon atoms, a polyoxypropylene group with 3 to 200 repeating units, a polyoxyethylene group with 3 to 200 repeating units, a polyoxytetramethylene group with 3 to 200 repeating units, or a polysiloxane group with 3 to 200 repeating units.

[0035] The repeating unit of the polysiloxane contains a siloxane having two substituents selected from the group consisting of a straight-chain or branched alkyl group having 1 to 10 carbon atoms, a straight-chain or branched alkoxy group having 1 to 10 carbon atoms, and an aromatic group having 6 to 10 carbon atoms.

[0036] X2 is a straight-chain or branched alkylene group with 12 to 30 carbon atoms, a polyoxypropylene group with 3 to 200 repeating units, a polyoxyethylene group with 3 to 200 repeating units, or a polyoxytetramethylene group with 3 to 200 repeating units.

[0037] X1 and X2 are different groups.

[0038] X2 and X3 are different groups.

[0039] X1 and X3 can be the same type of functional group.

[0040] When X2 in formula (1) or X3 in formula (2) is a straight-chain or branched alkylene group with 12 to 30 carbon atoms, Z is a hydrogen atom, a methyl group, or an alkoxy group with 1 to 10 carbon atoms. When X2 in formula (1) or X3 in formula (2) is a polyoxypropylene group with 3 to 200 repeating units, a polyoxyethyl group with 3 to 200 repeating units, a polyoxytetramethylene group with 3 to 200 repeating units, or a polysiloxane group with 3 to 200 repeating units formed from a methylene siloxy group, Z is a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, or an alkoxy group with 1 to 10 carbon atoms. The methylene siloxy group has two substituents selected from the group consisting of a straight-chain or branched alkyl group with 1 to 10 carbon atoms, a straight-chain or branched alkoxy group with 1 to 10 carbon atoms, and an aromatic group with 6 to 10 carbon atoms.

[0041] L1 is a direct bond or a divalent atomic bond.

[0042] L2 represents a direct bond or an m+1 valence atomic bond.

[0043] L3 represents a direct bond or a l+1 valence atomic bond.

[0044] n is an integer from 1 to 8, m is an integer from 1 to 4, and l is an integer from 1 to 4.

[0045] The second embodiment is a photochromic curable composition containing the photochromic compound and polymeric compound involved in the embodiments.

[0046] The third embodiment is a cured product obtained by polymerizing the photochromic curable composition involved in the embodiment.

[0047] The fourth embodiment is a lens containing the cured material involved in the embodiment.

[0048] The fifth embodiment is a pair of eyeglasses containing the lens described in the embodiment.

[0049] The effects of the invention

[0050] The photochromic compound of the present invention exhibits excellent photochromic properties in a solid matrix. Furthermore, while conventional polymeric photochromic compounds sometimes produce problems such as cloudiness in the cured product, the photochromic compound of the present invention enables the production of transparent photochromic cured products with excellent photochromic properties. Detailed Implementation

[0051] According to an embodiment, a photochromic compound can be provided, which is represented by the following formula (1).

[0052]

[0053] In formula (1), PC is a group having at least one photochromic site.

[0054] X1 is an alkylene group, polyoxypropylene group, polyoxyethylene group, polyoxytetramethylene group, or polysiloxane group.

[0055] X2 is an alkylene group, polyoxypropylene group, polyoxyethylene group, or polyoxytetramethylene group.

[0056] X1 and X2 are different groups.

[0057] When X2 is an alkylene group, Z is a hydrogen atom, a methyl group, or an alkoxy group with 1 to 10 carbon atoms. When X2 is polyoxypropylene, polyoxyethylene, polyoxytetramethylene, or polysiloxane, Z is a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, or an alkoxy group with 1 to 10 carbon atoms.

[0058] L1 is a direct bond or a divalent atomic bond.

[0059] L2 represents a direct bond or an m+1 valence atomic bond.

[0060] n is an integer from 1 to 8, and m is an integer from 1 to 4.

[0061] In addition, according to an embodiment, a photochromic compound can be provided, which is shown in the following formula (2).

[0062]

[0063] In equation (2), PC, X1, X2, L1, L2, m and n are defined in the same way as in equation (1).

[0064] X3 is an alkylene group, polyoxypropylene group, polyoxyethylene group, polyoxytetramethylene group, or polysiloxane group.

[0065] X1 and X2 are different groups. X2 and X3 are different groups. X1 and X3 can be the same group or different groups.

[0066] When X3 is an alkylene group, Z is a hydrogen atom, a methyl group, or an alkoxy group with 1 to 10 carbon atoms. When Z is X3, which is polyoxypropylene, polyoxyethylene, polyoxytetramethylene, or polysiloxane, Z is a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, or an alkoxy group with 1 to 10 carbon atoms.

[0067] L3 represents a direct bond or an atomic bond with a valence of l+1.

[0068] l is an integer from 1 to 4.

[0069] In X1, X2, or X3, the alkylene group has 12 to 30 carbon atoms, more preferably 12 to 20. The alkylene group can be linear or branched, but linear is preferred.

[0070] In X1, X2, or X3, the repeating unit of the polyoxypropylene group is represented by (-CH2-CH(CH3)-O-). The number of repeating units is 3 to 200, preferably 5 to 150, more preferably 5 to 100, and even more preferably 10 to 50.

[0071] In X1, X2, or X3, the repeating unit of the polyoxyethylene is represented by (-CH2-CH2-O-). The number of repeating units is 3 to 200, preferably 5 to 150, more preferably 5 to 100, and even more preferably 10 to 50.

[0072] In X1, X2, or X3, the repeating unit of polyoxytetramethylene is represented by (-CH2-CH2-CH2-CH2-O-). The number of repeating units is 3 to 200, preferably 5 to 150, more preferably 5 to 100, and even more preferably 10 to 50.

[0073] In X1, X2, or X3, the repeating unit of the polysiloxane is composed of (-Si(R) 10 The methylenesilyloxy group (siloxane) is represented by )2-O-). R 10 It is a straight-chain or branched alkyl group having 1 to 10 carbon atoms, a straight-chain or branched alkoxy group having 1 to 10 carbon atoms, or an aromatic group having 6 to 10 carbon atoms. R 10 Preferably alkyl, more preferably methyl. It should be noted that the two Rs... 10 They may be different from or the same as each other, but are preferably the same. The number of repeating units of the polysiloxane is 3 to 200, preferably 5 to 150, more preferably 5 to 100, and even more preferably 10 to 50.

[0074] The photochromic compounds involved in the embodiments contain oligomer chains with structures different from X1 and X2. It can be considered that the compatibility of X1 and X2 differs in a particular matrix. X1, exhibiting higher compatibility in a particular matrix, helps to prevent the photochromic compound from agglomerating. X2, with lower compatibility, helps to form free spaces in the matrix that facilitate structural changes in the photochromic compound. In other matrices, X1 may exhibit lower compatibility, and X2 may exhibit higher compatibility. Therefore, when using a composition containing photochromic compounds possessing both X1 and X2, a cured product with excellent photochromic properties and high transparency can be obtained regardless of the type of matrix.

[0075] Furthermore, in the photochromic compound involved in the embodiments, Z is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. Having such a structure allows for more efficient formation of microlayer separation structures.

[0076] Furthermore, the photochromic compound involved in the embodiment may contain a linking group L2 between X1 and X2. Since the photochromic compound containing a linking group L2 between X1 and X2 can clearly separate the parts with different compatibility through the linking group L1, it can more effectively form a microlayer separation structure.

[0077] Next, we will provide a detailed explanation.

[0078] <X1, X2, X3>

[0079] In the photochromic compound, X1 and X3 are each independently selected from the following oligomer chain groups: linear or branched alkylene groups with 12 to 30 carbon atoms, polyoxypropylene groups with 3 to 200 repeating units, polyoxyethylene groups with 3 to 200 repeating units, polyoxytetramethylene groups with 3 to 200 repeating units, or polysiloxane groups with 3 to 200 repeating units formed from methylenesiloxy groups, wherein the methylenesiloxy group has two substituents selected from linear or branched alkyl groups with 1 to 10 carbon atoms, linear or branched alkoxy groups with 1 to 10 carbon atoms, and aromatic groups with 6 to 10 carbon atoms as substituents.

[0080] X2 is selected from the following oligomer chain groups: linear or branched alkylene groups with 12 to 30 carbon atoms, polyoxypropylene with 3 to 200 repeating units, polyoxyethylene with 3 to 200 repeating units, or polyoxytetramethylene with 3 to 200 repeating units.

[0081] As the aforementioned straight-chain or branched alkylene groups having 12 to 30 carbon atoms, straight-chain alkylene groups are preferred.

[0082] Furthermore, the polysiloxane group containing a methylenesiloxane group having two substituents selected from the above-mentioned straight-chain or branched alkyl groups having 1 to 10 carbon atoms, straight-chain or branched alkoxy groups having 1 to 10 carbon atoms, and aromatic groups having 6 to 10 carbon atoms is preferably polydimethylsiloxane, polymethylphenylsiloxane, or polydiphenylsiloxane.

[0083] In the photochromic compound, X1 and X2, which are bonded by atomic bond L2 (described later), and / or X2 and X3, which are bonded by atomic bond L3, are selected from different functional groups. X1 and X3 can be the same functional group or different functional groups. It can be considered that by making X1 and X2, and X2 and X3, different functional groups, thereby creating a block polymer-like structure, the inventive effect can be achieved.

[0084] For example, when X2 is a polyoxypropylene group with 3 to 200 repeating units, X1 and X3 are groups other than polyoxypropylene groups with 3 to 200 repeating units, that is, oligomer chains selected from linear or branched alkylene groups with 12 to 30 carbon atoms, polyoxyethylene groups with 3 to 200 repeating units, polyoxytetramethylene groups with 3 to 200 repeating units, or polysiloxane groups with 3 to 200 repeating units formed by methylene siloxy groups, wherein the methylene siloxy group has two substituents selected from linear or branched alkyl groups with 1 to 10 carbon atoms, linear or branched alkoxy groups with 1 to 10 carbon atoms, and aromatic groups with 6 to 10 carbon atoms as substituents.

[0085] The combination of X1, X2, and X3 can be appropriately determined based on the desired photochromic properties and the type of solid matrix in which the photochromic compound is dispersed.

[0086] In the case of the photochromic compound represented by formula (1), the preferred option is:

[0087] The following combination is used: X1 is an oligomer chain selected from linear or branched alkylene groups with 12 to 30 carbon atoms, polyoxypropylene with 3 to 200 repeating units, or polysiloxane groups with 3 to 200 repeating units formed by methylene siloxy groups, wherein the methylene siloxy group has two substituents selected from linear or branched alkyl groups with 1 to 10 carbon atoms, linear or branched alkoxy groups with 1 to 10 carbon atoms, and aromatic groups with 6 to 10 carbon atoms; X2 is an oligomer chain selected from polyoxyethylene with 3 to 200 repeating units, or polyoxytetramethylene with 3 to 200 repeating units.

[0088] The following combinations are possible: X1 is a polyoxyethylene with 3 to 200 repeating units; X2 is an oligomer chain selected from linear or branched alkylene groups with 12 to 30 carbon atoms, polyoxypropylene with 3 to 200 repeating units, or polyoxytetramethylene with 3 to 200 repeating units; or

[0089] The following combination is used: X1 is a polyoxytetramethylene compound with 3 to 200 repeating units; X2 is an oligomer chain selected from linear or branched alkylene compounds with 12 to 30 carbon atoms, polyoxypropylene compounds with 3 to 200 repeating units, or polyoxyethylene compounds with 3 to 200 repeating units.

[0090] Furthermore, in the case of the photochromic compound shown in formula (2), it is preferable to:

[0091] The following combinations are used: X1 is a polyoxyethylene with 3 to 200 repeating units; X2 is an oligomer chain selected from linear or branched alkylene groups with 12 to 30 carbon atoms, polyoxypropylene with 3 to 200 repeating units, or polyoxytetramethylene with 3 to 200 repeating units; X3 is a polyoxyethylene group selected from linear or branched alkylene groups with 12 to 30 carbon atoms, polyoxyethylene with 3 to 200 repeating units, or polyoxytetramethylene with 3 to 200 repeating units. The polyoxypropylene, polyoxytetramethylene with 3 to 200 repeating units, or polysiloxane with 3 to 200 repeating units, wherein the repeating unit of the polysiloxane contains a methylenesiloxy group having two substituents selected from a straight-chain or branched alkyl group with 1 to 10 carbon atoms, a straight-chain or branched alkoxy group with 1 to 10 carbon atoms, and an aromatic group with 6 to 10 carbon atoms as substituents, X2 and X3 are different;

[0092] The following combination is used: X1 is an oligomer chain selected from linear or branched alkylene groups with 12 to 30 carbon atoms, polyoxypropylene with 3 to 200 repeating units, or polysiloxane groups with 3 to 200 repeating units formed from methylenesiloxy groups, wherein the methylenesiloxy group has two substituents selected from linear or branched alkyl groups with 1 to 10 carbon atoms, linear or branched alkoxy groups with 1 to 10 carbon atoms, and aromatic groups with 6 to 10 carbon atoms; X2 is an oligomer chain selected from polyoxyethylene with 3 to 200 repeating units, or polyoxytetramethylene with 3 to 200 repeating units. Polymer chain group; X3 is an oligomer chain group selected from linear or branched alkylene groups with 12 to 30 carbon atoms, polyoxyethylene with 3 to 200 repeating units, polyoxypropylene with 3 to 200 repeating units, polyoxytetramethylene with 3 to 200 repeating units, or polysiloxane with 3 to 200 repeating units formed by methylene siloxy groups, wherein the methylene siloxy group has two substituents selected from linear or branched alkyl groups with 1 to 10 carbon atoms, linear or branched alkoxy groups with 1 to 10 carbon atoms, and aromatic groups with 6 to 10 carbon atoms as substituents, X2 is different from X3; or

[0093] The following combinations are used: X1 is a polyoxytetramethylene compound with 3 to 200 repeating units; X2 is an oligomer chain selected from linear or branched alkylene groups with 12 to 30 carbon atoms, polyoxyethylene groups with 3 to 200 repeating units, or polyoxypropylene groups with 3 to 200 repeating units; X3 is a polyoxytetramethylene compound with 12 to 30 carbon atoms, linear or branched alkylene groups, polyoxyethylene groups with 3 to 200 repeating units, or polyoxypropylene groups with 3 to 200 repeating units. The oligomer chain group of polyoxypropylene, polyoxytetramethylene with 3 to 200 repeating units, or polysiloxane with 3 to 200 repeating units formed by methylenesiloxy group, wherein the methylenesiloxy group has two substituents selected from linear or branched alkyl groups with 1 to 10 carbon atoms, linear or branched alkoxy groups with 1 to 10 carbon atoms, and aromatic groups with 6 to 10 carbon atoms as substituents, and X2 is different from X3.

[0094] Although X1, X2, and X3 are not specifically limited, they are also greatly affected by the structure of the solid matrix, so they can be appropriately selected considering their compatibility with the solid matrix.

[0095] For example, in the case of a thiocarbamate or urethane-based solid matrix, oligomer chains with excellent compatibility can be selected from polyoxymethylene groups with 3 to 200 repeating units or polyoxytetramethylene groups with 3 to 200 repeating units; oligomer chains with poor compatibility can be selected from linear or branched alkylene groups with 12 to 30 carbon atoms, polyoxypropylene groups with 3 to 200 repeating units, or polysiloxane groups with 3 to 200 repeating units formed by methylene siloxy groups, wherein the methylene siloxy group has two substituents selected from linear or branched alkyl groups with 1 to 10 carbon atoms, linear or branched alkoxy groups with 1 to 10 carbon atoms, and aromatic groups with 6 to 10 carbon atoms; preferably, these oligomer chains are combined into block polymer-like groups.

[0096] In the case of an acrylic solid matrix, oligomer chains with excellent compatibility can be selected from polyoxymethylene groups with 3 to 200 repeating units or polyoxytetramethylene groups with 3 to 200 repeating units; oligomer chains with poor compatibility can be selected from polyoxypropylene groups with 3 to 200 repeating units or polysiloxane groups with 3 to 200 repeating units formed by methylene siloxy groups, wherein the methylene siloxy group has two substituents selected from linear or branched alkyl groups with 1 to 10 carbon atoms, linear or branched alkoxy groups with 1 to 10 carbon atoms, and aromatic groups with 6 to 10 carbon atoms; preferably, these oligomer chains are combined into a block polymer-like group.

[0097] The polyoxypropylene group with 3 to 200 repeating units, the polyoxymethylene group with 3 to 200 repeating units, the polyoxytetramethylene group with 3 to 200 repeating units, or the polysiloxane group with 3 to 200 repeating units formed by methylene siloxy groups more preferably has 4 to 150 repeating units, further preferably has 5 to 120 repeating units, and most preferably has 6 to 100 repeating units. The methylene siloxy group has two substituents selected from straight-chain or branched alkyl groups with 1 to 10 carbon atoms, straight-chain or branched alkoxy groups with 1 to 10 carbon atoms, and aromatic groups with 6 to 10 carbon atoms as substituents.

[0098] In formulas (1) and (2), the number-average molecular weight of the portion other than the PC group having the photochromic site is not particularly limited as long as it falls within the range of the aforementioned repeating units. For one group having the photochromic site, it is preferably 300 to 20,000, more preferably 400 to 15,000, further preferably 500 to 12,000, and most preferably 600 to 10,000. By setting the number-average molecular weight to the lower limit or above, a nano- to micron-scale phase-separated structure is formed, and the formation of free space in the solid matrix becomes sufficient, tending to improve photochromic properties. Furthermore, by setting the number-average molecular weight to the upper limit or below, the concentration of the photochromic compound per unit weight does not decrease, and it is not necessary to add an excessive amount exceeding the required amount.

[0099] <PC>

[0100] It is essential that a photochromic compound has at least one PC group within its molecule that has a photochromic site. Known photochromic sites can be used as the photochromic site.

[0101] Furthermore, there are no particular limitations on the photochromic compound as long as it has at least one group with a photochromic site. However, considering the productivity and photochromic properties of the photochromic compound itself, the number of groups with photochromic sites is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 4, and particularly preferably 1 to 2. When multiple groups with photochromic sites are present, they can be photochromic sites of the same structure, or they can be two or more different photochromic sites.

[0102] Examples of such photochromic sites include naphthopyran, spiroxazine, spiropyran, succinic anhydride, succinic imide, and diarylethylene.

[0103] In particular, from the perspective of exhibiting excellent photochromic properties in terms of color concentration and fading speed, naphthopyran, spiroxazine, and spiropyran are preferred, naphthopyran is more preferred, indenenaphthopyran is even more preferred, and indene[2,1-f]naphtho[1,2-b]pyran is especially preferred.

[0104] An example of a particularly preferred photochromic site is indo[2,1-f]naphtho[1,2-b]pyran, which is a compound represented by the following formula (6).

[0105]

[0106] (In equation (6), R) 1 and R 2Each of these groups is independently a group bonded to L1 as described below, or a hydroxyl, alkyl, haloalkyl, optionally substituted cycloalkyl, alkoxy, amino, substituted amino, amide, substituted amide, optionally substituted heterocyclic, cyano, halogen atom, alkylthio, optionally substituted arylthio, nitro, formyl, hydroxycarbonyl, alkylcarbonyl, alkoxycarbonyl, optionally substituted aralkyl, optionally substituted arylalkoxy, optionally substituted aryl, optionally substituted aryl, optionally substituted heteroaryl, thiol, alkoxyalkylthio, haloalkylthio, or optionally substituted cycloalkylthio.

[0107] a is an integer from 0 to 4, b is an integer from 0 to 4.

[0108] When a is 2 to 4, multiple R 2 Choose either the same or different from each other.

[0109] When b is 2 to 4, multiple R 1 Choose either the same or different from each other.

[0110] Additionally, when a is 2 to 4, there exist adjacent R. 2 At that time, two adjacent R 2 Optional to become one and with these R 2 The bonded carbon atoms together form a ring optionally containing oxygen, carbon, sulfur, or nitrogen atoms, and the ring optionally has substituents.

[0111] Additionally, when b is between 2 and 4, there exist adjacent R... 1 At that time, two adjacent R 1 Optional to become one and with these R 1 The bonded carbon atoms together form a ring optionally containing oxygen, carbon, sulfur, or nitrogen atoms, and the ring optionally has substituents.

[0112] R 3 and R 4 Each is independently an aryl or heteroaryl group that is optionally substituted with a substituent, which is a group optionally bonded to said L1.

[0113] R 5 and R 6 Each of these groups, independently bonded to L1 as described below, or a hydrogen atom, is a hydroxyl, alkyl, haloalkyl, cycloalkyl, alkoxy, alkoxyalkyl, formyl, hydroxycarbonyl, alkylcarbonyl, alkoxycarbonyl, halogen atom, optionally a substituted aralkyl, optionally a substituted aralkoxy, optionally a substituted aroxy, optionally a substituted aryl, or optionally a substituted heterocyclic group.

[0114] Additionally, R 5 and R6 Either of the following can be combined to form an aliphatic ring with 3 to 20 carbon atoms bonded to it, a fused polycyclic ring with an aromatic ring or aromatic heterocycle fused to the aliphatic ring, a heterocycle with 3 to 20 cyclic atoms, or a fused polycyclic ring with an aromatic ring or aromatic heterocycle fused to the heterocycle, wherein these rings optionally have substituents.

[0115] Among them, selected from R 1 R 2 R 3 Substituents on aryl or heteroaryl groups, R 4 Substituents on aryl or heteroaryl groups, R 5 and R 6 At least one of them is a group bonded to L1 as described later.

[0116] Furthermore, for each of the groups exemplified above, the preferred carbon number is as follows: alkyl preferably has 1 to 10 carbon atoms, haloalkyl preferably has 1 to 10 carbon atoms, cycloalkyl preferably has 3 to 8 carbon atoms, alkoxy preferably has 1 to 10 carbon atoms, alkylcarbonyl preferably has 2 to 7 carbon atoms, alkoxycarbonyl preferably has 2 to 7 carbon atoms, aralkyl preferably has 7 to 11 carbon atoms, aralkoxy preferably has 7 to 11 carbon atoms, aroxy preferably has 6 to 12 carbon atoms, aryl preferably has 6 to 12 carbon atoms, alkylthio preferably has 1 to 10 carbon atoms, cycloalkoxy preferably has 3 to 8 carbon atoms, and arylthio preferably has 6 to 12 carbon atoms.

[0117] The R 1 R 2 R 3 R 4 R 5 and R 6 In this process, the substituents that these groups, or the cyclic groups formed by these groups, are optionally introduced to control the color hue, etc., and therefore, of course, the effect will not be impaired by these substituents.

[0118] In order to exert excellent photochromic properties, the following groups are preferred.

[0119] R 1 Preferably, the alkyl group has 1 to 10 carbon atoms, the alkoxy group has 1 to 10 carbon atoms, the substituted amino group has substituted heterocyclic group, the alkylthio group has substituted alkyl group, the arylthio group has substituted alkyl group, or the aryl group has substituted alkyl group with 6 to 12 carbon atoms. More preferably, these groups are present at the 6-position and / or the 7-position of inden[2,1-f]naphtho[1,2-b]pyran. Furthermore, it is also preferable that R is present at the 6-position and the 7-position. 1The two components are integrated to form an aliphatic ring optionally containing oxygen, nitrogen, or sulfur atoms (optionally also having substituents). In this case, the number of atoms in the aliphatic ring containing oxygen, nitrogen, or sulfur atoms (including heteroatoms and the number of carbon atoms located at positions 6 and 7) is preferably 5 to 8. Furthermore, the aliphatic ring may optionally have substituents, but these substituents are preferably alkyl groups having 1 to 6 carbon atoms.

[0120] R 2 Preferably, the group comprises a hydrogen atom (when a=0), an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a substituted amino group, a heterocyclic group optionally having a substituent, a haloalkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms optionally having a substituent, a cyano group, or an arylthio group. More preferably, these groups are located at the 11 position of inden[2,1-f]naphtho[1,2-b]pyran.

[0121] R 3 and R 4 Preferably, the aryl group has 6 to 12 carbon atoms in the cyclic ring. Substituents in the aryl group are preferably alkyl groups with 1 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, substituted amino groups, heterocyclic groups having a cyclic nitrogen atom bonded to the carbon atom thereto (optionally having substituents), and optionally arylthio groups having substituents. Particularly preferred is at least one of the substituents being an atomic bond L1 as described in the detailed description below.

[0122] R 5 and R 6 More preferably, they are alkyl groups having 1 to 10 carbon atoms or L1 as described in the detailed description below. Additionally, R... 5 and R 6 More preferably, the two elements are integrated and together with the carbon atom at position 13 bonded to form an aliphatic ring with 3 to 20 carbon atoms, a fused polycyclic ring with an aromatic ring or aromatic heterocycle fused onto the aliphatic ring, a heterocycle with 3 to 20 cyclic atoms, or a fused polycyclic ring with an aromatic ring or aromatic heterocycle fused onto the heterocycle. Particularly preferred are rings selected from cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, and spirobicyclohexane. It should be noted that the spirocycle may optionally have 1 to 10 alkyl groups having 1 to 6 carbon atoms or 5 to 7 cycloalkyl groups as substituents, and the 5 to 7 cycloalkyl groups may optionally be fused rings. If more preferred groups are illustrated, groups represented by the following formulas can be listed.

[0123]

[0124] The indo[2,1-f]naphtho[1,2-b]pyran that forms the photochromic region described above can be used without restriction, for example, in International Publication No. 1996 / 014596, International Publication No. 2001 / 019813, International Publication No. 2001 / 060811, International Publication No. 2005 / 028465, International Publication No. 2006 / 110221, International Publication No. 2007 / 073462, International Publication No. 2007 / 140071, and International Publication No. 2008 / 0549. The compounds described in pamphlets 42, International Publication No. 2010 / 065393, International Publication No. 2011 / 10744, International Publication No. 2011 / 016582, International Publication No. 2011 / 025056, International Publication No. 2011 / 034202, International Publication No. 2011 / 078030, International Publication No. 2012 / 102409, International Publication No. 2012 / 102410, and International Publication No. 2012 / 121414.

[0125] The group bonded to L1 can be in R 1 R 2 R 3 Substituents on aryl or heteroaryl groups, R 4 Substituents on aryl or heteroaryl groups, R 5 and R 6 The substituents can be selected from the groups described herein. The group bonded to L1 is preferably substituted at the 3, 6, 7, 11, or 13 positions of indo-naphthopyran. The 3 and 13 positions are particularly preferred as they can improve the yield of the photochromic compound itself.

[0126] <Z>

[0127] When X2 in formula (1) or X3 in formula (2) is a straight-chain or branched alkylene group having 12 to 30 carbon atoms, Z is a hydrogen atom, a methyl group, or an alkoxy group having 1 to 10 carbon atoms. Z is preferably methyl.

[0128] When X2 in formula (1) or X3 in formula (2) is a polyoxypropylene, polyoxyethyl, polyoxytetramethylene, or polysiloxane with 3 to 200 repeating units, Z is a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, or an alkoxy group with 1 to 10 carbon atoms, and the repeating unit of the polysiloxane contains a methylenesiloxy group having two substituents selected from the group consisting of a straight-chain or branched alkyl group with 1 to 10 carbon atoms, a straight-chain or branched alkoxy group with 1 to 10 carbon atoms, and an aromatic group with 6 to 10 carbon atoms. Z is preferably an alkyl group with 1 to 10 carbon atoms or an alkoxy group with 1 to 10 carbon atoms.

[0129] <L1>

[0130] L1 is a divalent atomic bond that is directly bonded to or bonds the photochromic site PC to the oligomer chain group X1.

[0131] Preferably, the group is represented by the following formula (3).

[0132]

[0133] (In formula (3), Y1 and Y2 are divalent groups, each independently being a directly bonded, or -O-, -S-, amino, substituted amino, carbonyl, and groups containing combinations thereof (as examples of combinations, ester groups combining -O- and carbonyl can be listed), or substituted methylene silyl groups,

[0134] A1 is a divalent group, which is a directly bonded alkylene group with optional substituents having 1 to 10 carbon atoms, a cycloalkylene group with optional substituents having 3 to 12 carbon atoms forming a ring, an aryl group with optional substituents having 6 to 12 carbon atoms forming a ring, or a heterocyclic group with optional substituents having 3 to 12 carbon atoms forming a ring.

[0135] o is an integer from 1 to 3, and p is an integer from 1 to 5.

[0136] When there are 2 or more o, the divalent groups of the multiple existing o units can be chosen to be the same or different from each other.

[0137] When p is 2 or more, the divalent groups of multiple existing p units can be chosen to be the same or different from each other.

[0138] Where a particularly preferred group is exemplified, then

[0139] A1 is preferably a group selected from those obtained by directly bonding, methylene, ethylene, propylene, butylene, pentylene, hexylene, cyclohexylene, phenylene, and cyclohexylene by substituting the methylene group with NH.

[0140] Y1 and Y2 are preferably groups selected from direct bonding, -O-, -S-, carbonyl, ester, thioester, amide, carbamate, thiocarbamate, dimethylmethylenesilyl, and amino groups, respectively.

[0141] As for L1, there are no particular limitations, but it is preferred to use directly bonded groups or groups described below as combinations of the particularly preferred groups mentioned above.

[0142] (The dashed lines represent the portions bonded to the PC and X1 regions in the photochromic area.)

[0143]

[0144] L1 is preferably a divalent atomic bond as shown in the following formula (3').

[0145]

[0146] In formula (3'), V1, V2, V3, and V4 are each independently an oxygen atom, a sulfur atom, an amino group, a substituted amino group, a dimethylmethylenesilyl group, a dimethylmethylenesiloxy group, a carbonyl group, a carbonyloxy group, an aminocarbonyloxy group, an aminooxycarbonyl group, an alkylene group with 1 or more carbon atoms and 10 or less, an oxoalkylene group with 1 or more carbon atoms and 10 or less, an oxoalkylene group with 1 or more carbon atoms and 10 or less having a hydroxyl group, a dioxoalkylene group with 1 or more carbon atoms and 10 or less, a carbonylalkylene group with 2 or more carbon atoms and 10 or less, a dicarbonylalkylene group with 3 or more carbon atoms and 10 or less, or a carbonylalkylene group with 1 or more carbon atoms and 10 or less. The following are included: thioalkylene, aminoalkylene with 1 or more but less than 10 carbon atoms, oxycarbonylene with 2 or more but less than 10 carbon atoms, carbonyloxyalkylene with 2 or more but less than 10 carbon atoms, aminocarbonyloxyalkylene with 2 or more but less than 10 carbon atoms, cycloalkylene with 3 or more but less than 10 carbon atoms, cycloalkylene carbonyl with 4 or more but less than 10 carbon atoms, cycloalkoxycarbonyl with 4 or more but less than 10 carbon atoms, cycloalkylene carbonyloxy with 4 or more but less than 10 carbon atoms, heterocyclic alkylene with 1 or more but less than 10 carbon atoms, or heterocyclic alkylene carbonyl with 2 or more but less than 10 carbon atoms.

[0147] α, β, γ, and δ are 0 or 1. α+β+γ+δ is greater than 1 and less than 4. The atomic bonds of the dashed lines extending from V4 are bonded to X1. The atomic bonds of the solid lines extending from V1 are bonded to PC.

[0148] <L2, L3>

[0149] L2 represents an atomic bond with an m+1 valence that is directly bonded or bonds two different oligomer chain groups X1 and X2.

[0150] Preferably, the group is represented by the following formula (4).

[0151]

[0152] In formula (4), Y3 and Y4 are divalent groups, each independently being a directly bonded, or -O-, -S-, amino, substituted amino, carbonyl, and combinations thereof, or a substituted methylene silyl group.

[0153] A2 is an m-valent group, which can be directly bonded (only when m=1) or optionally have a hydrocarbon group with 1 to 10 carbon atoms having substituents.

[0154] q is an integer from 1 to 3, and r is an integer from 1 to 5.

[0155] When q is 2 or more, the groups of multiple existing q can be chosen to be the same or different from each other.

[0156] When r is 2 or more, the groups of multiple existing r can be chosen to be the same or different from each other.

[0157] Where a particularly preferred group is exemplified, then

[0158] A2 is preferably directly bonded, or has a substituent selected from alkoxy, methyl, ethyl, propyl, hydroxyl as a substituent, such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, or the following formula.

[0159]

[0160] (In the formula, the dashed part represents the bond with Y3 or Y4, and B is a hydrogen atom or a substituent selected from methyl, ethyl, propyl, hydroxy, and alkoxy.)

[0161] Y3 and Y4 are preferably groups containing direct bonding, -O-, -S-, carbonyl, ester, thioester, amide, carbamate, thiocarbamate, dimethylmethylenesilyl, and amino groups, respectively.

[0162] L3 is an atomic bond with a valence of 1+1 that is directly bonded or bonds two different oligomer chain groups X2 and X3.

[0163] Preferably, the group is represented by the following formula (5).

[0164]

[0165] In formula (5), Y5 and Y6 are divalent groups, each independently being a directly bonded group, or a group consisting of -O-, -S-, amino, substituted amino, carbonyl, or combinations thereof, or a substituted methylene silyl group.

[0166] A3 is a l-valent group, which can be directly bonded (only when l=1) or optionally a hydrocarbon group with 1 to 10 carbon atoms having substituents.

[0167] s is an integer from 1 to 3, and t is an integer from 1 to 5.

[0168] When s is 2 or more, the groups of multiple existing s can be chosen to be the same or different from each other.

[0169] When t is 2 or more, the groups of multiple existing t can be chosen to be the same or different from each other.

[0170] Where a particularly preferred group is exemplified, then

[0171] A3 is preferably directly bonded, or has a substituent selected from alkoxy, methyl, ethyl, propyl, hydroxyl as a substituent, such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, or the following formula.

[0172]

[0173] (Where, the dashed part represents the bond with Y5 or Y6, and B is a hydrogen atom or a substituent selected from methyl, ethyl, propyl, hydroxy, and alkoxy.)

[0174] Y5 and Y6 are preferably groups containing direct bonding, -O-, -S-, carbonyl, ester, thioester, amide, carbamate, thiocarbamate, dimethylmethylenesilyl, and amino groups, respectively.

[0175] There are no particular limitations on L2 and L3, but when m and l are 1, it is preferable to use directly bonded groups, which are combinations of the groups described below as particularly preferred groups.

[0176] (The dashed part represents the key to X1, X2, or X3.)

[0177]

[0178] Furthermore, when m and l are 2 or more, the following groups are preferred. (In the formula, the dashed part represents the bond with X1, X2, or X3.)

[0179]

[0180] L2 and L3 can be divalent atomic bonds as shown in equation (4').

[0181]

[0182] In formula (4'), V5, V6, V7, and V8 are each independently an oxygen atom, a sulfur atom, an amino group, a substituted amino group, a dimethylmethylenesilyl group, a dimethylmethylenesiloxy group, a carbonyl group, a carbonyloxy group, an aminocarbonyloxy group, an aminooxycarbonyl group, an alkylene group with 1 or more carbon atoms and less than 10 carbon atoms, an oxoalkylene group with 1 or more carbon atoms and less than 10 carbon atoms in a substituent having a hydroxyl group, an oxoalkylene group with 1 or more carbon atoms and less than 10 carbon atoms, a dioxoalkylene group with 1 or more carbon atoms and less than 10 carbon atoms, a carbonylalkylene group with 2 or more carbon atoms and less than 10 carbon atoms, a dicarbonylalkylene group with 3 or more carbon atoms and less than 10 carbon atoms, or a carbonylalkylene group with 1 or more carbon atoms and less than 10 carbon atoms. The following are included: thioalkylene, aminoalkylene with 1 or more but less than 10 carbon atoms, oxycarbonylene with 2 or more but less than 10 carbon atoms, carbonyloxyalkylene with 2 or more but less than 10 carbon atoms, aminocarbonyloxyalkylene with 2 or more but less than 10 carbon atoms, cycloalkylene with 3 or more but less than 10 carbon atoms, cycloalkylene carbonyl with 4 or more but less than 10 carbon atoms, cycloalkoxycarbonyl with 4 or more but less than 10 carbon atoms, cycloalkylene carbonyloxy with 4 or more but less than 10 carbon atoms, heterocyclic alkylene with 1 or more but less than 10 carbon atoms, or heterocyclic alkylene carbonyl with 2 or more but less than 10 carbon atoms.

[0183] ε, ζ, η, and θ are 0 or 1. ε+ζ+η+θ is greater than 1 and less than 4. In the case of L2, the atomic bonds of the dashed lines extending from V5 are bonded to X1, and the atomic bonds of the solid lines extending from V8 are bonded to X2. In the case of L3, the atomic bonds of the dashed lines extending from V5 are bonded to X2, and the atomic bonds of the solid lines extending from V8 are bonded to X3.

[0184] L2 and L3 can be chosen as trivalent atomic bonds as shown in the following formula (5').

[0185]

[0186] In formula (5'), W1 is CH, CW8, or a trivalent group that serves as a nitrogen atom. W8 is a straight-chain or branched alkyl group with 1 or more but less than 10 carbon atoms.

[0187] W2, W3, W4, W5, W6, and W7 are each independently an oxygen atom, a sulfur atom, an amino group, a substituted amino group, a dimethylmethylenesilyl group, a dimethylmethylenesiloxy group, a carbonyl group, a carbonyloxy group, an aminocarbonyloxy group, an aminooxycarbonyl group, an alkylene group with 1 or more carbon atoms and 10 or less, an oxoalkylene group with 1 or more carbon atoms and 10 or less, an oxoalkylene group with 1 or more carbon atoms and hydroxyl groups, a dioxoalkylene group with 1 or more carbon atoms and 10 or less, a carbonylalkylene group with 2 or more carbon atoms and 10 or less, a dicarbonylalkylene group with 3 or more carbon atoms and 10 or more carbon atoms, or a dicarbonylalkylene group with 1 or more carbon atoms and 10 or more carbon atoms. The following are included: thioalkylene, aminoalkylene with 1 or more and 10 or less carbon atoms, oxycarbonylene with 2 or more and 10 or less carbon atoms, carbonyloxyalkylene with 2 or more and 10 or less carbon atoms, aminocarbonyloxyalkylene with 2 or more and 10 or less carbon atoms, cycloalkylene with 3 or more and 10 or less carbon atoms, cycloalkylene carbonyl with 4 or more and 10 or less carbon atoms, cycloalkoxycarbonyl with 4 or more and 10 or less carbon atoms, cycloalkylcarbonyloxy with 4 or more and 10 or less carbon atoms, heterocyclic alkylene with 1 or more and 10 or less carbon atoms, or heterocyclic alkylene carbonyl with 2 or more and 10 or less carbon atoms.

[0188] κ, λ, and ν are 0 or 1, respectively.

[0189] In case L2, the atomic bonds along the dashed lines extending from W3 are bonded to X1, and the atomic bonds along the solid lines extending from W5 and W7 are bonded to X2. In case L3, the atomic bonds along the dashed lines extending from W3 are bonded to X2, and the atomic bonds along the solid lines extending from W5 and W7 are bonded to X3.

[0190] L2 and L3 can each be a tetravalent atomic bond as shown in the following formula (6').

[0191]

[0192] In formula (6'), U1, U2, U3, U4, U5, U6, U7, U8, and U9 are each independently an oxygen atom, a sulfur atom, an amino group, a substituted amino group, a dimethylmethylenesilyl group, a dimethylmethylenesiloxy group, a carbonyl group, a carbonyloxy group, an aminocarbonyloxy group, an aminooxycarbonyl group, an alkylene group with 1 or more carbon atoms and less than 10 carbon atoms, an oxoalkylene group with 1 or more carbon atoms and less than 10 carbon atoms in which a hydroxyl group is present, an oxoalkylene group with 1 or more carbon atoms and less than 10 carbon atoms, a dioxoalkylene group with 1 or more carbon atoms and less than 10 carbon atoms, a carbonylalkylene group with 2 or more carbon atoms and less than 10 carbon atoms, a dicarbonylalkylene group with 3 or more carbon atoms and less than 10 carbon atoms, and a carbon atom. The following are compounds with 1 or more but less than 10 carbon atoms: thioalkylene, aminoalkylene, oxycarbonylene, carbonyloxyalkylene, aminocarbonyloxyalkylene, cycloalkylene, cycloalkylene, cycloalkylene, carbonylene, carbonyloxycarbonylene, cycloalkylene, cycloalkylene, cycloalkylene, cycloalkylene, cycloalkoxycarbonylene, cycloalkylene, cycloalkylene, cycloalkylene, heteroalkylene, or heteroalkylene, cycloalkylene.

[0193] ξ, π, ρ and σ are 0 or 1 respectively.

[0194] In case L2, the atomic bonds of the dashed lines extending from U3 are bonded to X1, and the atomic bonds of the solid lines extending from U5, U7, and U9 are bonded to X2. In case L3, the atomic bonds of the dashed lines extending from U3 are bonded to X2, and the atomic bonds of the solid lines extending from U5, U7, and U9 are bonded to X3.

[0195] <Specific examples of photochromic compounds>

[0196] The compounds illustrated in the following formulas and examples represent photochromic compounds, but are merely examples and are not limited thereto.

[0197] In the formula, x, y, and z represent the number of repeating units, selected from 3 to 200. It should be noted that since oligomer chains typically have multiple molecular weights, they are expressed as number-average molecular weights. Therefore, x, y, and z can also take values ​​other than integers. Furthermore, x, y, and z can be different values ​​or the same value. It should be noted that "Me" in the formula refers to a methyl group.

[0198]

[0199]

[0200] <Methods for manufacturing photochromic compounds>

[0201] Photochromic compounds can be manufactured by any synthetic method. Representative examples of methods for manufacturing photochromic compounds are described, but are not limited to these methods.

[0202] For example, the synthesis of the photochromic compound of formula (1) will be described.

[0203] Block polymers with reactive substituents such as OH groups at the ends can be synthesized in advance using the same method as described in the international publication WO2019 / 013249.

[0204] In addition to block polymers having reactive substituents, compounds having a photochromic site and having at least one group capable of reacting with the reactive substituents introduced into the photochromic site are also synthesized. Preferably, this group is the group that forms L1.

[0205] Then, the reactive substituents of the block polymer are reacted with groups capable of forming L1 to produce a photochromic compound. It should be noted that the photochromic site and the reactive substituents can also react directly (in which case L1 becomes directly bonded).

[0206] There are no particular limitations on the reactive substituents of the block polymer compound and the groups capable of forming L1. Alternatively, the OH group of the block polymer compound can be converted into other reactive groups using known methods, and then reacted with a compound having a photochromic site with a group that can react with that reactive group. For example, L1 can be formed by esterification with a photochromic compound (site) terminated in a carboxylic acid. Specifically, the esterification reaction can be carried out as follows: in the presence of inorganic acids such as sulfuric acid and hydrochloric acid, organic acids such as aromatic sulfonic acids, or Lewis acids such as boron fluoride ethers, in a solvent such as toluene, water is removed by azeotropic heating and stirring as needed. It should be noted that, as a method for removing water in the esterification reaction, the following methods can be listed: removing water using desiccants such as anhydrous magnesium sulfate or molecular sieves; or removing water in the presence of dehydrating agents such as dicyclohexylcarbodiimide.

[0207] Alternatively, L1 can be formed by esterification with a compound terminally carboxyl halogen. Specifically, this can be achieved by removing the generated hydrogen halide in the presence of a base such as pyridine or dimethylaniline in an ether solvent such as tetrahydrofuran, with heating and stirring as needed.

[0208] Furthermore, L1 can also be formed by esterification with a compound that is terminally anhydride. Specifically, this can be achieved by heating and stirring in a solvent such as toluene in the presence of a catalyst such as sodium acetate or pyridine.

[0209] Alternatively, L1 can be formed by urethane esterification with a compound terminally composed of an NCO group. Specifically, this can be achieved by using an amine catalyst such as triethylenediamine or a tin catalyst such as dibutyltin dilaurate, in a solvent-free environment or in a solvent such as toluene, with heating and stirring as needed.

[0210] Alternatively, L1 can be formed by Michael addition reaction with a compound terminal to an SH group, a primary amino group, or a secondary amino group. Specifically, this can be achieved by heating and stirring as needed in the presence of a tertiary amine such as triethylamine, a base such as a metal alkoxide, or a solid catalyst such as alumina, in a solvent-free environment or in a solvent such as toluene.

[0211] As another method for synthesizing photochromic compounds, a polymer having a photochromic site and a reactive substituent such as an OH group at the end is synthesized first. In addition to the polymer having a photochromic site and a reactive substituent, a polymer incorporating a group capable of reacting with the reactive substituent is also synthesized. Preferably, this group is a group that forms L2. Then, the reactive substituent of the polymer having a photochromic site and a reactive substituent is reacted with the group capable of forming L2 to form a block polymer, thereby producing the photochromic compound. The reactive substituent and the group capable of forming L2 are not particularly limited. Of course, as described above, the OH group can also be converted into other reactive groups using known methods, and then reacted with a polymer incorporating a group capable of reacting with that reactive group to form a block polymer.

[0212] The photochromic compound shown in formula (2) can also be manufactured using the method described above.

[0213] <Identification of Photochromic Compounds>

[0214] Photochromic compounds typically exist as solids or viscous liquids at room temperature and pressure, and can be identified using the following methods. Specifically, separation techniques such as thin-layer chromatography, silica gel column chromatography, high-performance liquid chromatography, and gas chromatography are used to confirm that, apart from the photochromic compound, there are no byproducts such as starting material compounds or coloring components.

[0215] Using proton nuclear magnetic resonance spectroscopy ( 1 The obtained photochromic compounds were measured by ¹H-NMR. Peaks based on aromatic and alkene protons appeared in the vicinity of δ: 5.0–9.0 ppm, and peaks based on alkyl and alkylene protons appeared in the vicinity of δ: 1.0–4.0 ppm. In addition, the number of protons in each bonding group can be determined by comparing their respective spectral intensities.

[0216] Photochromic compounds are readily soluble in common organic solvents such as toluene, chloroform, and tetrahydrofuran. When the photochromic compound of formula (1) or (2) is dissolved in such solvents, the solution is usually almost colorless and transparent. When exposed to sunlight or ultraviolet light, it will quickly develop color and will quickly return to its original colorless state when the light is blocked, thus exhibiting a good photochromic effect.

[0217] <Instructions for using photochromic compounds>

[0218] Photochromic compounds can be widely used as photochromic materials (photochromic optical articles). For example, they can be used as substitutes for silver halide photosensitive materials in various memory materials, photocopying materials, photosensitive materials for printing, memory materials for cathode ray tubes, photosensitive materials for lasers, photosensitive materials for holography, and other memory materials. Furthermore, photochromic materials using photochromic compounds can also be used as photochromic lens materials, optical filter materials, display materials, photometers, decorative photochromic optical articles, etc. For example, as described later, these photochromic optical articles can be manufactured by curing a photochromic curable composition containing a photochromic compound and a polymeric compound. Alternatively, they can be made by laminating layers of cured materials containing photochromic compounds onto the surface of substrates such as plastic lenses.

[0219] Since photochromic compounds exhibit excellent photochromic properties even in solid matrices, they can be dispersed within polymeric solid matrices for use. Furthermore, polymeric molded articles with photochromic compounds internally dispersed can be manufactured. Known methods can be used for dispersion. Examples include: mixing the photochromic compound and a solid matrix such as a thermoplastic resin in a molten state to disperse the photochromic compound in the solid matrix; dissolving the polymeric photochromic compound in a polymeric compound, adding a polymerization catalyst, and then curing it using heat or light to disperse the photochromic compound in the cured product; or dyeing the surface of a solid matrix to disperse the photochromic compound in the solid matrix, etc.

[0220] If the solid matrix is ​​exemplified, then optically preferred materials are, for example, polyacrylates, polymethacrylates, and poly(C) acrylates. l -C l2Alkyl methacrylates, polyoxy(alkylene methacrylates), poly(alkoxylated phenol methacrylates), cellulose acetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, poly(vinyl acetate), poly(vinyl alcohol), poly(vinyl chloride), poly(vinylidene chloride), poly(vinylpyrrolidone), poly((meth)acrylamide), poly(dimethacrylamide), poly(hydroxyethyl methacrylate), poly((meth)acrylic acid), thermoplastic polycarbonates, polyesters, polyurethanes, polythiourethanes, polyethylene terephthalate, polystyrene, poly(α-methylstyrene).

[0221] For example, when using photochromic compounds in photochromic lenses, there are no particular limitations on the method as long as uniform dimming performance can be obtained. Examples include: sandwiching a polymer film formed by uniformly dispersing the photochromic compound in a lens; or dispersing the photochromic compound in a polymerizable compound and polymerizing it using a prescribed method; or dissolving the photochromic compound in, for example, silicone oil, impregnating the lens surface at 150–200°C for 10–60 minutes, and then covering the surface with a curing substance to produce a photochromic lens. Furthermore, a method can also be used to coat the aforementioned polymer film onto the lens surface and cover the surface with a curing substance to produce a photochromic lens. Furthermore, a coating agent containing a photochromic compound curable composition containing the photochromic compound described later can be coated onto the surface of a lens substrate, and the coating can be cured. At this point, the lens substrate can be pre-treated with an alkaline solution or plasma treatment. Alternatively, a primer can be applied together with or without these surface treatments to improve the adhesion between the substrate and the coating.

[0222] <Photochromic Curable Composition>

[0223] By compounding a photochromic compound into a polymeric compound, it can be used as a photochromic curable composition. The photochromic compound can be used alone or in combination with other photochromic compounds, depending on the purpose, such as to obtain various hues required for a photochromic lens. Known photochromic compounds can be used without any limitations in the combined photochromic compound. Examples include naphthopyran, spiroxazine, spiropyran, succinic anhydride, and succinic imide. Among these, naphthopyran is preferred, and indene-naphthopyran is particularly preferred, from the perspective of uniformly maintaining the hue during color development and fading, suppressing color shift during color development accompanied by the deterioration of the photochromic compound, and further, from the perspective of suppressing initial coloring. Additionally, from the perspective of suppressing color shift during color development and fading caused by matrix-dependent differences, other photochromic compounds having oligomer chain groups are also preferred. Furthermore, when using photochromic compounds with oligomer chain groups, from the perspective of suppressing the whitening of the cured product, it is optimal to use a variety of photochromic compounds to adjust the hue.

[0224] In photochromic curable compositions, the amount of photochromic compound is not particularly limited; it can be appropriately selected considering the color intensity of the photochromic compound and the thickness of the resulting photochromic cured product. Specifically, relative to 100 parts by mass of the polymeric compound, it is preferable to set the amount of photochromic compound to 0.0001 to 30 parts by mass, more preferably to 0.0003 to 20 parts by mass, and most preferably to 0.0005 to 10 parts by mass.

[0225] Since the color intensity of photochromic cured products depends on the thickness of the cured product, considering the thickness is particularly important. For example, when molding a film of 100 μm or less using a photochromic curable composition, it is preferable to use 0.001 to 10 parts by mass of a photochromic compound containing a polymeric photochromic compound to adjust the hue, relative to 100 parts by mass of the polymeric compound. Furthermore, when producing a photochromic cured product with a thickness of 1 mm or more, it is preferable to use 0.0005 to 5 parts by mass of a photochromic compound containing a polymeric photochromic compound to adjust the hue, relative to 100 parts by mass of the polymeric compound.

[0226] <Polymerizing compounds>

[0227] As previously mentioned, photochromic compounds can be combined with polymeric compounds to be used as photochromic curable compositions. Examples of polymeric compounds include urethane or urea-based polymeric compounds, free radical polymeric compounds, and epoxy polymeric compounds capable of forming urethane bonds, urea bonds, etc. These polymeric compounds are not particularly limited; for example, polymeric compounds described in International Publication No. WO2018-235771 may be suitably used. Among these, urethane-based polymeric compounds or free radical polymeric compounds as shown below are particularly suitable.

[0228] (Carbamate polymeric compounds)

[0229] As a urethane-based polymerizable compound, compositions containing isocyanate compounds and compounds with active hydrogen can be suitably used. It should be noted that isocyanate compounds refer to compounds having an isocyanate group or an isothiocyanate group, or compounds having both an isocyanate group and an isothiocyanate group.

[0230] The isocyanate compound can use known substances without particular limitation, preferably containing polyisocyanate groups having at least two isocyanate groups in one molecule; particularly preferred are polyisocyanate compounds containing aromatic rings such as m-xylene diisocyanate and 4,4'-diphenylmethane diisocyanate; and aliphatic polyisocyanate compounds such as norbornane diisocyanate and dicyclohexylmethane-4,4'-diisocyanate.

[0231] Compounds containing active hydrogen can be used without particular restriction, but compounds containing amino and / or hydroxyl and / or thiol groups are preferred. Particularly preferred are polyfunctional compounds containing two or more active hydrogens in one molecule. Examples of compounds containing active hydrogen include difunctional amine compounds such as isophorone diamine, bis-(4-aminocyclohexyl)methane, and norbornene diamine; polyfunctional alcohol compounds such as pentaerythritol hexa(3-mercaptopropionate), trimethylolpropane tri(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), and 4-mercaptomethyl-3,6-dithia-octanedithiol; and polyfunctional alcohols such as trimethylolpropane and pentaerythritol, preferably in the form of compositions containing these compounds.

[0232] In addition, considering the durability of the obtained photochromic cured product, it is preferable to use an active hydrogenated compound having at least one piperidine structure, hindered phenolic structure, triazine structure, or benzotriazole structure in the molecule.

[0233] (Free radical polymeric compounds)

[0234] Free radical polymerizable compounds can be divided into polyfunctional free radical polymerizable compounds and monofunctional free radical polymerizable compounds, which can be used individually or in combination. As substituents for free radical polymerization, groups with unsaturated double bonds can be listed, namely vinyl groups (including styryl, (meth)acryloyl, allyl, etc.).

[0235] Polyfunctional radical polymerizable compounds are compounds that have two or more radical polymerizable substituents within their molecules. These polyfunctional radical polymerizable compounds can be divided into first-order polyfunctional radical polymerizable compounds with 2 to 10 radical polymerizable substituents and second-order polyfunctional radical polymerizable compounds with more than 10 radical polymerizable substituents.

[0236] There are no particular limitations on the first polyfunctional radical polymerizable compound, but more preferably, the number of radical polymerizable substituents is 2 to 6. Specifically, examples of first polyfunctional radical polymerizable compounds include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, ethylene glycol diglycidyl(meth)acrylate, bisphenol A di(meth)acrylate, 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(3,5-dibromo-4-(meth)acryloyloxyethoxyphenyl)propane, and other polyfunctional (meth)acrylate compounds; phthalic acid di... Polyfunctional allyl compounds including allyl esters, diallyl terephthalate, diallyl isophthalate, diallyl tartrate, diallyl epoxysuccinate, diallyl fumarate, diallyl chloramphenicol, diallyl hexahydrophthalate, diallyl carbonate, allyl diethylene glycol carbonate, and trimethylolpropane triallyl carbonate; polyfunctional thio(meth)acrylate compounds including 1,2-bis(methacryloylthio)ethane, bis(2-acryloylthioethyl) ether, and 1,4-bis(methacryloylthiomethyl)benzene; and vinyl compounds such as divinylbenzene.

[0237] Examples of compounds with high molecular weight include silsesquioxanes with radical polymerizable substituents and polyrotaxanes with radical polymerizable substituents.

[0238] Monofunctional free radical polymerizable compounds are compounds that have one or more free radical polymerizable substituents within their molecules. Examples of monofunctional free radical polymerizable compounds include: unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and maleic anhydride; methyl methacrylate, benzyl methacrylate, phenyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, β-methylglycidyl methacrylate, bisphenol A-monoglycidyl ether-methacrylate, 4-epoxypropoxy methacrylate, 3-(glycidyl-2-oxyethoxy)-2-hydroxypropyl methacrylate, and propylene. (Meth)acrylate compounds such as 3-(epoxypropoxy-1-isopropoxy)-2-hydroxypropyl acrylate and 3-(epoxypropoxy-2-hydroxypropoxy)-2-hydroxypropyl acrylate; fumarate compounds such as diethyl fumarate and diphenyl fumarate; thioacrylic acid compounds such as methyl thioacrylate, benzyl thioacrylate, and benzyl thiomethacrylate; and vinyl compounds such as styrene, chlorostyrene, methylstyrene, vinylnaphthalene, α-methylstyrene dimer, and bromostyrene.

[0239] The free radical polymerizable compound can be used alone or in mixtures of multiple types. In this case, relative to a total of 100 parts by mass of the free radical polymerizable compound, it is preferable to set 80-100 parts by mass of the multifunctional free radical polymerizable compound and 0-20 parts by mass of the monofunctional free radical polymerizable compound; more preferably, it is preferable to set 90-100 parts by mass of the multifunctional free radical polymerizable compound and 0-10 parts by mass of the monofunctional free radical polymerizable compound. Furthermore, relative to a total of 100 parts by mass of the free radical polymerizable compound, it is preferable to set 80-100 parts by mass of the first multifunctional free radical polymerizable compound, 0-20 parts by mass of the second free radical polymerizable compound, and 0-20 parts by mass of the monofunctional free radical polymerizable compound; even more preferably, it is preferable to set 85-100 parts by mass of the first multifunctional free radical polymerizable compound, 0-10 parts by mass of the second multifunctional free radical polymerizable compound, and 0-10 parts by mass of the monofunctional free radical polymerizable compound.

[0240] <Other Additives>

[0241] In photochromic curable compositions, various known additives can be mixed in as needed, without impairing the effect, such as release agents, ultraviolet absorbers, infrared absorbers, ultraviolet stabilizers, antioxidants, anti-coloring agents, antistatic agents, fluorescent dyes, dyes, pigments, fragrances, and other stabilizers, additives, solvents, and leveling agents; furthermore, thiols such as tert-dodecyl mercaptan can be used as polymerization regulators.

[0242] Among these, the use of UV stabilizers can improve the durability of photochromic sites, and is therefore preferred. Such UV stabilizers include hindered amine light stabilizers, hindered phenolic antioxidants, and sulfur-based antioxidants. Particularly suitable UV stabilizers are described below. Examples include bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, manufactured by Asahi Denka Kogyo Co., Ltd. as Adekastab LA-52, LA-57, LA-62, LA-63, LA-67, LA-77, LA-82, and LA-87; 2,6-di-tert-butyl-4-methylphenol; and ethylene bis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], manufactured by Ciba Specialty Chemicals, Inc. as IRGANOX 1010, 1035, 1075, 1098, 1135, 1141, 1222, 1330, 1425, 1520, 259, 3114, 3790, 5057, and 565.

[0243] There are no particular restrictions on the amount of such UV stabilizer used as long as it does not impair the effect. Generally, it is 0.001 to 10 parts by weight relative to 100 parts by weight of the photochromic curing composition, preferably 0.01 to 5 parts by weight.

[0244] In addition to UV stabilizers, UV absorbers can also be used. Known UV absorbers such as benzotriazole-based, triazine-based, benzophenone-based, cyanoacrylate-based, diphenylacrylate-based, phenol-based, oxaloyl aniline-based, malonate-based, and cinnamic acid ester-based UV absorbers can be used as UV absorbers. Particularly preferred are cyanoacrylate-based, benzophenone-based, oxaloyl aniline-based, malonate-based, and cinnamic acid ester-based UV absorbers, with oxaloyl aniline-based, malonate-based, and cinnamic acid ester-based UV absorbers being particularly preferred. The UV stabilizer is preferably used in the range of 0.001 to 5 parts by weight relative to 100 parts by weight of the photochromic curable composition.

[0245] In photochromic curable compositions, polymeric compounds other than those mentioned above may also be mixed in, provided that the effect is not impaired. The mixing ratio can be appropriately determined according to the application.

[0246] <Instructions for use of photochromic curable compositions; photochromic optical articles>

[0247] Photochromic curable compositions can be used as photochromic optical articles by polymerizing cured products. These compositions are prepared by mixing the photochromic compound, polymerizable compound, and additives as needed, using known methods. The polymerization used to prepare the cured product is carried out through free radical polymerization, ring-opening polymerization, anionic polymerization, or polycondensation using active energy rays such as ultraviolet light, alpha rays, beta rays, and gamma rays, heat, or a combination of both. In other words, an appropriate polymerization method is chosen based on the type of polymerizable compound, the type of polymerization accelerator, and the morphology of the resulting cured product.

[0248] When photochromic curable compositions are thermally polymerized, temperature, in particular, affects the properties of the resulting cured product. Since the temperature conditions are influenced by the type and amount of the thermal polymerization initiator and the type of polymerizable compound, a general rule cannot be applied. However, it is generally suitable to begin polymerization at a lower temperature and then slowly increase the temperature. The polymerization time, like temperature, varies depending on various factors; therefore, it is advisable to predetermine the optimal time corresponding to these conditions. Generally, conditions that allow polymerization to conclude within 2 to 48 hours are preferred.

[0249] Furthermore, during the photopolymerization of photochromic curable compositions, the polymerization conditions, particularly the UV intensity, affect the properties of the resulting cured product. The irradiation conditions are influenced by the type and amount of the photopolymerization initiator and the type of polymerizable monomer; therefore, generalizations are not possible. However, it is generally preferred to irradiate the product with 50–500 mW / cm² light at a wavelength of 365 nm for 0.5–5 minutes. 2 The selection criteria for UV light mode.

[0250] For example, when making a photochromic lens from a cured material, the known methods described below can be used as long as a method that can obtain uniform light-modulating performance is available.

[0251] When the photochromic lens is manufactured by the mixing method, the above-mentioned photochromic curable composition is injected into the glass mold held by the elastomeric gasket or spacer. Depending on the type of polymerizable compound and polymerization curing accelerator, the photochromic optical article shaped into a lens or the like can be obtained by casting polymerization based on heating in an air furnace and irradiation by active energy rays such as ultraviolet light.

[0252] In the case of manufacturing photochromic lenses by a lamination method, a photochromic curable composition is appropriately dissolved in an organic solvent to prepare a coating liquid. The coating liquid is then applied to the surface of an optical substrate such as a lens substrate by spin coating, dipping, etc. After drying and removing the organic solvent, polymerization is carried out by UV irradiation in an inert gas such as nitrogen, heating, etc., to obtain a photochromic lens with a photochromic layer formed on the surface of the optical substrate (coating method).

[0253] Alternatively, by arranging an optical substrate such as a lens substrate in a manner that forms a specified gap, and injecting a photochromic curable composition into the gap, a photochromic lens with a photochromic layer formed on the surface of the optical substrate can also be obtained by casting polymerization based on an inner mold, which is carried out by UV irradiation, heating, etc. (cast polymerization method).

[0254] When a photochromic layer is formed on the surface of an optical substrate using the aforementioned lamination methods (coating and casting polymerization), the adhesion between the photochromic layer and the optical substrate can be improved by pre-treating the surface of the optical substrate with chemical treatment using alkaline solutions, acidic solutions, etc., or with physical treatment using corona discharge, plasma discharge, grinding, etc. Alternatively, a transparent adhesive resin layer can be pre-applied to the surface of the optical substrate.

[0255] Furthermore, in the case of manufacturing photochromic lenses by adhesive method, firstly, a photochromic sheet is made by sheet molding using a photochromic curable composition, and then the sheet is sandwiched between two transparent sheets (optical sheets) and the aforementioned polymerization is carried out, thereby obtaining a photochromic laminate with a photochromic layer as the adhesive layer.

[0256] Alternatively, in this case, to produce photochromic sheets, the following method can be used: coating with a coating solution prepared by dissolving the photochromic curing composition in an organic solvent.

[0257] The photochromic laminate thus produced is mounted in a mold, and then an optical substrate such as a lens is injection molded with a thermoplastic resin (e.g., polycarbonate) to obtain a photochromic lens of a predetermined shape with the photochromic laminate stacked thereon. Alternatively, the photochromic laminate can be bonded to the surface of an optical substrate using an adhesive or the like, thereby also obtaining a photochromic lens.

[0258] It should be noted that, in the case of fabricating photochromic laminates as described above, especially from the perspective of high adhesion to the optical substrate, urethane or urea-based polymeric compounds, particularly urethane-based polymeric compounds, are preferably used as polymeric compounds to form polyurethane.

[0259] The cured product obtained by polymerizing the above-mentioned photochromic curable composition has a high color concentration at high temperature and can exhibit excellent photochromic properties.

[0260] In addition, the cured product obtained by polymerizing the photochromic curable composition can be subjected to various post-processing methods depending on its application, such as dyeing with dyes such as disperse dyes, forming hard coating films using hard coating agents with sols of silane coupling agents, silicon, zirconium, antimony, aluminum, tin, tungsten, etc. as the main components, forming thin films based on the vapor deposition of metal oxides such as SiO2, TiO2, ZrO2, anti-reflective treatment of thin films based on coated organic polymers, and antistatic treatment.

[0261] Example

[0262] Next, the present invention will be described in detail using examples and comparative examples, but the present invention is not limited to these examples.

[0263] It should be noted that the number of repeating units of the polymer specified in the embodiments is an average value obtained using proton nuclear magnetic resonance spectroscopy.

[0264] <Example 1>

[0265] Process 1

[0266] 75 g (10 mmol) of polyethylene glycol monomethyl ether with a number average molecular weight of 750, 100 mL of dichloromethane, and succinic anhydride (1.5 g, 15 mmol) were added and stirred. Triethylamine (2.0 g, 20 mmol) was then added, and the mixture was stirred at room temperature for 12 hours. After the reaction was complete, 10% hydrochloric acid was added to the ice-hydrated reaction solution, and the mixture was separated. The solvent was removed by distillation from the organic layer to obtain the compound shown in formula (7).

[0267]

[0268] It should be noted that the number of repeating units such as polyoxyethylene and polyoxypropylene may change during the reaction or purification process. In this embodiment, the number of repeating units after the reaction or purification in each step is also marked.

[0269] Process 2

[0270] Add 4.3 g (5.0 mmol) of the compound represented by formula (7) and the following formula (8).

[0271]

[0272] The compound shown was mixed with 5.5 g (4.9 mmol) of dichloromethane and 20 mL of water-soluble carbodiimide (WSC) and 63 mg of DMAP (dimethylaminopyridine). The mixture was stirred for 12 hours.

[0273] After the reaction was complete, 10 mL of water was added, and the mixture was separated. Anhydrous magnesium sulfate was added to the organic layer, dried, and the magnesium sulfate was filtered off. The solvent of the filtrate was concentrated. After concentration, 15 mL of tetrahydrofuran was added, and the mixture was stirred while being cooled with ice water. 7.5 mL of tetrabutylammonium fluoride (1 mM tetrahydrofuran solution) was added, and the mixture was stirred for 12 hours. After the reaction was complete, water was added, and the mixture was separated. The solvent of the concentrated organic layer was purified by silica gel column chromatography to obtain the compound shown in formula (9).

[0274]

[0275] Process 3

[0276] Perform the same operation as in step 1, adding the compound of formula (9) to succinic anhydride to obtain the compound shown in formula (10).

[0277]

[0278] Process 4

[0279] 4.62 g (10 mmol) of the compound shown in formula (11) below,

[0280]

[0281] The compound represented by formula (12) below, 4.48 g (15 mmol),

[0282]

[0283] 0.25 g (1.0 mmol) of p-toluenesulfonic acid pyridinium salt was added to 100 mL of toluene and heated and stirred at 75 °C for 2 hours. After cooling to room temperature, 100 mL of water was added, and the mixture was separated. The solvent of the concentrated organic layer was purified by silica gel column chromatography to obtain the chromene compound shown in formula (13).

[0284]

[0285] Process 5

[0286] 1.56 g (2.1 mmol) of the chromene compound shown in formula (13) and 4.24 g (2.0 mmol) of the compound shown in formula (10) were added to 20 mL of dichloromethane. After stirring, 380 mg of WSC and 120 mg of DMAP were added, and the mixture was stirred while protected from light. After the reaction was completed, 10 mL of water was added, and the mixture was separated. The solvent of the obtained organic layer was concentrated and purified by silica gel column chromatography to obtain the compound shown in formula (14).

[0287]

[0288] The yield was 60%.

[0289] In addition, the proton nuclear magnetic resonance spectrum was measured, and the results showed that, compared with the 21H peak based on aromatic protons and alkene protons in the vicinity of δ5.6 to 9.0 ppm from the photochromic compound, the peak of about 40.5H based on cyclohexane ring and methyl, succinic acid site and propylene protons in the vicinity of 1.0 to 3.0 ppm, and the peak of 143.7H based on methoxy, propylene, and ethoxy in the vicinity of δ3.0 to 5.5 ppm, the structure was confirmed to be consistent with the structure of formula (14).

[0290] <Example 2>

[0291] Process 1

[0292] 35.0 g (50.0 mmol) of polypropylene glycol (number average molecular weight 700), 6.31 g (62.5 mmol) of triethylamine, and 1 L of dichloromethane were added and the mixture was cooled. Acryloyl chloride (5.43 g (60.0 mmol)) was slowly added dropwise over one hour. After the reaction was complete, 1 L of water was added, and the mixture was separated. The solvent of the resulting organic layer was concentrated and purified by silica gel column chromatography to obtain polypropylene glycol monoacrylate with a number average molecular weight of 700.

[0293] Process 2

[0294] 14.1 g (18.7 mmol) of polypropylene glycol monoacrylate with a number average molecular weight of 700, 7.0 mg of butylated hydroxytoluene (BHT), 2.0 g (20.0 mmol) of succinic anhydride, and 500 mL of dichloromethane were added. While stirring under ice-cold conditions, 2.52 g (25 mmol) of triethylamine was slowly added. After stirring for 12 hours, 200 mL of water was added, and the mixture was separated. The solvent of the obtained organic layer was concentrated to obtain the compound shown in formula (15).

[0295]

[0296] Process 3

[0297] 3.61 g (5.0 mmol) of the chromene compound shown in formula (16) below,

[0298]

[0299] 4.19 g (4.9 mol) of the compound represented by formula (15) was added to 50 mL of dichloromethane and stirred. Then, 950 mg of WSC and 300 mg of DMAP were added, and the mixture was stirred while being protected from light. After the reaction was completed, 30 mL of water was added, and the mixture was separated. The solvent of the obtained organic layer was concentrated and purified by silica gel column chromatography to obtain the compound represented by formula (17) in 85% yield.

[0300]

[0301] Process 4

[0302] 6.76 g (4.2 mmol) of the compound represented by formula (17) was dissolved in 30 mL of toluene, and 1.29 g (4.5 mmol) of 1-octadecylthiol and 5 g of neutral alumina were added. The mixture was stirred at room temperature. After the reaction was complete, the neutral alumina was filtered off, and the solvent of the resulting organic layer was concentrated and purified by silica gel column chromatography to obtain the compound represented by formula (18) in 90% yield.

[0303]

[0304] In addition, the proton nuclear magnetic resonance spectrum was measured, and the results showed that, compared with the 17H ​​peak based on aromatic protons and olefin protons in the vicinity of δ5.6 to 9.0 ppm from the photochromic compound, the peak of about 96.5H based on cyclohexane ring and octadecyl, succinic acid site, and propoxy protons in the vicinity of 1.0 to 3.0 ppm, and the peak of 56.5H based on methoxy, propoxy, ethoxy, and morpholino groups in the vicinity of δ3.0 to 5.5 ppm, the structure was confirmed to be consistent with the structure of formula (18).

[0305] <Example 3>

[0306] Process 1

[0307] 40.0 g (100.0 mmol) of polyethylene glycol monoethyl ether with a number average molecular weight of 400 and 21.0 g (110.0 mmol) of toluenesulfonyl chloride were dissolved in 500 ml of pyridine. 2.2 g (20.0 mmol) of 1,4-diazabicyclo[2.2.2]octane was added while stirring under ice-cold conditions, and the mixture was heated to room temperature while stirring for 12 hours. After the reaction was complete, the reaction solution was added to ice water and extracted with dichloromethane. The resulting organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent of the organic layer was concentrated and purified by silica gel column chromatography to obtain the compound shown in formula (19).

[0308]

[0309] Process 2

[0310] While stirring 5.44 g (40.0 mmol) of 2-(methoxymethoxy)-1,3-propanediol, 100 mL of dimethylformamide (DMF), and 4.0 g (100.0 mmol) of sodium hydride (containing 40% mineral oil product) under ice-cold conditions, 49.87 g (90.0 mol) of the compound of formula (19) was slowly added, allowing the reaction to proceed for 24 hours. After the reaction, 300 mL of water, 500 mL of THF, and 500 mL of toluene were added, and the mixture was separated. The organic layer obtained was dried over anhydrous magnesium sulfate, filtered, and the solvent of the obtained organic layer was concentrated and purified by silica gel column chromatography.

[0311] Add 200 mL of methanol and 50 mL of hydrochloric acid to the mixture and stir at room temperature for 24 hours. After the reaction, neutralize with sodium bicarbonate, concentrate the methanol, add 500 mL of ethyl acetate and 200 mL of water, and separate the layers. Dry the obtained organic layer with anhydrous magnesium sulfate, filter it, concentrate the solvent of the obtained organic layer, and purify it by silica gel column chromatography to obtain the compound shown in formula (20) below.

[0312]

[0313] Process 3

[0314] Using the compound of formula (20), the same reaction as the first step of Example 1 was carried out to obtain the compound shown in formula (21) below.

[0315]

[0316] Process 4

[0317] Except in the second step of Example 1, where the compound of formula (21) is used instead of the compound of formula (7), the following formula (22) is used.

[0318]

[0319] In addition to the compound of formula (8), the reaction is carried out in the same manner to obtain the compound shown in formula (23).

[0320]

[0321] Process 5

[0322] Using the compound of formula (23), the same reaction as the first step of Example 1 was carried out to obtain the compound shown in formula (24).

[0323]

[0324] Process 6

[0325] In addition to using the compound shown in formula (25) instead of the compound shown in formula (13),

[0326]

[0327] Except for replacing the compound of formula (10) with the compound of formula (24), the procedure was carried out in the same manner as step 5 of Example 1 to obtain the compound shown in formula (26).

[0328]

[0329] The yield was 65%.

[0330] In addition, the proton nuclear magnetic resonance spectrum was measured, and the results showed that, compared with the 16H peak based on aromatic protons and alkene protons in the vicinity of δ5.6 to 9.0 ppm from the photochromic compound, the peak of about 136.2H based on cyclooctane ring, succinic acid site, and propoxy protons in the vicinity of 1.0 to 3.0 ppm, and the peak of 207.2H based on methoxy, propoxy, ethoxy, morpholino, and glycerol groups in the vicinity of δ3.0 to 5.5 ppm, the structure was confirmed to be consistent with the structure of formula (26).

[0331] <Example 4>

[0332] Except for the use of 17.1 g (50.0 mmol) eicosanoic acid and 37.5 g (50.0 mmol) polyethylene glycol monomethyl ether with a number average molecular weight of 750, the process was carried out in the same manner as step 2 of Example 1 to synthesize the compound shown in formula (27).

[0333]

[0334] Process 2

[0335] In the fourth step of Example 3, the reaction was carried out in the same manner except that the compound of Formula (27) was used instead of the compound of Formula (21) to synthesize the compound shown in Formula (28).

[0336]

[0337] Process 3

[0338] Using the product of step 2, the same reaction as step 1 of Example 1 was carried out to synthesize the compound shown in formula (29) below.

[0339]

[0340] Process 4

[0341] In step 4 of Example 1, except that the compound represented by the following formula (30) is used instead of the compound of formula (11),

[0342]

[0343] The same process was repeated to obtain the chromene compound shown in formula (31).

[0344]

[0345] Process 5

[0346] The compound shown in formula (32) is obtained by reacting the formula (29) obtained in step 3 and the formula (31) obtained in step 4 in the same manner as step 5 of Example 1.

[0347]

[0348] The yield was 69%.

[0349] In addition, the proton nuclear magnetic resonance spectrum was measured, and the results showed that, compared with the 16H peak based on aromatic protons and alkene protons in the vicinity of δ5.6 to 9.0 ppm from the photochromic compound, the peak of about 148.9H based on cyclooctane ring, succinic acid site, and propoxy protons in the vicinity of 1.0 to 3.0 ppm, and the peak of 188.1H based on methoxy, propoxy, and ethoxy in the vicinity of δ3.0 to 5.5 ppm, the structure was confirmed to be consistent with the structure of formula (32).

[0350] <Example 5>

[0351] Process 1

[0352] In Example 1, except that tetracosanoic acid was used instead of the compound of formula (7), the same procedure as in Example 1 was followed to obtain the compound shown in formula (33).

[0353]

[0354] Process 2

[0355] In step 5 of Example 1, except that the compound of formula (33) is used instead of the compound of formula (10), and the compound of formula (34) is used instead of the compound of formula (13),

[0356]

[0357] The reaction was carried out in the same manner to obtain the compound shown in the following formula (35).

[0358]

[0359] The yield was 72%.

[0360] In addition, the proton nuclear magnetic resonance spectrum was measured, and the results showed that, compared with the 19H peak based on aromatic protons and alkene protons in the vicinity of δ5.6 to 9.0 ppm from the photochromic compound, the peak of about 130.5H based on cyclohexane ring, succinic acid site, and propoxy protons in the vicinity of 1.0 to 3.0 ppm, and the peak of 76.5H based on morpholino, methoxy, propoxy, and ethoxy in the vicinity of δ3.0 to 5.5 ppm, the structure was confirmed to be consistent with the structure of formula (35).

[0361] (Preparation and evaluation of cured products (thiocarbamate-based molded articles))

[0362] A photochromic curable composition was prepared by mixing the components according to the following formulation. The mixing amounts are shown below. The results of the photochromic properties of the cured products using the photochromic compounds of Examples 1-5 in Table 1 are shown in Table 1.

[0363] (Composition of polymeric compounds)

[0364] m-Xylene diisocyanate: 43.1 parts by weight

[0365] Pentaerythritol tetra(3-mercaptopropionate): 49.7 parts by weight

[0366] 1-Decanethiol: 2.7 parts by weight

[0367] RX-1 prepared by the method described in International Publication WO2016 / 143910: 4.5 parts by mass

[0368] Dimethyltin dichloride: 0.05 parts by weight

[0369] JP-506H (manufactured by Johoku Chemical Industry Co., Ltd.): 0.1 parts by weight

[0370] Ethylene bis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate]: 0.1 parts by weight

[0371] <Examples 6-10, Comparative Examples 1-3>

[0372] The photochromic curable composition is prepared by adding a photochromic compound to the above-mentioned polymeric compound compounding mixture at a rate of 0.53 μmol of photochromic portion per 100 g of polymeric compound. Using the resulting photochromic curable composition, a photochromic cured product is obtained by polymerization via a compounding method. The polymerization method is described below.

[0373] (Aggregation Method)

[0374] After thoroughly degassing the photochromic curable composition, it was cast into a mold consisting of a glass mold and a 2mm thick mold containing a gasket of ethylene-vinyl acetate copolymer. Then, it was cured over 24 hours while gradually increasing the temperature from 25°C to 70°C. After polymerization, the photochromic cured material was removed from the glass mold and annealed at 100°C for 1 hour.

[0375] (Solidified material: Evaluation method)

[0376] The obtained cured material was used as a sample, and a xenon lamp L-2480 (300W) SHL-100 manufactured by Hamamatsu Photonics Co., Ltd. was used, with an air mass filter (manufactured by Corning Inc.) between the lamps, at 20±1℃ and a beam intensity of 365nm = 2.4mW / cm² on the surface of the cured material. 2 245nm = 24μW / cm 2 Irradiate it for 300 seconds to induce color development, and measure the photochromic properties of the cured material.

[0377] The photochromic properties and the whitening of the cured product are evaluated using the following methods.

[0378] (1) Photochromic properties

[0379] • Maximum absorption wavelength (λmax):

[0380] The maximum absorption wavelength after color development was determined using a spectrophotometer (instantaneous multi-channel photodetector MCPD1000) manufactured by Otsuka Electronics Co., Ltd. This maximum absorption wavelength is related to the hue during color development.

[0381] • Colorimetric concentration {ε(300)-ε(0)}:

[0382] At the maximum absorption wavelength, the difference between the absorbance {ε(300)} after 300 seconds of light irradiation and the absorbance ε(0) before light irradiation. The higher this value, the better the photochromic property.

[0383] • Fading rate [t1 / 2(sec.)]:

[0384] The time required for the absorbance at the maximum absorption wavelength of the sample to decrease to half of {ε(300)-ε(0)} after 300 seconds of light irradiation and then stopping the irradiation is considered. The shorter this time, the better the photochromic property.

[0385] (2) Leukorrhea

[0386] For the solidified material, the turbidity is evaluated visually.

[0387] 1: The turbidity cannot be confirmed by visual inspection, and even when light passes through it, the turbidity cannot be confirmed at all.

[0388] 2: The turbidity cannot be confirmed by visual inspection, but a faint turbidity can be confirmed when light passes through it.

[0389] 3: The turbidity cannot be confirmed by visual inspection, but when light passes through, a turbidity that is more concentrated than that in 2 can be confirmed.

[0390] 4: A slight cloudiness can also be observed visually.

[0391] 5: The white turbidity can also be clearly identified by visual inspection.

[0392] (Comparative compound)

[0393] Comparative Examples 1-4 used photochromic compounds with the following structures.

[0394] (Compare Examples 1 and 4)

[0395]

[0396] (Comparative Example 2)

[0397]

[0398] (Comparative Example 3)

[0399]

[0400] [Table 1]

[0401]

[0402] It should be noted that in Table 1, the column labeled "Maximum Absorption Wavelength" records the positions (wavelengths) of the two peaks appearing in the spectroscopic spectrum. Of the two peaks, the one occurring at the shorter wavelength is designated as peak 1, and its wavelength is recorded in the upper part of the cell; the one occurring at the longer wavelength is designated as peak 2, and its wavelength is recorded in the lower part of the cell. In the column labeled "Color Development Concentration at 23℃," the color development concentration of peak 1 at 23℃ is recorded in the upper part of the cell, and the color development concentration of peak 23℃ is recorded in the lower part. In the column labeled "Fading Rate at 23℃," the fading rate of peak 1 at 23℃ is recorded in the upper part of the cell, and the fading rate of peak 23℃ is recorded in the lower part. The same applies to Tables 2-4.

[0403] As can also be seen from Table 1, the photochromic compound of the present invention exhibits superior photochromic properties compared to the photochromic compound of Comparative Example 1, which does not have oligomer chain groups.

[0404] Furthermore, it is known that, compared to the photochromic compound of Comparative Example 2 which consists only of polyoxypropylene chain groups, the aggregation of the photochromic compound was suppressed.

[0405] The photochromic compound of Comparative Example 3, which has oligomer chains of random polymer type with polyethylene glycol, has improved compatibility (dispersibility in solid matrix) and suppressed turbidity compared to the photochromic compound of Comparative Example 2, which has only polypropylene glycol chains. However, in the case of random polymers, due to insufficient formation of microphase separation structure, its dispersibility is poor compared to the photochromic compound of Example 1, which has block oligomer chains of polyethylene glycol.

[0406] As can be seen from these results, the photochromic compound of the present invention exhibits excellent photochromic properties even in a solid matrix, and also has excellent dispersibility.

[0407] <Example 11>

[0408] Except that polyethylene glycol monoceryl ether with a number average molecular weight of 770 was used instead of polyethylene glycol monomethyl ether with a number average molecular weight of 750, the reaction was carried out in the same manner as in Example 1 to obtain the compound shown in the following formula (39).

[0409]

[0410] The yield was 65%.

[0411] In addition, the proton nuclear magnetic resonance spectrum was measured, and the results showed that, compared with the 21H peak based on aromatic protons and olefin protons in the vicinity of δ5.6 to 9.0 ppm from the photochromic compound, the 52H peak based on cyclohexane ring and methyl, succinic acid site and hexadecyl protons in the vicinity of 1.0 to 3.0 ppm, and the approximately 58.4H peak based on methoxy, propoxy and ethoxy in the vicinity of δ3.0 to 5.5 ppm, the structure was confirmed to be consistent with the structure of formula (39).

[0412] <Example 12>

[0413] Process 1

[0414] Add the following formula (40)

[0415]

[0416] 115.4 g (100.0 mmol) of the compound shown, 1000 mL of DMF, and 17.0 g (250.0 mmol) of imidazole were stirred under ice. 14.9 g (99.0 mmol) of tert-butyldimethylchlorosilane dissolved in 150 mL of DMF was slowly added dropwise. After stirring for 12 hours, 1000 mL of water and 1500 mL of toluene were added, and the mixture was separated. The solvent of the concentrated organic layer was purified by silica gel column chromatography to obtain the compound shown in formula (41).

[0417]

[0418] Process 2

[0419] Using the formula (41), the same operation as in Example 1 was performed to obtain the compound shown in the following formula (42).

[0420]

[0421] Process 3

[0422] In step 5 of Example 1, the same procedure is followed except that the compound represented by formula (42) is used instead of the compound represented by formula (10), and the compound represented by formula (43) is used instead of the compound represented by formula (13).

[0423]

[0424] The compound shown in formula (44) was obtained.

[0425]

[0426] The yield was 65%.

[0427] In addition, the proton nuclear magnetic resonance spectrum was measured, and the results showed that, compared with the 17H ​​peak based on aromatic protons and alkene protons in the vicinity of δ5.6 to 9.0 ppm from the photochromic compound, the approximately 100H peak based on dimethylsilyl, succinic acid, and methyl protons in the vicinity of -1.0 to 3.0 ppm, and the approximately 90H peak based on methoxy and ethoxy groups in the vicinity of δ3.0 to 5.5 ppm, the structure was confirmed to be consistent with the structure of formula (44).

[0428] (Preparation and evaluation of cured products (acrylic molded products))

[0429] A photochromic curable composition was prepared by mixing the components according to the following formulation. The mixing amounts are shown below. The results of the photochromic properties of the cured products using the photochromic compounds of the examples described in Table 2 are shown in Table 2.

[0430] (Composition of polymeric compounds)

[0431] Propylene glycol diacrylate: 45 parts by weight

[0432] Trimethylolpropane triacrylate: 11 parts by weight

[0433] Polyethylene glycol diacrylate: 17 parts by weight

[0434] Kyoei Chemical Co., Ltd. manufactured UA-306T: 27 parts by weight

[0435] Ethylene bis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate]: 0.1 parts by weight

[0436] Bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate: 0.1 parts by weight

[0437] Di-tert-butyl peroxide: 1.75 parts by weight

[0438] <Examples 13-16, Comparative Example 4>

[0439] The photochromic curable composition is prepared by adding a photochromic compound to the above-mentioned polymeric compound compounding mixture at a rate of 0.53 μmol of photochromic portion per 100 g of polymeric compound. Using the resulting photochromic curable composition, a photochromic cured product is obtained by polymerization via a compounding method. The polymerization method is described below.

[0440] (Aggregation Method)

[0441] After thoroughly degassing the photochromic curable composition, it was cast into a mold consisting of a glass mold and a 2 mm thick mold containing a gasket of ethylene-vinyl acetate copolymer. Then, it was cured for 24 hours while gradually increasing the temperature from 25°C to 90°C. After polymerization, the photochromic cured material was removed from the glass mold and annealed at 100°C for 2 hours. The results are shown in Table 2.

[0442] [Table 2]

[0443]

[0444] It is evident that the photochromic compound of the present invention also exhibits excellent effects in acrylic substrates.

[0445] <Example 17>

[0446] Process 1

[0447] In the first step of Example 1, polypropylene glycol monobutyl ether with a number average molecular weight of 1500 was used instead of polyethylene glycol monomethyl ether with a number average molecular weight of 750. Otherwise, the same procedure was carried out to obtain the compound shown in the following formula (45).

[0448]

[0449] Process 2

[0450] In the first step of Example 12, polytetramethylene glycol with a number average molecular weight of 2000 was used instead of the compound of formula (40), and otherwise the same procedure was carried out to obtain the compound shown in formula (46).

[0451]

[0452] Process 3

[0453] In the second step of Example 1, the reaction was carried out in the same manner except that the compound of Formula (45) was used instead of the compound of Formula (7) and the compound of Formula (46) was used instead of the compound of Formula (8), to obtain the compound shown in Formula (47).

[0454]

[0455] Process 4

[0456] Perform the same operation as in step 3 of Example 1, adding succinic anhydride to the compound of formula (47) to obtain the compound shown in formula (48).

[0457]

[0458] Process 5

[0459] In the third step of Example 2, the compound of formula (48) was used instead of the compound of formula (15), and otherwise the same procedure was carried out to obtain the compound of formula (49) in 67% yield.

[0460]

[0461] In addition, the proton nuclear magnetic resonance spectrum was measured, and the results showed that, compared with the 17H ​​peak based on aromatic protons and olefin protons in the vicinity of δ5.6 to 9.0 ppm from the photochromic compound, the peak of about 149.5H based on cyclohexane ring and butyl, succinic acid site, propoxy, tetramethylene glycol group in the vicinity of 1.0 to 3.0 ppm, and the peak of 133.5H based on methoxy, propoxy, ethoxy, morpholino, polytetramethylene glycol group in the vicinity of δ3.0 to 5.5 ppm, the structure was confirmed to be consistent with the structure of formula (49).

[0462] Example 18

[0463] Process 1

[0464] In the third step of Example 17, the following formula (50) is used.

[0465]

[0466] The compound of formula (45) is replaced by the compound of formula (45), and the reaction is carried out in the same manner to obtain the compound of formula (51) below.

[0467]

[0468] Process 2

[0469] Perform the same operation as step 4 of Example 17, adding succinic anhydride to the compound of formula (51) to obtain the compound shown in formula (52).

[0470]

[0471] Process 3

[0472] In the fifth step of Example 1, the following formula (53) is used.

[0473]

[0474] The chromene compound shown is used instead of the chromene compound shown in formula (13), and the compound shown in formula (52) is used instead of the compound shown in formula (10). Otherwise, the same procedure is performed to obtain the compound shown in formula (54).

[0475]

[0476] The yield was 56%.

[0477] In addition, the proton nuclear magnetic resonance spectrum was measured, and the results showed that, compared with the 16H peak based on aromatic protons and olefin protons in the vicinity of δ5.6 to 9.0 ppm from the photochromic compound, the peak of about 166.4H based on cyclohexane ring and butyl, succinic acid, dimethylsilyl, polytetramethylene glycol protons in the vicinity of 0.0 to 3.0 ppm, and the peak of 55H based on methoxy, propoxy, ethoxy, polytetramethylene glycol in the vicinity of δ3.0 to 5.5 ppm, the structure was confirmed to be consistent with the structure of formula (54).

[0478] Example 19

[0479] In the third step of Example 17, the compound of formula (41) was used instead of the compound of formula (46), and otherwise the same procedure was performed to obtain the compound shown in formula (55).

[0480]

[0481] Process 2

[0482] Perform the same operation as step 4 of Example 17, adding succinic anhydride to the compound of formula (55) to obtain the compound shown in formula (56).

[0483]

[0484] Process 3

[0485] In step 5 of Example 17, the compound of formula (56) was used instead of the compound of formula (48), and otherwise the same procedure was carried out to obtain the compound of formula (57) in 54% yield.

[0486]

[0487] In addition, the proton nuclear magnetic resonance spectrum was measured, and the results showed that, compared with the 17H ​​peak based on aromatic protons and olefin protons in the vicinity of δ5.6 to 9.0 ppm from the photochromic compound, the peak of about 194.9H based on cyclohexane ring and butyl, succinic acid site, propoxy, and dimethylsiloxane protons in the vicinity of 0.0 to 3.0 ppm, and the peak of about 104.3H based on methoxy, propoxy, ethoxy, and morpholino groups in the vicinity of δ3.0 to 5.5 ppm, the structure was confirmed to be consistent with the structure of formula (57).

[0488] Example 20

[0489] Process 1

[0490] In the third step of Example 17, the compound of formula (7) was used instead of the compound of formula (45), and otherwise the reaction was carried out in the same manner to obtain the compound shown in formula (58).

[0491]

[0492] Process 2

[0493] Perform the same operation as step 4 of Example 17, adding succinic anhydride to the compound of formula (58) to obtain the compound shown in formula (59).

[0494]

[0495] Process 3

[0496] In step 5 of Example 1, the compound of formula (59) was used instead of the compound of formula (10), and otherwise the reaction was carried out in the same manner to obtain the compound shown in formula (60).

[0497]

[0498] The yield was 57%.

[0499] In addition, the proton nuclear magnetic resonance spectrum was measured, and the results showed that, compared with the 21H peak based on aromatic protons and olefin protons in the vicinity of δ5.6 to 9.0 ppm from the photochromic compound, the peak of about 67.6H based on cyclohexane ring and methyl, succinic acid site, and tetramethylene glycol protons in the vicinity of 1.0 to 3.0 ppm, and the peak of about 123H based on methoxy, polytetramethylene glycol group, and ethoxide group in the vicinity of δ3.0 to 5.5 ppm, the structure was confirmed to be consistent with the structure of formula (60).

[0500] Example 21

[0501] Process 1

[0502] In the first step of Example 1, polypropylene glycol monobutyl ether with a number average molecular weight of 2500 was used instead of polyethylene glycol monomethyl ether with a number average molecular weight of 750. Otherwise, the same procedure was carried out to obtain the compound shown in the following formula (61).

[0503]

[0504] Process 2

[0505] In the first step of Example 12, polyethylene glycol with a number average molecular weight of 1000 was used instead of the compound of formula (40), and otherwise the same procedure was carried out to obtain the compound shown in formula (62).

[0506]

[0507] Process 3

[0508] In the second step of Example 1, the reaction was carried out in the same manner except that the compound of formula (61) was used instead of the compound of formula (7) and the compound of formula (62) was used instead of the compound of formula (8), to obtain the compound shown in formula (63).

[0509]

[0510] Process 4

[0511] Perform the same operation as step 4 of Example 17, adding succinic anhydride to the compound of formula (63) to obtain the compound shown in formula (64).

[0512]

[0513] Process 5

[0514] In step 5 of Example 1, the reaction was carried out in the same manner except that the compound of formula (64) was used instead of the compound of formula (10) to obtain the compound shown in formula (65).

[0515]

[0516] The yield was 63%.

[0517] In addition, the proton nuclear magnetic resonance spectrum was measured, and the results showed that, compared with the 21H peak based on aromatic protons and olefin protons in the vicinity of δ5.6 to 9.0 ppm from the photochromic compound, the peak of about 160.2H based on cyclohexane ring and methyl, succinic acid site, and butyl protons in the vicinity of 1.0 to 3.0 ppm, and the peak of about 231.2H based on methoxy, ethylene glycol site, propylene glycol site, ethoxy, and butoxy in the vicinity of δ3.0 to 5.5 ppm, the structure was confirmed to be consistent with the structure of formula (65).

[0518] <Examples 22-25>

[0519] The photochromic cured products were evaluated using the same method as in Example 6. The results are shown in Table 3.

[0520] [Table 3]

[0521]

[0522] <Examples 26-28, Comparative Examples 5-7>

[0523] (Fabrication and Evaluation of Photochromic Laminates)

[0524] A photochromic curable composition is prepared by mixing the components according to the following formulation. The mixing amounts are shown below.

[0525] (Composition of polymeric compounds)

[0526] 32 parts by weight of polyethylene glycol dimethacrylate (average molecular weight 736).

[0527] 18 parts by weight of polyethylene glycol dimethacrylate (average molecular weight 536).

[0528] 37 parts by weight of trimethylolpropane trimethacrylate.

[0529] 2 parts by mass of γ-methacryloyloxypropyltrimethoxysilane.

[0530] 1 part by weight of glycidyl methacrylate.

[0531] 0.3 parts by weight of phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide (trade name: Irgacure 819, manufactured by BASF) (polymerization initiator).

[0532] 3 parts by weight of bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (molecular weight 508) (stabilizer).

[0533] Parts by weight of 1 part by weight of ethylene bis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] (CibaSpecialty Chemicals, Inc., Irganox 245) (stabilizer).

[0534] Dow Corning Toray Co. Ltd. manufactures product L7001 (leveling agent) 0.1 parts by weight.

[0535] The photochromic curable composition is added to the above-described formulation at a concentration of 2.5 mmol of photochromic compound per 100 g of polymerizable compound. Using the resulting photochromic curable composition, a photochromic laminate is obtained by coating. The polymerization method is described below.

[0536] First, a thiocarbamate-based plastic lens with a center thickness of 2 mm and a refractive index of 1.60 was prepared as the optical substrate. It should be noted that this thiocarbamate-based plastic lens was pre-etched with a 10% sodium hydroxide aqueous solution at 50°C for 5 minutes, followed by thorough cleaning with distilled water.

[0537] Using a spin coater (1H-DX2, manufactured by MIKASA), a moisture-curing primer (product name: TR-SC-P, manufactured by Tokuyama Corporation) was applied to the surface of the aforementioned plastic lens at a spin speed adjusted to achieve a film thickness of 7 μm. Then, approximately 2 g of the obtained photochromic composition was spin-coated at 100 rpm for 25 seconds, followed by spin-coating at 1000 rpm for 10–20 seconds to achieve a photochromic coating thickness of 40 μm.

[0538] In a nitrogen atmosphere, a power of 200 mW / cm is used. 2 A metal halide lamp was used to irradiate a lens coated with such a coating agent for 90 seconds to cure the coating. Then, the lens was further heated at 110°C for 1 hour to produce a photochromic laminate with a photochromic layer.

[0539] The obtained photochromic laminate was evaluated using the same method as in Example 6. The evaluation results are shown in Table 4.

[0540] [Table 4]

[0541]

Claims

1. A photochromic compound, which is represented by the following formula (1) or (2), In the formula, PC is a group having at least one photochromic site. X1 and X3 are each independently a straight-chain or branched alkylene group with 12 to 30 carbon atoms, a polyoxypropylene group with 3 to 200 repeating units, a polyoxyethylene group with 3 to 200 repeating units, a polyoxytetramethylene group with 3 to 200 repeating units, or a polysiloxane group with 3 to 200 repeating units formed from a methylenesiloxy group, wherein the methylenesiloxy group has two substituents selected from the group consisting of a straight-chain or branched alkyl group with 1 to 10 carbon atoms, a straight-chain or branched alkoxy group with 1 to 10 carbon atoms, and an aromatic group with 6 to 10 carbon atoms. X2 is a straight-chain or branched alkylene group with 12 to 30 carbon atoms, a polyoxypropylene group with 3 to 200 repeating units, a polyoxyethylene group with 3 to 200 repeating units, or a polyoxytetramethylene group with 3 to 200 repeating units. X1 and X2 are different groups, X2 and X3 are different groups, but X1 and X3 can be the same type of group. When X2 in formula (1) or X3 in formula (2) is a straight-chain or branched alkylene group with 12 to 30 carbon atoms, Z is a hydrogen atom, a methyl group, or an alkoxy group with 1 to 10 carbon atoms. When X2 in formula (1) or X3 in formula (2) is a polyoxypropylene group with 3 to 200 repeating units, a polyoxyethyl group with 3 to 200 repeating units, a polyoxytetramethylene group with 3 to 200 repeating units, or a polysiloxane group with 3 to 200 repeating units formed from a methylene siloxy group, Z is a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, or an alkoxy group with 1 to 10 carbon atoms. The methylene siloxy group has two substituents selected from the group consisting of a straight-chain or branched alkyl group with 1 to 10 carbon atoms, a straight-chain or branched alkoxy group with 1 to 10 carbon atoms, and an aromatic group with 6 to 10 carbon atoms. L1 is selected from the groups listed below: ， in, The dashed lines represent the portion bonded to PC and X1 in the photochromic region. In equation (1): L2 is selected from the groups listed below when m is 1: ， When L2 is 2 or more, it is selected from the groups listed below: ， The dashed part represents the key to X1 or X2. In equation (2): L2 and L3 are selected from the groups listed below when m and l are 1: ， When m and l are 2 or more, L2 and L3 are selected from the groups listed below: ， The dashed part represents the key to X1, X2, or X3. n is an integer from 1 to 8, m is an integer from 1 to 4, and l is an integer from 1 to 4.

2. The photochromic compound according to claim 1, wherein, X1 is a straight-chain or branched alkylene group with 12 to 30 carbon atoms, a polyoxypropylene group with 3 to 200 repeating units, or a polysiloxane group with 3 to 200 repeating units formed from methylenesiloxy groups. The methylenesiloxy group has two substituents selected from the group consisting of a straight-chain or branched alkyl group with 1 to 10 carbon atoms, a straight-chain or branched alkoxy group with 1 to 10 carbon atoms, and an aromatic group with 6 to 10 carbon atoms. X2 is either polyoxyethylene with 3 to 200 repeating units or polyoxytetramethylene with 3 to 200 repeating units.

3. The photochromic compound according to claim 1, wherein, X1 is a polyoxyethylene compound with 3 to 200 repeating units. X2 is a linear or branched alkylene group with 12 to 30 carbon atoms, a polyoxypropylene group with 3 to 200 repeating units, or a polyoxytetramethylene group with 3 to 200 repeating units.

4. The photochromic compound according to claim 1, wherein, X1 is a polyoxytetramethylene compound with 3 to 200 repeating units. X2 is a linear or branched alkylene group with 12 to 30 carbon atoms, a polyoxypropylene group with 3 to 200 repeating units, or a polyoxyethylene group with 3 to 200 repeating units.

5. The photochromic compound according to any one of claims 1 to 4, wherein, The photochromic region has at least one structure selected from the group consisting of naphthopyran, spiroxazine, spiropyran, succinic anhydride, succinic imide, and diarylethylene.

6. The photochromic compound according to claim 5, wherein, The naphthopyran portion is the indo-naphthopyran portion.

7. The photochromic compound according to claim 6, wherein, The indo-naphtho-pyran portion is shown in the following formula (6). In the formula, R 1 and R 2 Each of the following can be an atomic bond bonded to L1: hydroxyl, alkyl, haloalkyl, optionally substituted cycloalkyl, alkoxy, amino, substituted amino, amide, substituted amide, optionally substituted heterocyclic, cyano, halogen atom, alkylthio, optionally substituted arylthio, nitro, formyl, hydroxycarbonyl, alkylcarbonyl, alkoxycarbonyl, optionally substituted aralkyl, optionally substituted arylalkoxy, optionally substituted aryl, optionally substituted aryl, optionally substituted heteroaryl, thiol, alkoxyalkylthio, haloalkylthio, or optionally substituted cycloalkylthio. a is an integer from 0 to 4, b is an integer from 0 to 4. When a is 2 to 4, multiple R 2 Choose either the same or different from each other. When b is 2 to 4, multiple R 1 Choose either the same or different from each other. When a is 2 to 4 and there are adjacent R 2 At that time, two adjacent R 2 Optional to become one and with these R 2 The bonded carbon atoms together form a ring optionally containing oxygen, carbon, sulfur, or nitrogen atoms, and the ring optionally has substituents. When b is 2 to 4 and there are adjacent R 1 At that time, two adjacent R 1 Optional to become one and with these R 1 The bonded carbon atoms together form a ring optionally containing oxygen, carbon, sulfur, or nitrogen atoms, and the ring optionally has substituents. R 3 and R 4 Each of the substituents is an aryl group optionally having a substituent, or a heteroaryl group optionally having a substituent, which is optionally bonded to the L1. R 5 and R 6 Each of the following is independently an atomic bond bonded to L1: a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a halogen atom, an aralkyl group optionally having a substituent, an aralkoxy group optionally having a substituent, an aryl group optionally having a substituent, or a heterocyclic group optionally having a substituent. R 5 and R 6 Both can be integrated and together with the carbon atom at position 13 bonded to form an aliphatic ring with 3 to 20 cyclic carbon atoms, a fused polycyclic ring with an aromatic ring or aromatic heterocycle fused onto the aliphatic ring, a heterocycle with 3 to 20 cyclic atoms, or a fused polycyclic ring with an aromatic ring or aromatic heterocycle fused onto the heterocycle, wherein these rings optionally have substituents. Choose freely R 1 R 2 R 3 aryl substituents, R 3 Substituents of heteroaryl groups, R 4 aryl substituents, heteroaryl substituents, R 5 and R 6 The n groups in the group are bonded to L1.

8. A photochromic curable composition comprising the photochromic compound and a polymeric compound as described in any one of claims 1 to 7.

9. A cured product, which is a polymer of the photochromic curable composition of claim 8.

10. A lens comprising the cured material of claim 9.

11. A pair of eyeglasses having the lens of claim 10.

Images