Photochromic curable composition and photochromic optical article

Abstract

The present invention provides: a photochromic curable composition which contains (A) a (meth)acrylate composition that contains from 24 to 100% by mass of a polyfunctional (meth)acrylate which has three or more (meth)acryloyl groups in each molecule and (B) a photochromic compound that is obtained by bonding at least one specific naphthopyran to a long-chain group having a number average molecular weight of from 300 to 10,000; and a photochromic optical article which is obtained by polymerizing this photochromic curable composition.

Description

[Technical Field]

[0001] The present invention relates to photochromic curable compositions and photochromic optical articles. [Background technology]

[0002] Photochromic compounds, such as naphthopyran compounds, fulgide compounds, and spirooxazine compounds, are compounds that can reversibly convert into two isomers with different absorption spectra when irradiated with ultraviolet light, such as sunlight or mercury lamp light. Photochromic compounds generally have the property that when irradiated with ultraviolet light from a colorless, bleached compound, they quickly isomerize (color-developing reaction) to a colored state, and then return to their original color when the light irradiation is stopped and the compound is placed in a dark place (hereinafter also referred to as "photochromic property"). Taking advantage of this property, they are used in a variety of applications, particularly as optical materials.

[0003] For example, photochromic eyeglass lenses, which are given photochromic properties by using a photochromic compound, quickly become colored and function as sunglasses when exposed outdoors to light containing ultraviolet rays, such as sunlight, and fade and function as clear, ordinary eyeglasses indoors when not exposed to such light, and demand for such lenses has been increasing in recent years.

[0004] In order to impart photochromic properties to an optical article, a photochromic compound and a plastic material are generally used in combination, and specifically, the following methods are known. (a) A method in which a photochromic compound is mixed with a polymerizable monomer and polymerized to directly mold an optical article such as a lens. (b) A method in which a resin layer in which a photochromic compound is dispersed is provided on the surface of a plastic molded product such as a lens by coating or cast polymerization. (c) A method in which two optical sheets are bonded together with an adhesive layer formed from a resin composition in which a photochromic compound is dispersed.

[0005] Among these, as disclosed in Patent Document 1, a coating method in which a photochromic curable composition is applied to a plastic lens by spin coating or the like and then photocured to form a photochromic coating layer is particularly effective because it can be applied to various existing lenses.

[0006] Among the photochromic compounds used in photochromic optical articles, those that not only block light of a specific wavelength when isomerizing from a colored state to a colorless state (fading reaction), but also return to their original colorless state when exposed to heat, are called T-type photochromic compounds. T-type photochromic compounds have been extensively studied as materials for photochromic lenses. Generally, the following properties are required of T-type photochromic compounds: (1) The degree of coloration in the visible light region before irradiation with ultraviolet light (hereinafter referred to as "initial coloration") is small. (2) The color density reaches saturation quickly after UV irradiation begins (i.e., the color sensitivity is high). (3) The speed at which the color returns to its original state after UV irradiation is stopped (hereinafter referred to as the "fading speed"). (4) Good durability for repeated reversible reactions. (5) To enhance dispersibility in the host material used, the compound dissolves at a high concentration in the monomer composition that will become the host material after curing.

[0007] Many studies have been conducted on chromene compounds as photochromic compounds that satisfy these properties. In recent years, the requirements for photochromic glasses have become more stringent, for example, there is a demand for reduced temperature dependency.

[0008] It is generally known that T-type photochromic compounds have a trade-off between fading speed and color density. Therefore, when used in high temperatures, such as in the summer when sunlight is strong, fading reactions are more likely to occur, resulting in a decrease in color density. This means that they are susceptible to the effects of ambient temperature (high temperature dependency). For this reason, there is a particular demand for the development of photochromic lenses that have high color density even in high temperatures, such as in the summer (hereinafter, the property of having high color density even at high temperatures may also be referred to as "low temperature dependency").

[0009] Generally, to obtain high color density at high temperatures, it is necessary to improve the thermal stability of a photochromic compound in the colored state, i.e., to obtain a photochromic compound with a slow fading rate. Therefore, it is generally difficult to achieve both the property (3) above and a low temperature dependency. The present inventors have proposed a chromene compound with reduced temperature dependency by having a substituent at a specific position (see Patent Document 2). Although this compound can achieve relatively low temperature dependency, the color tone is limited because it has a substituent at a specific position, and there is still room for further improvement in the fading rate in a solid matrix.

[0010] In a solid matrix, structural changes associated with isomerization of photochromic compounds are limited, which generally leads to a slower fading rate. Therefore, to improve the fading rate, it is possible to soften the substrate by lowering the glass transition temperature of the solid matrix (polymer) or to increase the free space in the matrix. However, while it is possible to create an environment in which structural changes of the photochromic compound are more likely to occur by using a solid matrix with a low glass transition temperature or a matrix with a large free space, the crosslinking density is insufficient, which increases the temperature dependence of the solid matrix. As a result, the temperature dependence of the photochromic properties is increased, making it impossible to achieve the high photochromic properties currently required. Furthermore, the strength and hardness of the resulting photochromic lenses are insufficient. When photochromic properties are imparted by a coating method, the photochromic compounds tend to leach out when a hard coat layer is formed on the photochromic coating layer, leaving room for improvement.

[0011] Another method for improving the fading rate in a solid matrix is ​​to use a photochromic compound having an oligomer chain group (see Patent Documents 3 to 5). However, the compatibility of the oligomer chain group photochromic compound with the solid matrix used is important. If the compatibility is low, the solid matrix becomes cloudy, which limits the types of solid matrix that can be used, leaving room for improvement. Furthermore, when expressing photochromic properties in a thin film by a coating method or the like, the photochromic compound must be added at a high concentration. However, the oligomer chain group reduces the concentration of the photochromic compound in the molecule, so a higher concentration is required. As a result, there are problems such as a significant decrease in the hardness of the photochromic coating layer. [Prior art documents] [Patent documents]

[0012] [Patent Document 1] International Publication No. 2011 / 125956 [Patent Document 2] Japanese Patent Application Publication No. 2018-062496 [Patent Document 3] International Publication No. 2004 / 041961 [Patent Document 4] International Publication No. 2000 / 015630 [Patent Document 5] International Publication No. 2019 / 013249 Summary of the Invention [Problem to be solved by the invention]

[0013] As described above, further improvements are necessary to meet the recent demand for high photochromic properties (particularly reduced temperature dependency), and further improvements are also necessary in terms of the strength and hardness of host materials such as resins.

[0014] Therefore, an object of the present invention is to provide a photochromic curable composition that achieves sufficient strength and hardness as well as high photochromic properties, and a photochromic optical article that uses the photochromic curable composition. [Means for solving the problem]

[0015] The present inventors have conducted extensive research to solve the above problems, and as a result have found that the above problems can be solved not only by using a photochromic compound having an oligomer chain group but also by using a specific host material, thereby completing the present invention.

[0016] That is, the photochromic curable composition according to the present invention comprises: (A) a (meth)acrylate composition having a content of a polyfunctional (meth)acrylate having three or more (meth)acryloyl groups in the molecule of 24 to 100 mass %; (B) at least one of the following formula (1): [ka] (In the formula, R 1and R 2 each independently represent a group bonded to a long-chain group having a number average molecular weight of 300 to 10,000, or a hydroxy group, an alkyl group, a haloalkyl group, a cycloalkyl group which may have a substituent, an alkoxy group, an amino group, a substituted amino group, a heterocyclic group which may have a substituent, a cyano group, a halogen atom, an alkylthio group, an arylthio group which may have a substituent, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aralkyl group which may have a substituent, an aralkoxy group which may have a substituent, an aryloxy group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, a thiol group, an alkoxyalkylthio group, a haloalkylthio group, or a cycloalkylthio group which may have a substituent; a represents an integer of 0 to 2, b represents an integer of 0 to 4, If a is 2, multiple R 1 may be the same or different from each other, a is 2 and adjacent R 1 If there is a 1 Together they R 1 may form a ring together with the carbon atom bonded to it which may contain an oxygen atom, a sulfur atom, or a nitrogen atom, and the ring may further have a substituent, When b is 2 to 4, multiple R 2 may be the same or different from each other, b is 2 to 4, and adjacent R 2 If there is a 2 Together they R 2 may form a ring together with the carbon atom bonded to it which may contain an oxygen atom, a sulfur atom, or a nitrogen atom, and the ring may further have a substituent, If neither a nor b is 0, then at least one R 1 and at least one R 2 may be taken together to form a ring, and the ring may further have a substituent, R 3 and R4 each independently represents a group bonded to a long-chain group having a number average molecular weight of 300 to 10,000, or an aryl group which may have a substituent, or a heteroaryl group which may have a substituent, R 1 , R 2 , R 3 , and R 4 At least one of the groups is a group that bonds to a long-chain group having a number average molecular weight of 300 to 10,000.) and a photochromic compound in which naphthopyran represented by the formula (I) is bonded to a long chain group having a number average molecular weight of 300 to 10,000. It contains:

[0017] The photochromic optical article according to the present invention is obtained by polymerizing the photochromic curable composition according to the present invention. [Effects of the Invention]

[0018] According to the present invention, it is possible to provide a photochromic curable composition that achieves sufficient strength and hardness as well as high photochromic properties, and a photochromic optical article using the photochromic curable composition. [Brief explanation of the drawings]

[0019] [Figure 1] FIG. 1 is a graph showing the relationship between temperature dependency and fading half-life for compounds of Examples and Comparative Examples. DETAILED DESCRIPTION OF THE INVENTION

[0020] <Photochromic curable composition> The photochromic curable composition according to this embodiment contains (A) a (meth)acrylate composition (hereinafter also referred to as "Component A") containing 24 to 100 mass% of a polyfunctional (meth)acrylate having three or more (meth)acryloyl groups in the molecule, and (B) a photochromic compound (hereinafter also referred to as "Component B") in which at least one specific naphthopyran is bonded to a long-chain group having a number-average molecular weight of 300 to 10,000. This photochromic curable composition makes it possible to obtain a photochromic optical article having sufficient strength and hardness while exhibiting high photochromic properties. The inventors of the present invention consider the reason for this effect as follows.

[0021] Specifically, a host material obtained by polymerizing a (meth)acrylate composition containing 24 to 100% by mass of a multifunctional (meth)acrylate having three or more (meth)acryloyl groups per molecule can provide sufficient strength and hardness as a solid matrix. Normally, such solid matrices lack sufficient free space, making photochromic properties difficult to achieve. However, in the case of a photochromic compound in which at least one naphthopyran is bonded to a long-chain group having a number-average molecular weight of 300 to 10,000, an environment in which structural change is likely to occur only near the long-chain group can be formed. This is believed to enable the realization of sufficient strength and hardness while maintaining an environment in which structural change is likely to occur. Furthermore, the high crosslink density of the resulting solid matrix reduces the temperature dependence of the solid matrix, thereby maintaining low temperature dependence of photochromic properties. This allows for the production of photochromic optical articles with high color density, even at high temperatures such as those found in summer.

[0022] The term "(meth)acryloyl group" means both "acryloyl group" and "methacryloyl group." The same applies to other terms such as "(meth)acrylate."

[0023] <(A) (Meth)acrylate Composition> The (meth)acrylate composition of component A is not particularly limited, and a known polyfunctional (meth)acrylate may be used alone, or a known polyfunctional (meth)acrylate may be used in combination with other polymerizable monomers. Typically, a combination of (A1) a polyfunctional (meth)acrylate having three or more (meth)acryloyl groups in the molecule (hereinafter also referred to as "component A1") and (A2) a bifunctional (meth)acrylate (hereinafter also referred to as "component A2") is used, and, if necessary, a combination of (A3) a monofunctional (meth)acrylate (hereinafter also referred to as "component A3") or (A4) a polymerizable monomer other than (A1) to (A3) (hereinafter also referred to as "component A4") is preferably used. The various compounds used as component A are described in detail below.

[0024] [A1 component] The component A1 is not particularly limited as long as it is a polyfunctional (meth)acrylate having three or more (meth)acryloyl groups in the molecule, and polyfunctional (meth)acrylates represented by the following formula (3), polyfunctional (meth)acrylates having a urethane bond, and polyfunctional (meth)acrylates other than those described above are preferably used.

[0025] ((A1-1) Polyfunctional (meth)acrylate represented by the following formula (3)) [ka]

[0026] In the formula, R 10 represents a hydrogen atom or a methyl group, and R 11 represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and R 12 represents a trivalent to hexavalent organic group having 1 to 10 carbon atoms, e represents an average value of 0 to 3, and f represents an integer of 3 to 6. 11 As the alkyl group having 1 to 2 carbon atoms represented by R, a methyl group is preferred. 12 Examples of the organic group represented by the formula (I) include a group derived from a polyol, a trivalent to hexavalent hydrocarbon group, and an organic group containing a trivalent to hexavalent urethane bond.

[0027] Specific examples of the polyfunctional (meth)acrylate represented by the above formula (3) include trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetramethacrylate, tetramethylolmethane tetraacrylate, trimethylolpropane triethylene glycol trimethacrylate, trimethylolpropane triethylene glycol triacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetramethacrylate, ditrimethylolpropane tetramethacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexamethacrylate, and dipentaerythritol hexaacrylate.

[0028] ((A1-2) Polyfunctional (meth)acrylate having a urethane bond) (A1-2) The polyfunctional (meth)acrylate having a urethane bond is obtained by reacting a polyisocyanate compound having two or more isocyanate groups in the molecule, a polyol compound having two or more hydroxy groups in the molecule, and a hydroxy group-containing (meth)acrylate, and has three or more (meth)acryloyl groups in the molecule.

[0029] Specific examples of polyisocyanate compounds having two or more isocyanate groups in the molecule include hexamethylene diisocyanate, isophorone diisocyanate, lysine isocyanate, 2,2,4-hexamethylene diisocyanate, dimer acid diisocyanate, isopropylidenebis-4-cyclohexyl isocyanate, dicyclohexylmethane diisocyanate, norbornene diisocyanate, and methylcyclohexane diisocyanate.

[0030] Specific examples of polyol compounds having two or more hydroxy groups in the molecule include glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol.

[0031] As the polyfunctional (meth)acrylate having a urethane bond, commercially available products can also be used, such as U-4HA (molecular weight: 596, number of functional groups: 4), U-6HA (molecular weight: 1019, number of functional groups: 6), U-6LPA (molecular weight: 818, number of functional groups: 6), and U-15HA (molecular weight: 2300, number of functional groups: 15), all manufactured by Shin-Nakamura Chemical Co., Ltd.

[0032] ((A1-3) Polyfunctional (meth)acrylates not falling under the above categories) (A1-3) Examples of polyfunctional (meth)acrylates not falling under the above-mentioned category include compounds in which the terminals of polyester compounds are modified with (meth)acryloyl groups. Various polyester (meth)acrylate compounds are commercially available, varying in molecular weight from the raw polyester compound and the amount of (meth)acryloyl group modification, and these commercially available products can be used. Specific examples of polyester (meth)acrylate compounds include tetrafunctional polyester oligomers (molecular weight: 2500 to 3500, manufactured by Daicel-Allnex Corporation, EB80, etc.), hexafunctional polyester oligomers (molecular weight: 6000 to 8000, manufactured by Daicel-Allnex Corporation, EB450, etc.), hexafunctional polyester oligomers (molecular weight: 45000 to 55000, manufactured by Daicel-Allnex Corporation, EB1830, etc.), and tetrafunctional polyester oligomers (molecular weight: 10000, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., GX8488B, etc.).

[0033] By using the above-exemplified A1 component, it is possible to improve strength and hardness while maintaining photochromic properties.

[0034] The above-mentioned A1 components may be used singly or in combination of two or more types for each of the individually described components. Furthermore, the individually described components may be used in combination with each other. When multiple types of A1 components are used in combination, the reference mass of the A1 component is the total amount of these.

[0035] Among the above-mentioned components A1, trimethylolpropane trimethacrylate, ditrimethylolpropane tetramethacrylate, and dipentaerythritol hexaacrylate are preferred.

[0036] [A2 component] The component A2 is not particularly limited as long as it is a bifunctional (meth)acrylate, and bifunctional (meth)acrylates represented by the following formula (4), (5), or (6), bifunctional (meth)acrylates having a urethane bond, and bifunctional (meth)acrylates other than those listed above are preferably used.

[0037] ((A2-1) Bifunctional (meth)acrylate represented by the following formula (4)) [ka]

[0038] In the formula, R 13 and R 14 each independently represents a hydrogen atom or a methyl group, g and h each independently represents an integer of 0 or greater, and g+h is an integer of 2 or greater. Note that the bifunctional (meth)acrylate represented by the above formula (4) is often obtained as a mixture in production. Therefore, g+h is an average number of 2 or greater, and preferably an average number of 2 to 50.

[0039] Specific examples of the bifunctional (meth)acrylate represented by the above formula (4) include diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, pentaethylene glycol dimethacrylate, pentapropylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, pentaethylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, pentapropylene glycol diacrylate, dimethacrylate consisting of a mixture of polypropylene glycol and polyethylene glycol (having two polyethylene and two polypropylene repeating units), polyethylene glycol dimethacrylate (particularly, g=4, h=0, average molecular weight Amount: 330), polyethylene glycol dimethacrylate (particularly, g = 9, h = 0, average molecular weight: 536), polyethylene glycol dimethacrylate (particularly, g = 14, h = 0, average molecular weight: 736), tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, polypropylene glycol dimethacrylate (particularly, g = 0, h = 7, average molecular weight: 536), polyethylene glycol diacrylate (particularly, average molecular weight: 258), polyethylene glycol diacrylate (particularly, g = 4, h = 0, average molecular weight: 308), polyethylene glycol diacrylate (particularly, g = 9, h = 0, average molecular weight: 508), polyethylene glycol diacrylate (particularly, g = 14, h = 0, average molecular weight: 708), polyethylene glycol methacrylate acrylate (particularly, g = 9, h = 0, average molecular weight: 522), and the like.

[0040] ((A2-2) Bifunctional (meth)acrylate represented by the following formula (5)) [ka]

[0041] In the formula, R 15 and R 16each independently represents a hydrogen atom or a methyl group, and R 17 and R 18 each independently represents a hydrogen atom or a methyl group, and R 19 represents a hydrogen atom or a halogen atom, and A represents -O-, -S-, -(SO2)-, -CO-, -CH2-, -CH=CH-, -C(CH3)2-, or -C(CH3)(CH6H5)-. i and j each independently represent an integer of 1 or more, and i+j is an average value of 2 to 30. The bifunctional (meth)acrylate represented by the above formula (5) is usually obtained in the form of a mixture of molecules with different molecular weights. Therefore, i+j is expressed as an average value.

[0042] Specific examples of the bifunctional (meth)acrylate represented by the above formula (5) include 2,2-bis[4-(methacryloyloxyethoxy)phenyl]propane (i+j=2, average molecular weight: 452), 2,2-bis[4-(methacryloyloxydiethoxy)phenyl]propane (i+j=4, average molecular weight: 540), 2,2-bis[4-(methacryloyloxypolyethoxy)phenyl]propane (i+j=7, average molecular weight: 540), and Average molecular weight: 672), 2,2-bis[3,5-dibromo-4-(methacryloyloxyethoxy)phenyl]propane (i+j=2, average molecular weight: 768), 2,2-bis(4-(methacryloyloxydipropoxy)phenyl)propane (i+j=4, average molecular weight: 596), 2,2-bis[4-(acryloyloxydiethoxy)phenyl]propane (i+j=4, average molecular weight: 512), 2,2-bis[4-( 2,2-bis[4-(acryloyloxypolyethoxy)phenyl]propane (i+j=3, average molecular weight: 466), 2,2-bis[4-(acryloyloxypolyethoxy)phenyl]propane (i+j=7, average molecular weight: 642), 2,2-bis[4-(methacryloyloxypolyethoxy)phenyl]propane (i+j=10, average molecular weight: 804), 2,2-bis[4-(methacryloyloxypolyethoxy)phenyl]propane (i +j=17, average molecular weight: 1116), 2,2-bis[4-(methacryloyloxypolyethoxy)phenyl]propane (i+j=30, average molecular weight: 1684), 2,2-bis[4-(acryloyloxypolyethoxy)phenyl]propane (i+j=10, average molecular weight: 776), 2,2-bis[4-(acryloyloxypolyethoxy)phenyl]propane (i+j=20, average molecular weight: 1216), etc.

[0043] ((A2-3) Bifunctional (meth)acrylate represented by the following formula (6)) [ka]

[0044] In the formula, R 20 and R 21each independently represents a hydrogen atom or a methyl group, k represents an average value of 1 to 20, and B and B' each independently represent a linear or branched alkylene group having 2 to 15 carbon atoms. When there are multiple Bs, the multiple Bs may be the same or different groups.

[0045] The bifunctional (meth)acrylate represented by the above formula (6) can be produced by reacting a polycarbonate diol with (meth)acrylic acid.

[0046] Specific examples of polycarbonate diols include polycarbonate diols (average molecular weight: 500 to 2000) obtained by phosgenation of trimethylene glycol, polycarbonate diols (average molecular weight: 500 to 2000) obtained by phosgenation of tetramethylene glycol, polycarbonate diols (average molecular weight: 500 to 2000) obtained by phosgenation of pentamethylene glycol, polycarbonate diols (average molecular weight: 500 to 2000) obtained by phosgenation of hexamethylene glycol, polycarbonate diols (average molecular weight: 500 to 2000) obtained by phosgenation of octamethylene glycol, polycarbonate diols (average molecular weight: 500 to 2000) obtained by phosgenation of nonamethylene glycol, and phosgenated polycarbonate diols of triethylene glycol and tetramethylene glycol. Examples of the polycarbonate diol include polycarbonate diol (average molecular weight: 500 to 2000) obtained by phosgenation of tetramethylene glycol and hexamethylene glycol, polycarbonate diol (average molecular weight: 500 to 2000) obtained by phosgenation of pentamethylene glycol and hexamethylene glycol, polycarbonate diol (average molecular weight: 500 to 2000) obtained by phosgenation of tetramethylene glycol and octamethylene glycol, polycarbonate diol (average molecular weight: 500 to 2000) obtained by phosgenation of hexamethylene glycol and octamethylene glycol, and polycarbonate diol (average molecular weight: 500 to 2000) obtained by phosgenation of 1-methyltrimethylene glycol.

[0047] ((A2-4) Bifunctional (meth)acrylate having a urethane bond) (A2-4) As the bifunctional (meth)acrylate having a urethane bond, one obtained by reacting a polyisocyanate compound having two or more isocyanate groups in the molecule, a polyol compound having two or more hydroxy groups in the molecule, and a hydroxy group-containing (meth)acrylate is suitable.

[0048] Specific examples of polyisocyanate compounds having two or more isocyanate groups in the molecule include hexamethylene diisocyanate, isophorone diisocyanate, lysine isocyanate, 2,2,4-hexamethylene diisocyanate, dimer acid diisocyanate, isopropylidenebis-4-cyclohexyl isocyanate, dicyclohexylmethane diisocyanate, norbornene diisocyanate, and methylcyclohexane diisocyanate.

[0049] Specific examples of polyol compounds having two or more hydroxy groups in the molecule include polyalkylene glycols having repeating units of ethylene oxide, propylene oxide, or hexamethylene oxide; polyester diols such as polycaprolactone diol; polycarbonate diol, polybutadiene diol, pentaerythritol, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, glycerin, and trimethylolpropane.

[0050] Furthermore, examples of the bifunctional (meth)acrylate having a urethane bond that can be used include a reaction mixture obtained by reacting a urethane prepolymer having an isocyanate group at the molecular end, obtained by reacting the polyisocyanate compound with the polyol compound, with 2-hydroxy(meth)acrylate, and a urethane(meth)acrylate that is a reaction mixture obtained by directly reacting the A1 component with 2-hydroxy(meth)acrylate.

[0051] Specific examples of hydroxy group-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

[0052] Commercially available bifunctional (meth)acrylates having urethane bonds can also be used, such as U-2PPA (molecular weight: 482), UA-122P (molecular weight: 1100), and U-122P (molecular weight: 1100) manufactured by Shin-Nakamura Chemical Co., Ltd., and EB4858 (molecular weight: 454) manufactured by Daicel-Allnex Corporation.

[0053] ((A2-5) Bifunctional (meth)acrylates not falling under the above) (A2-5) Examples of bifunctional (meth)acrylates not falling under the above-mentioned category include compounds having (meth)acryloyl groups at both ends of an alkylene group which may have a substituent. Among these, compounds having an alkylene group having 6 to 20 carbon atoms are preferred. Specific examples include 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol diacrylate, and 1,10-decanediol dimethacrylate.

[0054] Furthermore, examples of bifunctional (meth)acrylates that do not fall under the above category include bifunctional (meth)acrylates containing a sulfur atom, preferably a sulfur atom that forms a part of the molecular chain as a sulfide group. Specific examples include bis(2-methacryloyloxyethylthioethyl)sulfide, bis(methacryloyloxyethyl)sulfide, bis(acryloyloxyethyl)sulfide, 1,2-bis(methacryloyloxyethylthio)ethane, 1,2-bis(acryloyloxyethyl)ethane, bis(2-methacryloyloxyethylthioethyl)sulfide, bis(2-acryloyloxyethylthioethyl)sulfide, 1,2-bis(methacryloyloxyethylthioethylthio)ethane, 1,2-bis(acryloyloxyethylthioethylthio)ethane, 1,2-bis(methacryloyloxyisopropylthioisopropyl)sulfide, and 1,2-bis(acryloyloxyisopropylthioisopropyl)sulfide.

[0055] The above-mentioned A2 components may be used singly or in combination of two or more types for each of the individually described components. Furthermore, the individually described components may be used in combination with each other. When multiple types of A2 components are used in combination, the standard mass of the A2 component is the total amount of these.

[0056] Among the above-mentioned components A2, polyethylene glycol dimethacrylate (particularly, g=4, h=0, average molecular weight: 330), polyethylene glycol dimethacrylate (particularly, g=9, h=0, average molecular weight: 536), polyethylene glycol dimethacrylate (particularly, g=14, h=0, average molecular weight: 736), 2,2-bis[4-(methacryloyloxypolyethoxy)phenyl]propane (i+j=7, average molecular weight: 672), 2,2-bis[4-(methacryloyloxypolyethoxy)phenyl]propane (i+j = 10, average molecular weight: 804), 2,2-bis[4-(methacryloyloxypolyethoxy)phenyl]propane (i + j = 17, average molecular weight: 1116), 2,2-bis[4-(acryloyloxypolyethoxy)phenyl]propane (i + j = 7, average molecular weight: 642), 2,2-bis[4-(acryloyloxypolyethoxy)phenyl]propane (i + j = 10, average molecular weight: 776), 2,2-bis[4-(acryloyloxypolyethoxy)phenyl]propane (i + j = 20, average molecular weight 1216) are preferred.

[0057] [A3 component] The component A3 is not particularly limited as long as it is a monofunctional (meth)acrylate, and a monofunctional (meth)acrylate represented by the following formula (7) is preferably used.

[0058] [ka]

[0059] In the formula, R 22 represents a hydrogen atom or a methyl group, and R 23 represents a hydrogen atom, a methyldimethoxysilyl group, a trimethoxysilyl group, or a glycidyl group; l represents an integer of 0 to 10; and m represents an integer of 0 to 20.

[0060] Specific examples of the monofunctional (meth)acrylate represented by the above formula (7) include, for example, methoxypolyethylene glycol methacrylate (particularly, average molecular weight: 293), methoxypolyethylene glycol methacrylate (particularly, average molecular weight: 468), methoxypolyethylene glycol acrylate (particularly, average molecular weight: 218), methoxypolyethylene glycol acrylate (particularly, average molecular weight: 454), stearyl methacrylate, lauryl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, lauryl acrylate, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and glycidyl methacrylate.

[0061] Among the above-mentioned components A3, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and glycidyl methacrylate are preferred.

[0062] [A4 component] The component A4 is not particularly limited as long as it is another radically polymerizable monomer, and radically polymerizable polyrotaxanes, radically polymerizable silsesquioxane compounds, allyl compounds, and vinyl compounds are preferably used.

[0063] ((A4-1) Radical polymerizable polyrotaxane) (A4-1) A radically polymerizable polyrotaxane has a composite molecular structure including an axis molecule and a plurality of cyclic molecules that encapsulate the axis molecule, and in which side chains having hydroxy groups have been introduced into the cyclic molecules, the hydroxy groups in the side chains are modified with a radically polymerizable compound in an amount of 1 mol % to less than 100 mol %. Note that in this specification, the reaction of the hydroxy groups in the side chains with another compound to introduce a structure derived from the other compound is also referred to as "modification."

[0064] Polyrotaxanes have a complex molecular structure formed from a chain-like axis molecule and cyclic molecules. That is, multiple cyclic molecules are enclosed around the axis molecule, and the axis molecule penetrates the interior of the rings of the cyclic molecules. The cyclic molecules can slide freely on the axis molecule, but bulky terminal groups are formed on both ends of the axis molecule, preventing the cyclic molecules from falling off the axis molecule.

[0065] Various types of axial molecules are known for polyrotaxanes. For example, the axial molecule may be linear or branched as long as it can penetrate the rings of the cyclic molecules, and linear or branched polymers are generally used.

[0066] Specific examples of polymers that form the axial molecule include polyvinyl alcohol, polyvinylpyrrolidone, cellulose-based resins (carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, etc.), polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyvinyl acetal, polyvinyl methyl ether, polyamine, polyethyleneimine, casein, gelatin, starch, olefin-based resins (polyethylene, polypropylene, etc.), polyester, polyvinyl chloride, styrene-based resins (polystyrene, acrylonitrile-styrene copolymer resin, etc.), acrylic resins (poly(meth)acrylamide, etc.), and the like. Examples of the polymer include poly(vinyl chloride), polymethyl methacrylate, polymethyl acrylate, acrylonitrile-methyl acrylate copolymer resin, polycarbonate, polyurethane, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral, polyisobutylene, polytetrahydrofuran, polyaniline, acrylonitrile-butadiene-styrene terpolymer resin (ABS resin), polyamide (nylon, etc.), polyimide, polydienes (polyisoprene, polybutadiene, etc.), polysiloxane (polydimethylsiloxane, etc.), polysulfone, polyimine, polyacetic anhydride, polyurea, polysulfide, polyphosphazene, polyketone polyphenylene, polyhaloolefin, etc. These polymers may be copolymerized or modified as appropriate.

[0067] Among these, polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, polypropylene, polyvinyl alcohol, and polyvinyl methyl ether are preferred, and polyethylene glycol is more preferred.

[0068] The bulky groups formed at both ends of the axial molecule are not particularly limited as long as they prevent the cyclic molecules from being detached from the axial molecule. From the viewpoint of bulkiness, an adamantyl group, a trityl group, a fluoresceinyl group, a dinitrophenyl group, and a pyrenyl group are preferred, and from the viewpoint of ease of introduction, an adamantyl group is more preferred.

[0069] The weight-average molecular weight (Mw) of the axial molecule is not particularly limited, but if it is too large, compatibility with other components (e.g., other polymerizable monomers) tends to be poor, and if it is too small, the mobility of the cyclic molecules tends to decrease, resulting in poor photochromic properties. From this perspective, the weight-average molecular weight of the axial molecule is preferably in the range of 1,000 to 100,000, more preferably in the range of 5,000 to 80,000, and even more preferably in the range of 8,000 to 50,000. Note that this weight-average molecular weight is a value measured by the GPC measurement method described in the Examples below.

[0070] The cyclic molecule has a ring large enough to include an axial molecule. Examples of such rings include a cyclodextrin ring, a crown ether ring, a benzocrown ring, a dibenzocrown ring, and a dicyclohexanocrown ring, with a cyclodextrin ring being preferred. The cyclodextrin ring includes an α-form (inner ring diameter: 0.45 to 0.6 nm), a β-form (inner ring diameter: 0.6 to 0.8 nm), and a γ-form (inner ring diameter: 0.8 to 0.95 nm). An α-cyclodextrin ring and a γ-cyclodextrin ring are preferred, with an α-cyclodextrin ring being more preferred.

[0071] Generally, one axis molecule includes multiple cyclic molecules. When the maximum inclusion number of cyclic molecules that can be included per axis molecule is 1.0, the inclusion number of cyclic molecules is generally in the range of 0.001 to 0.6, preferably in the range of 0.002 to 0.5, and more preferably in the range of 0.003 to 0.4.

[0072] The maximum number of inclusions of cyclic molecules per axial molecule can be calculated from the length of the axial molecule and the ring thickness of the cyclic molecule. For example, when the axial molecule is formed of polyethylene glycol and the cyclic molecule is an α-cyclodextrin ring, the maximum number of inclusions is calculated as follows. That is, two repeating units of polyethylene glycol [-CH2-CHO-] approximate the thickness of one α-cyclodextrin ring. Therefore, the number of repeating units is calculated from the molecular weight of this polyethylene glycol, and half of this number of repeating units is determined as the maximum number of inclusions of cyclic molecules. This maximum number of inclusions is set to 1.0, and the inclusion number of cyclic molecules is adjusted to be within the above-mentioned range.

[0073] Polyrotaxanes having radically polymerizable groups are produced using polyrotaxanes in which side chains having hydroxy groups have been introduced into the above-mentioned cyclic molecules (hereinafter also referred to as "polyrotaxanes having side chain hydroxy groups"). Introducing such side chains into the rings makes it possible to more reliably form an appropriate space between adjacent axial molecules. This ensures that gaps that allow for the reversible reaction of the photochromic compound molecules are secured, enabling the development of excellent photochromic properties. Furthermore, such side chains form a pseudo-crosslinked structure in the polyrotaxane, thereby improving the photochromic properties of the photochromic resin layer.

[0074] The side chain preferably has a hydroxy group and is formed by repeating an organic chain having 3 to 20 carbon atoms. The average molecular weight of such a side chain is preferably in the range of 200 to 10,000, more preferably in the range of 250 to 8,000, even more preferably in the range of 300 to 5,000, and particularly preferably in the range of 300 to 1,500. If the side chain is too small, the function of ensuring a gap that allows the reversible reaction of the photochromic compound molecules tends to be insufficient. On the other hand, if the side chain is too large, it tends to be difficult to intimately mix the photochromic compound (described later) with the polyrotaxane, making it difficult to fully utilize the space ensured by the polyrotaxane. The average molecular weight of the side chain can be adjusted by the amount used when introducing the side chain, and can be determined by calculation, or 1 It can also be determined from H-NMR measurements.

[0075] The side chains can be introduced by modifying the functional groups of the cyclic molecules. For example, an α-cyclodextrin ring has 18 hydroxyl groups as functional groups, and side chains can be introduced via these hydroxyl groups. That is, up to 18 side chains can be introduced to one α-cyclodextrin ring. To fully utilize the functions of the side chains, it is preferable that 6% or more, particularly 30% or more of the total number of functional groups on such rings be modified with side chains.

[0076] The functional groups of the cyclic molecules may affect compatibility with other components, and hydroxyl groups in particular have a significant effect on compatibility with other components. Therefore, the degree of modification with the functional groups (modification degree) is preferably 6 to 80%, and more preferably 30 to 70%. Because the functional groups of the cyclic molecules are less reactive than the hydroxyl groups of the side chains, even a low degree of modification is unlikely to cause problems such as reduced compatibility and bleed-out. Therefore, a modification degree within the above range provides superior effects. Incidentally, if side chains are attached to 9 of the 18 hydroxyl groups of the α-cyclodextrin ring, the degree of modification is 50%.

[0077] The side chain may be linear or branched, as long as it is an organic chain containing a hydroxy group. The desired organic chain containing a hydroxy group can be introduced as a side chain by reacting a compound capable of introducing a hydroxy group with the functional group of a cyclic molecule using methods such as ring-opening polymerization, radical polymerization, cationic polymerization, anionic polymerization, and living radical polymerization such as atom transfer radical polymerization, RAFT polymerization, and NMP polymerization. Among these, considering the ease of introducing the side chain, the ease of adjusting the size (molecular weight) of the side chain, and the ability to modify the hydroxy group with a compound having a radical polymerizable group, it is preferable to use a method of introducing a side chain derived from a cyclic compound by ring-opening polymerization. It is also preferable to introduce a side chain having a hydroxy group at its terminal.

[0078] As the cyclic compound used in ring-opening polymerization, it is preferable to use a cyclic ether or lactone compound from the viewpoints of easy availability, high reactivity, and ease of size (molecular weight) adjustment. By using a cyclic ether or lactone compound, a hydroxy group can be introduced at the end of the side chain. Specific examples of these suitable cyclic ethers and lactone compounds are as follows:

[0079] Specific examples of cyclic ethers include ethylene oxide, 1,2-propylene oxide, epichlorohydrin, epibromohydrin, 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide, oxetane, 3-methyloxetane, 3,3-dimethyloxetane, tetrahydrofuran, 2-methyltetrahydrofuran, and 3-methyltetrahydrofuran.

[0080] Specific examples of lactone compounds include four-membered ring lactones such as β-propiolactone, β-methylpropiolactone, and L-serine-β-lactone; γ-butyrolactone, γ-hexanolactone, γ-heptanolactone, γ-octanolactone, γ-decanolactone, γ-dodecanolactone, α-hexyl-γ-butyrolactone, α-heptyl-γ-butyrolactone, α-hydroxy-γ-butyrolactone, γ-methyl-γ-decanolactone, α-methylene-γ-butyrolactone, α,α-dimethyl-γ-butyrolactone, and D-erythronolactone. 5-membered ring lactones such as α-methyl-γ-butyrolactone, γ-nonanolactone, DL-pantolactone, γ-phenyl-γ-butyrolactone, γ-undecanolactone, γ-valerolactone, 2,2-pentamethylene-1,3-dioxolan-4-one, α-bromo-γ-butyrolactone, γ-crotonolactone, α-methylene-γ-butyrolactone, α-methacryloyloxy-γ-butyrolactone, and β-methacryloyloxy-γ-butyrolactone; δ-valerolactone, δ-hexanolactone, δ-octanolactone, and δ-nonanolactone, Six-membered ring lactones such as δ-decanolactone, δ-undecanolactone, δ-dodecanolactone, δ-tridecanolactone, δ-tetradecanolactone, DL-mevalonolactone, 4-hydroxy-1-cyclohexanecarboxylic acid δ-lactone, monomethyl-δ-valerolactone, monoethyl-δ-valerolactone, monohexyl-δ-valerolactone, 1,4-dioxan-2-one, and 1,5-dioxepan-2-one; non-alkyl-ε-caprolactone, dialkyl-ε-caprolactone, monomethyl-ε-caprolactone, and monoethyl-ε-caprolactone. 7-membered ring lactones such as oxolactone, monohexyl-ε-caprolactone, dimethyl-ε-caprolactone, di-n-propyl-ε-caprolactone, di-n-hexyl-ε-caprolactone, trimethyl-ε-caprolactone, triethyl-ε-caprolactone, tri-n-ε-caprolactone, ε-caprolactone, 5-nonyl-oxepan-2-one, 4,4,6-trimethyl-oxepan-2-one, 4,6,6-trimethyl-oxepan-2-one, and 5-hydroxymethyl-oxepan-2-one; 8-membered ring lactones such as ζ-enantholactone;Other lactones such as lactone, lactide, dilactide, tetramethylglycoside, 1,5-dioxepan-2-one, and t-butylcaprolactone; etc. The above cyclic compounds may be used alone or in combination of two or more.

[0081] Among these cyclic compounds, lactone compounds such as ε-caprolactone, α-acetyl-γ-butyrolactone, α-methyl-γ-butyrolactone, γ-valerolactone, and γ-butyrolactone are preferred, with ε-caprolactone being more preferred.

[0082] When introducing a side chain by reacting a cyclic compound by ring-opening polymerization, the functional group (e.g., hydroxy group) attached to the cyclic molecule may have poor reactivity, and direct reaction with a larger molecule may be difficult due to steric hindrance, etc. In such cases, a method can be adopted in which a low molecular weight compound such as propylene oxide is reacted with the functional group attached to the cyclic molecule to hydroxypropylate it, thereby introducing a highly reactive functional group (hydroxy group), and then a side chain is introduced by ring-opening polymerization using the above-mentioned cyclic compound. In this case, the hydroxypropylated portion can also be considered as a side chain.

[0083] When a side chain is introduced by reacting a cyclic compound through ring-opening polymerization, the side chain introduced by the cyclic compound is referred to as a "side chain modified with the cyclic compound." For example, a side chain obtained by introducing a lactone compound is referred to as a "side chain modified with the lactone compound." In this embodiment, the side chain introduced into the side-chain hydroxy group-containing polyrotaxane is preferably a side chain modified with a lactone compound.

[0084] The polyrotaxane having a radical polymerizable group is produced by reacting the hydroxy group on the side chain of the polyrotaxane having a side chain hydroxy group with a compound having a radical polymerizable group, thereby introducing the radical polymerizable group into the side chain of the polyrotaxane having a side chain hydroxy group. Known reaction conditions can be used for the reaction between the hydroxy group on the side chain of the polyrotaxane having a side chain hydroxy group and the compound having a radical polymerizable group.

[0085] By introducing a radically polymerizable group capable of undergoing a polymerization reaction with the above-mentioned polymerizable monomer into the side chain of the cyclic molecule, it is believed that compatibility is improved and that the photochromic compound can be uniformly dispersed in the voids formed by the polyrotaxane. As a result, the resulting photochromic resin layer is believed to be able to continuously exhibit excellent photochromic properties and also to have high mechanical strength.

[0086] The compound having a radical polymerizable group is not particularly limited as long as it has both a functional group capable of reacting with a hydroxy group in a side chain and a radical polymerizable group in one molecule, but in consideration of compatibility with other components, it is preferable that the compound does not have a hydroxy group in the molecule.

[0087] Examples of functional groups that can react with hydroxy groups include isocyanate groups (-NCO), carboxy groups (-COOH), and acid chloride groups (-COCl). By reacting a compound having an isocyanate group, a radical polymerizable group is introduced via a urethane bond. Furthermore, by reacting a compound having a carboxy group, acid chloride group, or the like, a radical polymerizable group is introduced via an ester bond.

[0088] Specific examples of compounds having an isocyanate group and a radically polymerizable group include 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, and 1,1-(bisacryloyloxymethyl)ethyl isocyanate. Specific examples of compounds having a carboxy group and a radically polymerizable group include 2-methacryloyloxyethyl succinate and β-carboxyethyl acrylate. A compound having an acid chloride group and a radically polymerizable group can be synthesized by reacting a compound having a carboxy group and a radically polymerizable group with a chlorinating agent such as thionyl chloride.

[0089] The radically polymerizable polyrotaxane is not particularly limited as long as it has a radically polymerizable group in the molecule, but the modification ratio of the radically polymerizable group relative to the hydroxyl groups in the side chain, i.e., the reaction ratio of the compound having the radically polymerizable group relative to the total number of moles of hydroxyl groups in the side chain, is preferably 1 mol% or more and less than 100 mol%. The modification ratio can be calculated by (number of moles of radically polymerizable groups introduced) / (number of moles of all hydroxyl groups in the side chain) × 100. From the viewpoints of adhesion, mechanical strength, and photochromic properties of the resulting cured product, the modification ratio is preferably 10 to 95 mol%.

[0090] ((A4-2) Radical polymerizable silsesquioxane compounds) The radically polymerizable silsesquioxane compound has various molecular structures such as a cage structure, a ladder structure, and a random structure, and has a radically polymerizable group such as a (meth)acryloyl group.

[0091] Examples of such radical polymerizable silsesquioxane compounds include those represented by the following formula (8):

[0092] [ka]

[0093] In the formula, n is the degree of polymerization and represents an integer of 3 to 100. 24may be the same or different and represent a radical polymerizable group, an organic group containing a radical polymerizable group, a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, or a phenyl group, provided that at least one R 24 is a radically polymerizable group or an organic group containing a radically polymerizable group.

[0094] where R 24 Examples of the radical polymerizable group represented by the formula (I) or an organic group containing a radical polymerizable group include a (meth)acryloyl group; an organic group having a (meth)acryloyl group, such as a (meth)acryloyloxypropyl group or a (3-(meth)acryloyloxypropyl)dimethylsiloxy group; an allyl group; an organic group having an allyl group, such as an allylpropyl group or an allylpropyldimethylsiloxy group; a vinyl group; and an organic group having a vinyl group, such as a vinylpropyl group or a vinyldimethylsiloxy group.

[0095] ((A4-3) Allyl compounds) Specific examples of the allyl compounds include diethylene glycol bisallyl carbonate, methoxypolyethylene glycol allyl ether (particularly, average molecular weight: 550), methoxypolyethylene glycol allyl ether (particularly, average molecular weight: 350), methoxypolyethylene glycol allyl ether (particularly, average molecular weight: 1500), polyethylene glycol allyl ether (particularly, average molecular weight: 450), methoxypolyethylene glycol-polypropylene glycol allyl ether (particularly, average molecular weight: 750), butoxypolyethylene glycol-polypropylene glycol allyl ether (particularly, average molecular weight: 1600), methacryloyl methyl ... Examples thereof include hydroxypolyethylene glycol-polypropylene glycol allyl ether (particularly, average molecular weight: 560), phenoxypolyethylene glycol allyl ether (particularly, average molecular weight: 600), methacryloyloxypolyethylene glycol allyl ether (particularly, average molecular weight: 430), acryloyloxypolyethylene glycol allyl ether (particularly, average molecular weight: 420), vinyloxypolyethylene glycol allyl ether (particularly, average molecular weight: 560), styryloxypolyethylene glycol allyl ether (particularly, average molecular weight: 650), and methoxypolyethylene thioglycol allyl thioether (particularly, average molecular weight: 730).

[0096] ((A4-4) Vinyl compounds) Specific examples of vinyl compounds include methyl vinyl ketone, ethyl vinyl ketone, ethyl vinyl ether, styrene, vinylcyclohexane, butadiene, 1,4-pentadiene, divinyl sulfide, divinyl sulfone, 1,2-divinylbenzene, 1,3-divinyl-1,1,3,3-tetramethylpropanedisiloxane, diethylene glycol divinyl ether, divinyl adipate, divinyl sebacate, ethylene glycol divinyl ether, divinyl sulfoxide, divinyl persulfide, dimethyldivinylsilane, 1,2,4-trivinylcyclohexane, methyltrivinylsilane, α-methylstyrene, and α-methylstyrene dimer.

[0097] (Preferred component A and blending ratio) Among the above-mentioned A1 component, A2 component, and A3 component, trimethylolpropane trimethacrylate or dipentaerythritol hexaacrylate is used as the A1 component, and polyethylene glycol dimethacrylate (particularly, g=9, h=0, average molecular weight: 536), polyethylene glycol dimethacrylate (particularly, g=14, h=0, average molecular weight: 736), 2,2-bis[4-(methacryloyloxypolyethoxy)phenyl]propane (i+j=7 , average molecular weight: 672), 2,2-bis[4-(methacryloyloxypolyethoxy)phenyl]propane (i+j=10, average molecular weight: 804), 2,2-bis[4-(acryloyloxypolyethoxy)phenyl]propane (i+j=7, average molecular weight: 642), or 2,2-bis[4-(acryloyloxypolyethoxy)phenyl]propane (i+j=10, average molecular weight: 776) is used in combination with glycidyl methacrylate as component A3.

[0098] The blending ratios of the above-mentioned A1 component, A2 component, A3 component, and A4 component are not particularly limited as long as the blending ratio of the A1 component is 24 to 100% by mass. However, in consideration of the photochromic properties such as the color density and fading speed of the resulting photochromic optical article, it is preferable that the blending ratios are 24 to 100% by mass of the A1 component, 0 to 76% by mass of the A2 component, 0 to 76% by mass of the A3 component, and 0 to 76% by mass of the A4 component. It is more preferable that the A1 component be 24 to 75% by mass, the A2 component be 25 to 65% by mass, the A3 component be 0 to 5% by mass, and the A4 component be 0 to 10% by mass, it is even more preferable that the A1 component be 24% to 60% by mass, the A2 component be 40 to 76% by mass, the A3 component be 0 to 3% by mass, and the A4 component be 0 to 7% by mass, and it is particularly preferable that the A1 component be 25% to 50% by mass, the A2 component be 50 to 75% by mass, the A3 component be 0 to 2% by mass, and the A4 component be 0 to 5% by mass.

[0099] The total content of the component A is preferably 80.0 to 99.9 mass %, and more preferably 88.5 to 99.9 mass %, relative to the total amount of the photochromic curable composition according to this embodiment.

[0100] <(B) Photochromic Compound> The photochromic compound, component B, is a compound in which at least one naphthopyran represented by the following formula (1) is bonded to a long-chain group having a number-average molecular weight of 300 to 10,000. The use of such a photochromic compound allows for high color density and rapid fading speed, even in a solid matrix with a high crosslink density, such as component A, and tends to reduce temperature dependency. Furthermore, since the number-average molecular weight of the long-chain group used is 300 to 10,000, compatibility with the solid matrix of component A is excellent, and cloudiness tends to be suppressed.

[0101] [ka]

[0102] In the formula, R 1 and R 2 each independently represents a group bonded to a long-chain group having a number average molecular weight of 300 to 10,000, or a hydroxy group, an alkyl group, a haloalkyl group, a cycloalkyl group which may have a substituent, an alkoxy group, an amino group, a substituted amino group, a heterocyclic group which may have a substituent, a cyano group, a halogen atom, an alkylthio group, an arylthio group which may have a substituent, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aralkyl group which may have a substituent, an aralkoxy group which may have a substituent, an aryloxy group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, a thiol group, an alkoxyalkylthio group, a haloalkylthio group, or a cycloalkylthio group which may have a substituent. a represents an integer of 0 to 2, and b represents an integer of 0 to 4. When a is 2, multiple R 1 may be the same or different, and when a is 2, adjacent R 1 If there is a 1 Together they R 1and the carbon atom bonded to the R may form a ring which may contain an oxygen atom, a sulfur atom, or a nitrogen atom, and the ring may further have a substituent. 2 may be the same or different, b is 2 to 4, and adjacent R 2 If there is a 2 Together they R 2 and b may form a ring which may contain an oxygen atom, a sulfur atom, or a nitrogen atom together with the carbon atom bonded to the ring, and the ring may further have a substituent. When neither a nor b is 0, at least one R 1 and at least one R 2 may be joined together to form a ring, and the ring may further have a substituent. 3 and R 4 each independently represents a group bonded to a long-chain group having a number average molecular weight of 300 to 10,000, or an aryl group which may have a substituent, or a heteroaryl group which may have a substituent. 1 , R 2 , R 3 , and R 4 At least one of these is a group that bonds to a long-chain group having a number-average molecular weight of 300 to 10000. Note that "bonded to a long-chain group having a number-average molecular weight of 300 to 10000" means that the group is directly bonded to the long-chain group.

[0103] In this way, by using a photochromic compound in which at least one naphthopyran is bonded to a long-chain group having a number average molecular weight of 300 to 10,000, the naphthopyran itself can create an environment in which structural changes are likely to occur, and a photochromic curable composition with excellent photochromic properties can be obtained.

[0104] In order to exert the above-mentioned effects, naphthopyran represented by the above formula (1) has two adjacent R 1 are preferably indenonaphthopyran in which these are taken together to form a ring, and more preferably indeno[2,1-f]naphtho[1,2-b]pyran represented by the following formula (2).

[0105] [ka]

[0106] In the formula, R 2 , R 3 , R 4 and b are the same as in the above formula (1). 5 represents a group bonded to a long-chain group having a number average molecular weight of 300 to 10,000, or a hydroxy group, an alkyl group, a haloalkyl group, a cycloalkyl group which may have a substituent, an alkoxy group, an amino group, a substituted amino group, a heterocyclic group which may have a substituent, a cyano group, a halogen atom, an alkylthio group, an arylthio group which may have a substituent, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aralkyl group which may have a substituent, an aralkoxy group which may have a substituent, an aryloxy group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, a thiol group, an alkoxyalkylthio group, a haloalkylthio group, or a cycloalkylthio group which may have a substituent. c represents an integer of 0 to 4. When c is 2 to 4, multiple R 5 may be the same or different, c is 2 to 4, and adjacent R 5 If there is a 5 Together they R 5 R may form a ring together with the carbon atom to which it is bonded, which may contain an oxygen atom, a sulfur atom, or a nitrogen atom, and the ring may further have a substituent. 6 and R 7each independently represents a group bonded to a long-chain group having a number average molecular weight of 300 to 10,000, or a hydrogen atom, a hydroxy 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 which may have a substituent, an aralkoxy group which may have a substituent, an aryloxy group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent; R 6 and R 7 may be bonded together with the carbon atom at position 13 to form an aliphatic ring having 3 to 20 ring carbon atoms, a condensed polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is condensed to the aliphatic ring, a heterocyclic ring having 3 to 20 ring atoms, or a condensed polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is condensed to the heterocyclic ring, provided that R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 At least one of the groups is a group that bonds to a long-chain group having a number average molecular weight of 300 to 10,000.

[0107] With regard to each of the groups exemplified above, the alkyl group preferably has 1 to 6 carbon atoms, the haloalkyl group preferably has 1 to 6 carbon atoms, the cycloalkyl group preferably has 3 to 8 carbon atoms, the alkoxy group preferably has 1 to 6 carbon atoms, the alkylcarbonyl group preferably has 2 to 7 carbon atoms, the alkoxycarbonyl group preferably has 2 to 7 carbon atoms, the aralkyl group preferably has 7 to 11 carbon atoms, the aralkoxy group preferably has 7 to 11 carbon atoms, the aryloxy group preferably has 6 to 12 carbon atoms, the aryl group preferably has 6 to 12 carbon atoms, the alkylthio group preferably has 1 to 6 carbon atoms, the cycloalkylthio group preferably has 3 to 8 carbon atoms, and the arylthio group preferably has 6 to 12 carbon atoms.

[0108] Among them, R 2 , R 3 , R4 , and R 5 At least one of these is preferably a group that bonds to a long-chain group having a number average molecular weight of 300 to 10,000.

[0109] R 2 is preferably a group bonded to a long-chain group having a number average molecular weight of 300 to 10,000, or 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 which may have a substituent, an alkylthio group, an arylthio group which may have a substituent, or an aryl group having 6 to 12 carbon atoms which may have a substituent. Among these, it is more preferable that these groups are present at the 6th and / or 7th positions of the indeno[2,1-f]naphtho[1,2-b]pyran. Furthermore, R at the 6th and 7th positions of the indeno[2,1-f]naphtho[1,2-b]pyran is more preferable. 2 There are two R 2 are also preferably combined to form an aliphatic ring (which may further have a substituent) which may contain an oxygen atom, a nitrogen atom, or a sulfur atom. In this case, the number of atoms in the aliphatic ring containing an oxygen atom, a nitrogen atom, or a sulfur atom (the number of atoms including heteroatoms and the carbon atoms located at the 6th and 7th positions) is preferably 5 to 8. Furthermore, the aliphatic ring may have a substituent, and this substituent is preferably an alkyl group having 1 to 6 carbon atoms.

[0110] R 5 is preferably a group bonding to a long-chain group having a number average molecular weight of 300 to 10,000, a hydrogen atom (when b=0), an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms which may have a substituent, or an arylthio group. Among these, it is more preferable that these groups are present at the 11-position of indeno[2,1-f]naphtho[1,2-b]pyran.

[0111] R 3 and R 4 are preferably each independently a group bonded to a long-chain group having a number average molecular weight of 300 to 10,000, or an aryl group which may have a substituent, or a heteroaryl group which may have a substituent.

[0112] R 6 and R 7 In consideration of reducing the temperature dependency, each of R is preferably an alkyl group having 1 to 12 carbon atoms, or R 6 and R 7 are preferably taken together with the carbon atom at position 13 to which they are bonded to form a ring selected from an aliphatic ring having 3 to 20 ring carbon atoms, a fused polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is fused to the aliphatic ring, a heterocyclic ring having 3 to 20 ring atoms, or a fused polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is fused to the heterocyclic ring, i.e., a ring that forms a spiro structure with the carbon atom at position 13 of the 5-membered ring of indenonaphthopyran. 6 and R 7 are preferably combined together to form an aliphatic ring having 3 to 20 ring carbon atoms, and specific examples thereof include a ring selected from a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cycloundecane ring, a cyclododecane ring, and a spirodicyclohexane ring. The ring forming the spiro structure may have 1 to 10 alkyl groups having 1 to 3 carbon atoms or cycloalkyl groups having 5 to 7 carbon atoms as substituents, or may be condensed with cycloalkyl groups having 5 to 7 carbon atoms. More preferred examples include groups represented by the following formula:

[0113] [ka]

[0114] As the long chain group having a number average molecular weight of 300 to 10,000, any known long chain group can be used without any particular limitation, and examples thereof include polyalkylene groups, polyalkyleneoxy groups, polyfluoroalkylene groups, polyfluoroalkylenyloxy groups, polydialkylsilyl groups, polydialkylsilyloxy groups, polyester groups, etc. The long chain group may be a group having these groups alone, or may be a group having other groups interposed therebetween. For example, R 3 and / or R 4is a group that bonds to a long-chain group having a number-average molecular weight of 300 to 10,000, the bonded long-chain group having a number-average molecular weight of 300 to 10,000 is preferably an aryl group or heteroaryl group to which the long-chain group is bonded. Furthermore, a group containing an ether group, ester group, or the like may be present between the long-chain group and the aryl group or heteroaryl group.

[0115] Among these long-chain groups, polyalkylene groups, polyalkyleneoxy groups, polydialkylsilyloxy groups, polyester groups, and long-chain groups consisting of combinations thereof are preferred, polyalkyleneoxy groups, polydialkylsilyloxy groups, polyester groups, and long-chain groups consisting of combinations thereof are more preferred, polyalkyleneoxy groups and polydialkylsilyloxy groups are even more preferred, and polyalkyleneoxy groups are particularly preferred.

[0116] The number of naphthopyrans bonded to a long-chain group having a number-average molecular weight of 300 to 10,000 is not particularly limited, and at least one naphthopyran is required. For example, not only can two or more naphthopyrans be bonded to one long-chain group, but also one naphthopyran can be bonded to multiple long-chain groups. In these embodiments, the number of naphthopyrans is preferably 0.1 to 4, and more preferably 0.2 to 2. The number of naphthopyrans is 1 or less in a photochromic compound in which multiple long-chain groups are bonded to one naphthopyran. For example, a number of naphthopyrans of 0.25 indicates that four long-chain groups having a number-average molecular weight of 300 to 10,000 are bonded to one naphthopyran. When multiple long-chain groups having a number-average molecular weight of 300 to 10,000 are present, the long-chain groups having a number-average molecular weight of 300 to 10,000 may be the same or different.

[0117] The number average molecular weight of these long chain groups is preferably 400 to 7,500, and more preferably 450 to 5,000.

[0118] The naphthopyran used in the photochromic compound as component B is not particularly limited as long as it has the above-mentioned structure, and examples thereof include naphthopyrans described in Patent Documents 3 to 5 and naphthopyrans obtained by appropriately selecting the above-mentioned combinations.

[0119] Examples of the photochromic compound that is component B are shown below, but are not limited to these. In the examples below, n may be appropriately set so that the number average molecular weight of the long chain group is 300 to 10,000, and is usually selected from 1 to 250 (usually, long chain groups have multiple molecular weights, so they are expressed as number average molecular weights. Therefore, n can be a value other than an integer). Me represents a methyl group.

[0120] [ka]

[0121] The naphthopyran used in the photochromic compound (component B) may be a single type, or multiple types of naphthopyrans may be combined depending on the desired color tone to obtain various color tones required for photochromic lenses. Furthermore, depending on the intended application, other photochromic compounds having a number average molecular weight of 300 to 10,000 and no long-chain group may be combined, as long as the effects of the present invention are not impaired. Known compounds such as fulgides, fulgimides, spirooxazines, and chromenes can be used as the other photochromic compounds without any limitations.

[0122] The content of the component B in the photochromic curable composition according to this embodiment is preferably 0.01 to 15 parts by mass, and more preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the component A, from the viewpoint of photochromic properties such as color density and fading speed of the resulting photochromic optical article.

[0123] <Other ingredients> The photochromic curable composition according to the present embodiment may contain various known compounding agents within the range that does not impair the effects of the present invention, such as a polymerization initiator, an ultraviolet absorber, an infrared absorber, an ultraviolet stabilizer, an antioxidant, a coloring inhibitor, an antistatic agent, a dye, a pigment, a fragrance, a solvent, and a leveling agent.

[0124] Among the above-mentioned compounding ingredients, the polymerization initiator may be a thermal polymerization initiator, a photopolymerization initiator, or the like.

[0125] Examples of the thermal polymerization initiator include diacyl peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide, and acetyl peroxide; peroxyesters such as t-butylperoxy-2-ethylhexanate, t-butylperoxyneodecanate, cumylperoxyneodecanate, and t-butylperoxybenzoate; percarbonates such as diisopropyl peroxydicarbonate and di-sec-butylperoxydicarbonate; and azo compounds such as azobisisobutyronitrile.

[0126] Examples of the photopolymerization initiator include acetophenone-based compounds such as 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, and 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one; α-dicarbonyl-based compounds such as 1,2-diphenylethanedione and methylphenylglycoxylate; and acylphosphine oxide-based compounds such as 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine acid methyl ester, 2,6-dichlorobenzoyldiphenylphosphine oxide, and 2,6-dimethoxybenzoyldiphenylphosphine oxide.

[0127] When a photopolymerization initiator is used, a known polymerization curing accelerator such as a tertiary amine can also be used in combination.

[0128] The content of other components in the photochromic curable composition according to this embodiment is usually 0.001 to 10 parts by mass, and preferably 0.01 to 3 parts by mass, per 100 parts by mass of component A.

[0129] <Method for preparing photochromic curable composition> The photochromic curable composition according to this embodiment can be prepared by mixing the above-mentioned components A and B, and, if necessary, other components, by a known method.

[0130] <Photochromic optical article> The photochromic optical article according to this embodiment is obtained by polymerizing the photochromic curable composition described above. Polymerization for producing the photochromic optical article is carried out by irradiation with active energy rays (ultraviolet rays, α-rays, β-rays, γ-rays, etc.), heating, or a combination of both. That is, an appropriate polymerization method may be adopted depending on the types of component A and polymerization initiator used and the form of the photochromic optical article to be formed.

[0131] When a photochromic curable composition is thermally polymerized, the temperature conditions in particular affect the properties of the resulting photochromic optical article. The temperature conditions cannot be generally limited because they are affected by the type and amount of the thermal polymerization initiator and the type of component A. Generally, however, it is preferable to initiate polymerization at a relatively low temperature and slowly increase the temperature. Like the temperature, the polymerization time also varies depending on various factors. Therefore, it is preferable to determine the optimal time in advance based on these conditions. Generally, it is preferable to select conditions so that the polymerization is completed within 2 to 48 hours.

[0132] Furthermore, when photopolymerizing a photochromic curable composition, the polymerization conditions, particularly the illuminance conditions, affect the properties of the resulting photochromic optical article. The illuminance conditions cannot be generally limited because they are affected by the type and amount of the photopolymerization initiator and the type of component A. However, the illuminance conditions are generally 50 to 500 mW / cm at a wavelength of 365 nm.2 It is preferable to select the conditions so that the UV light is irradiated for 0.5 to 5 minutes.

[0133] When producing a photochromic lens as a photochromic optical article, any of the known methods described below can be used as long as the method can provide uniform photochromic performance.

[0134] For example, when a photochromic lens is produced by the kneading method, a photochromic curable composition is injected between glass molds held by an elastomer gasket or spacer, and polymerization is carried out by cast polymerization to obtain a photochromic optical article molded into the shape of a lens, etc. During polymerization, heating in an air oven or irradiation with active energy rays such as ultraviolet rays can be used depending on the types of component A and polymerization initiator.

[0135] Furthermore, when a photochromic lens is manufactured by a lamination method, a coating liquid is prepared by dissolving a photochromic curable composition in an appropriate organic solvent, and the coating liquid is applied to the surface of an optical substrate such as a lens substrate by spin coating, dipping, or the like, and the organic solvent is removed by drying. Subsequently, polymerization is carried out by UV irradiation or heating in an inert gas such as nitrogen, thereby obtaining a photochromic optical article in which a photochromic layer is formed on the surface of the optical substrate (coating method).

[0136] Alternatively, a photochromic optical article having a photochromic layer formed on the surface of the optical substrate can be obtained by cast polymerization using an inner mold in which an optical substrate such as a lens substrate is placed in a glass mold so as to form a predetermined void, a photochromic curable composition is injected into this void, and polymerization is carried out in this state by UV irradiation, heating, or the like (cast polymerization method).

[0137] When forming a photochromic layer on the surface of an optical substrate by the above-mentioned lamination methods (coating method and cast polymerization method), the adhesion between the photochromic layer and the optical substrate can be improved by previously subjecting the surface of the optical substrate to a chemical treatment using an alkaline solution, an acid solution, etc., or a physical treatment using corona discharge, plasma discharge, polishing, etc. Of course, it is also possible to provide a transparent adhesive resin layer on the surface of the optical substrate.

[0138] Furthermore, when a photochromic lens is manufactured by the binder method, a photochromic sheet is first produced by sheet molding using a photochromic curable composition, and this is then sandwiched between two transparent sheets (optical sheets) and polymerized to obtain a photochromic laminate in which the photochromic layer serves as an adhesive layer. The photochromic sheet can also be produced by a coating method using a coating liquid in which the photochromic curable composition is dissolved in an organic solvent.

[0139] The photochromic laminate thus produced is placed in a mold, and a thermoplastic resin (such as polycarbonate) for optical substrates such as lenses is injection molded to obtain a photochromic optical article such as a lens having a predetermined shape on which the photochromic laminate is laminated. Alternatively, a photochromic optical article can be obtained by adhering the photochromic laminate to the surface of an optical substrate with an adhesive or the like.

[0140] Depending on the application, photochromic optical articles can be subjected to post-processing such as dyeing using disperse dyes or other dyes; preparation of a hard coating film using a hard coating agent whose main component is a silane coupling agent or a sol of silicon, zirconium, antimony, aluminum, tin, tungsten, or the like; formation of a thin film by vapor deposition of metal oxides such as SiO2, TiO2, and ZrO2; and anti-reflection or anti-static treatment by applying an organic polymer to form a thin film. [Example]

[0141] Next, the present invention will be described in detail using examples and comparative examples, but the present invention is not limited to these examples. In the following, Examples 2 to 4, 6, 7, 10, and 11 shall all be read as Reference Examples. In the examples and comparative examples, the above-mentioned components and the methods for evaluating photochromic properties and the like are as follows.

[0142] <(A) (Meth)acrylate Composition> (A1) Polyfunctional (meth)acrylate having three or more (meth)acryloyl groups in the molecule TMPT: Trimethylolpropane triacrylate DTMP: Ditrimethylolpropane tetramethacrylate (A2) Difunctional (meth)acrylate PEG14: Polyethylene glycol dimethacrylate (average molecular weight: 736) BPA10: 2,2-bis[4-(methacryloyloxypolyethoxy)phenyl]propane (average molecular weight: 804) PEG9: Polyethylene glycol dimethacrylate (average molecular weight: 536) PEG9A: Polyethylene glycol diacrylate (average molecular weight: 508) C4PCDA: A reaction product of polycarbonate diol obtained by phosgenation of tetramethylene glycol with acrylic acid BPE-500: Ethoxylated bisphenol A dimethacrylate (Shin-Nakamura Chemical Co., Ltd.) (A3) Monofunctional (meth)acrylate GMA: Glycidyl methacrylate (A4) Polymerizable monomers other than (A1) to (A3) PR1: Polyrotaxane having a (meth)acryloyl group prepared in Preparation Example 1 below PS1: Silsesquioxane having a (meth)acryloyl group prepared in Preparation Example 2 below

[0143] <(B) Photochromic Compound> (B1) Photochromic compound having a polypropylene glycol monobutyl ether chain and a number average molecular weight of 1,000, represented by the following formula (n=17.2):

[0144] [ka]

[0145] (B2) Photochromic compound having a polyethylene glycol chain with a number average molecular weight of 3,000, represented by the following formula (n=68.2):

[0146] [ka]

[0147] (B3) Photochromic compound (n=12) having a polydimethylsiloxane chain with a number average molecular weight of 1100, represented by the following formula:

[0148] [ka]

[0149] (BR1, BR2) Photochromic compounds used in comparative examples

[0150] [ka]

[0151] <Other ingredients> PI1: Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide HA: Bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate HP: Ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate]

[0152] <Preparation Example 1: Preparation of PR1> (1) Preparation of the axial molecule (PEG-COOH) Linear polyethylene glycol (PEG) with a molecular weight of 20,000 was prepared as the axis molecule. PEG (10 g), TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy radical) (100 mg), and sodium bromide (1 g) were dissolved in 100 mL of water. 5 mL of commercially available aqueous sodium hypochlorite solution (5% available chlorine concentration) was added to this solution and stirred at room temperature for 10 minutes. The reaction was then terminated by adding ethanol up to 5 mL. After extraction with 50 mL of methylene chloride, the methylene chloride was removed by distillation. The solution was dissolved in 250 mL of ethanol and reprecipitated at -4 °C for 12 hours. PEG-COOH was recovered as the axis molecule and dried.

[0153] (2) Preparation of polyrotaxane without side chains The PEG-COOH (3 g) and α-cyclodextrin (α-CD) (12 g) prepared above were each dissolved in 50 mL of warm water at 70°C. The resulting solutions were mixed and shaken thoroughly. The mixed solution was then reprecipitated at 4°C for 12 hours, and the precipitated inclusion complex was recovered by lyophilization. Adamantanamine (0.13 g) was then dissolved in 50 mL of dimethylformamide (DMF) at room temperature, and the inclusion complex was added and quickly shaken thoroughly. A solution of BOP reagent (benzotriazol-1-yl-oxy-tris(dimethylamino)phosphonium hexafluorophosphate) (0.38 g) in DMF was then added and shaken thoroughly. A solution of diisopropylethylamine (0.14 mL) in DMF was then added and shaken thoroughly to obtain a slurry reagent. The resulting slurry reagent was then allowed to stand at 4°C for 12 hours. Subsequently, 50 mL of a DMF / methanol mixed solvent (volume ratio: 1 / 1) was added and mixed, followed by centrifugation and discarding the supernatant. The mixture was further washed with the DMF / methanol mixed solution, followed by washing with methanol and centrifugation to obtain a precipitate. The obtained precipitate was dried under vacuum and then dissolved in 50 mL of DMSO. The resulting clear solution was added dropwise to 700 mL of water to precipitate polyrotaxane with no side chains introduced. The precipitated polyrotaxane with no side chains introduced was recovered by centrifugation and dried under vacuum. The mixture was further dissolved in DMSO and precipitated in water, followed by recovery and drying to obtain purified polyrotaxane with no side chains introduced. The inclusion amount of α-CD at this time was 0.25.

[0154] Here, the inclusion amount was determined by dissolving polyrotaxane without side chains in DMSO-d6, 1 Measurements were made using a H-NMR measurement device (JNM-LA500 manufactured by JEOL Ltd.) and calculations were made using the following method, where X, Y, and X / (YX) have the following meanings. X: Integral value of protons derived from hydroxyl groups of cyclodextrins from 4 to 6 ppm Y: Integral value of protons derived from methylene groups of cyclodextrin and PEG at 3-4 ppm X / (YX): Proton ratio of cyclodextrin to PEG First, the theoretical maximum inclusion amount of 1.0 was calculated in advance as X / (YX), and the inclusion amount was calculated by comparing this value with the X / (YX) calculated from the analytical values ​​of the actual compound.

[0155] (3) Introduction of side chains into polyrotaxanes without side chains The purified polyrotaxane (500 mg) without side chains was dissolved in 50 mL of 1 mol / L aqueous NaOH solution, and propylene oxide (3.83 g, 66 mmol) was added. The mixture was stirred at room temperature for 12 hours under an argon atmosphere. The solution was then neutralized to a pH of 7–8 using 1 mol / L aqueous HCl solution. The solution was dialyzed using a dialysis tube and then freeze-dried to obtain a hydroxypropylated polyrotaxane. The degree of modification of the hydroxy groups of the cyclic molecules with hydroxypropyl groups was 50%. The resulting hydroxypropylated polyrotaxane (5 g) was dissolved in ε-caprolactone (30 g) at 80°C to prepare a mixed solution. This mixture was stirred at 110°C for 1 hour while blowing dry nitrogen. Then, a 50% by weight solution of tin(II) 2-ethylhexanoate in xylene (0.16 g) was added, and the mixture was stirred at 130°C for 6 hours. Then, xylene was added to obtain a xylene solution of polycaprolactone-modified polyrotaxane with side chains introduced therein, with a non-volatile concentration of approximately 35% by mass.

[0156] The polycaprolactone-modified polyrotaxane xylene solution prepared above was dropped into hexane, recovered, and dried to obtain a polycaprolactone-modified polyrotaxane, which is a polyrotaxane containing a side chain hydroxy group. 1 The polycaprolactone-modified polyrotaxane was identified by H-NMR and GPC, and was confirmed to have the desired structure. The degree of side chain modification was 50%, the side chain (average) molecular weight was approximately 500, and the mass-average molecular weight (Mw) measured by GPC was 700,000.

[0157] (4) Introduction of acryloyl groups into polyrotaxanes containing side chain hydroxyl groups The polycaprolactone-modified polyrotaxane (10.0 g), a polyrotaxane with side chain hydroxyl groups prepared in (3) above, was dissolved in 50 mL of methyl ethyl ketone, and 5 mg of dibutylhydroxytoluene (polymerization inhibitor) was added. Then, 1.94 g of 2-acryloyloxyethyl isocyanate was added dropwise. 10 mg of dibutyltin dilaurate was added as a catalyst, and the mixture was stirred at 70 °C for 4 hours to obtain a methyl ethyl ketone solution of a polyrotaxane with (meth)acryloyl groups, in which acryloyl groups had been introduced to the hydroxyl groups at the polycaprolactone terminals. This solution was then added dropwise to hexane, and the precipitated solid was collected and dried to obtain a polyrotaxane with (meth)acryloyl groups (PR1). This polyrotaxane (PR1) having (meth)acryloyl groups had a side chain (average) molecular weight of approximately 600, a mass average molecular weight (Mw) measured by GPC of 880,000, a modified acryloyl group ratio of 85 mol %, and a ratio of hydroxy groups remaining in the side chains of 15 mol %.

[0158] <Preparation Example 2: Preparation of PS1> Ethanol (248 mL) and water (54 g, 3.0 mol) were added to 3-trimethoxysilylpropyl methacrylate (248 g, 1.0 mol), and sodium hydroxide (0.20 g, 0.005 mol) was added as a catalyst, followed by a reaction at 30°C for 3 hours. After confirming the disappearance of the raw materials, the mixture was neutralized with dilute hydrochloric acid, and toluene (174 mL), heptane (174 mL), and water (174 g) were added, followed by removal of the aqueous layer. The organic layer was then washed with water until the aqueous layer became neutral, and the solvent was concentrated to obtain silsesquioxane (PS1) having a (meth)acryloyl group. 1 H-NMR confirmed that the raw material was completely consumed. 29 The resulting PS1 was confirmed to be a mixture of cage, ladder, and random structures by Si-NMR. The acid value of the resulting PS1 was 1.1 mg KOH / g, and the mass-average molecular weight (Mw) was 4,800.

[0159] <Evaluation method> The obtained photochromic optical article was used as a sample, and was irradiated with a xenon lamp L-2480 (300 W) SHL-100 manufactured by Hamamatsu Photonics Co., Ltd. through an Aeromass filter (manufactured by Corning Incorporated) at 23°C and 35°C, with a beam intensity of 365 nm = 2.4 mW / cm on the surface of the photochromic optical article. 2 , 245nm=24μW / cm 2 The photochromic properties of the photochromic optical article were measured. The photochromic properties, Vickers hardness, elution of the photochromic compound, etc. were evaluated by the following methods.

[0160] (1) Photochromic Maximum absorption wavelength (λmax): This is the maximum absorption wavelength after color development measured using a spectrophotometer (instant multichannel photodetector MCPD1000) manufactured by Otsuka Electronics Co., Ltd. The maximum absorption wavelength is related to the color tone at the time of color development. 23°C color density {ε(300)-ε(0)}: The difference between the absorbance {ε(300)} after 300 seconds of light exposure at the maximum absorption wavelength and the absorbance ε(0) before light exposure. The higher this value, the better the photochromic properties. 23°C fading rate [t1 / 2 (sec.)]: The time required for the absorbance at the maximum absorption wavelength of a sample to decrease to half of {ε(300) - ε(0)} after 300 seconds of light exposure and then the light exposure is stopped. The shorter this time, the better the photochromic properties. Temperature dependency: The ratio of the color density at 35°C to the color density at 23°C. The higher this value, the less temperature dependency there is, and the better it is.

[0161] (2) Vickers hardness (Hv) Vickers hardness was measured using a hardness tester with an automatic measurement (reading) device (PMT-X7A, manufactured by Matsuzawa Corporation). Specifically, a Vickers indenter was pressed into the sample surface at 10 gf for 30 seconds, and the Vickers hardness was obtained from the indentation. Vickers hardness is an indicator of whether scratches will occur during the lens processing process. As a guideline, if the Vickers hardness is above 4.5, scratches will be less likely to occur, and if it is below 4.5, scratches will easily occur.

[0162] (3) Dissolution The obtained photochromic optical article was immersed in 50 mL of methanol and heated under reflux for 24 hours. After removing the photochromic optical article, the methanol was concentrated under reduced pressure, and 5 mL of chloroform was added to the remaining residue to dissolve it uniformly. After that, the article was irradiated with ultraviolet light, and the presence or absence of color development was visually confirmed and evaluated according to the following evaluation criteria. -Evaluation criteria- 4: No color at all 3: Very slight color development can be seen 2: Light color development 1: Color development

[0163] Example 1 A photochromic curable composition was obtained by adding a photochromic compound to Component A and other components shown in Table 1 so that the amount was 26 mmol per 100 g of Component A. The values ​​in parentheses in Table 1 represent parts by mass. A photochromic optical article was obtained using the photochromic curable composition obtained in this manner by the following method.

[0164] First, a thiourethane-based plastic lens with a center thickness of 2 mm and a refractive index of 1.60 was prepared as an optical substrate. This thiourethane-based plastic lens was previously subjected to alkaline etching using a 10% aqueous sodium hydroxide solution at 50°C for 5 minutes, and then thoroughly washed with distilled water.

[0165] Using a spin coater (1H-DX2, manufactured by Mikasa Co., Ltd.), the surface of the plastic lens was coated with a moisture-curable primer (product name: TR-SC-P, manufactured by Tokuyama Corporation) at a rotation speed of 70 rpm for 15 seconds, followed by 1000 rpm for 10 seconds. Then, 2 g of the photochromic curable composition obtained above was applied by spin coating at a rotation speed of 60 rpm for 40 seconds, followed by 600 rpm for 10 to 20 seconds, so that the photochromic curable composition had a film thickness of 40 μm.

[0166] The lens having the photochromic curable composition applied to its surface was then heated in a nitrogen gas atmosphere at an output of 200 mW / cm 2 The photochromic curable composition was polymerized by irradiating it with light for 90 seconds using a metal halide lamp. It was then heated at 110°C for 1 hour to prepare a photochromic optical article having a photochromic layer. The evaluation results are shown in Table 2.

[0167] <Examples 2 to 5, Comparative Examples 1 to 3> Photochromic optical articles were produced in the same manner as in Example 1, except that component A, the photochromic compound, and other components were changed as shown in Table 1. The evaluation results are shown in Table 2.

[0168] [Table 1]

[0169] [Table 2]

[0170] The results of the temperature dependency and the results of the fading half-life at 23° C. for Examples 1, 3, and 5 and Comparative Examples 1 to 3 are shown in FIG.

[0171] As can be seen from Figure 1, in the photochromic optical articles of the comparative examples using photochromic compounds with number-average molecular weights of 300 to 10,000 that are not bonded to long-chain groups, the temperature dependence and the 23°C fading half-life are in a nearly linear relationship. In other words, compounds with a fast fading rate exhibit greater temperature dependence. Comparative Example 1 is an example with a low content of polyfunctional (meth)acrylate having three or more (meth)acryloyl groups in the molecule, and Comparative Examples 2 and 3 are examples using photochromic compounds with number-average molecular weights of 300 to 10,000 that are not bonded to long-chain groups.

[0172] On the other hand, in the photochromic optical articles in the examples, which use a (meth)acrylate composition containing 24 to 100 mass% of a polyfunctional (meth)acrylate having three or more (meth)acryloyl groups in the molecule and a photochromic compound having a long-chain group with a number average molecular weight of 300 to 10,000, the temperature dependency value is improved compared to the comparative examples when compared at the same 23°C fading half-life.

[0173] In summary, photochromic optical articles using a (meth)acrylate composition containing 24 to 100% by mass of a multifunctional (meth)acrylate having three or more (meth)acryloyl groups in the molecule and a photochromic compound having a long-chain group with a number-average molecular weight of 300 to 10,000 exhibit sufficient hardness and excellent photochromic properties. Specifically, the presence of a long-chain group with a number-average molecular weight of 300 to 10,000 significantly improves the fading rate, and increasing the content of the multifunctional acrylate having three or more (meth)acryloyl groups in the molecule improves the crosslink density, preventing deterioration of the temperature dependency of the photochromic optical article. As a result, photochromic optical articles that satisfy both requirements have improved temperature dependency compared to photochromic optical articles that do not satisfy at least one of the requirements.

[0174] <Examples 6 to 11> Photochromic optical articles were produced in the same manner as in Example 1, except that component A, the photochromic compound, and other components were changed as shown in Table 3. The evaluation results are shown in Table 4.

[0175] [Table 3]

[0176] [Table 4]

Claims

1. (A) a (meth)acrylate composition containing a polyfunctional (meth)acrylate having three or more (meth)acryloyl groups in the molecule in an amount of 50 to 100% by mass; (B) at least one of the following formula (1): 【Chemical 1】 (In the formula, R １ and R ２ each independently represent a group bonded to a long-chain group having a number average molecular weight of 300 to 10,000, or a hydroxy group, an alkyl group, a haloalkyl group, a cycloalkyl group which may have a substituent, an alkoxy group, an amino group, a substituted amino group, a heterocyclic group which may have a substituent, a cyano group, a halogen atom, an alkylthio group, an arylthio group which may have a substituent, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aralkyl group which may have a substituent, an aralkoxy group which may have a substituent, an aryloxy group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, a thiol group, an alkoxyalkylthio group, a haloalkylthio group, or a cycloalkylthio group which may have a substituent; a represents an integer of 0 to 2, b represents an integer of 0 to 4, When a is 2, a plurality of R １ may be the same or different from each other, a is 2, and adjacent R １ If there is a １ Together they １ may form a ring together with the carbon atom bonded to it which may contain an oxygen atom, a sulfur atom, or a nitrogen atom, and the ring may further have a substituent, When b is 2 to 4, multiple R ２ may be the same or different from each other, b is 2 to 4, and adjacent R ２ If there is a ２ Together they ２ may form a ring together with the carbon atom bonded to it which may contain an oxygen atom, a sulfur atom, or a nitrogen atom, and the ring may further have a substituent, When neither a nor b is 0, at least one R １ and at least one R ２ may be taken together to form a ring, and the ring may further have a substituent, R ３ and R ４ each independently represents a group bonded to a long-chain group having a number average molecular weight of 300 to 10,000, or an aryl group which may have a substituent, or a heteroaryl group which may have a substituent; R １ , R ２ , R ３ , and R ４ At least one of the groups is a group bonded to a long-chain group having a number average molecular weight of 300 to 10,000. and a photochromic compound in which naphthopyran represented by the formula (I) is bonded to a long chain group having a number average molecular weight of 300 to 10,000. Contains the long-chain group having a number average molecular weight of 300 to 10,000 is a polyalkylene group, a polyalkyleneoxy group, a polyfluoroalkylene group, a polyfluoroalkylenyloxy group, a polydialkylsilyl group, a polydialkylsilyloxy group, or a combination thereof.

2. The naphthopyran represented by the formula (1) is represented by the following formula (2): 【Chemistry 2】 (In the formula, R ２ , R ３ , R ４ and b are the same as in formula (1), R ５ represents a group bonded to a long-chain group having a number average molecular weight of 300 to 10,000, or a hydroxy group, an alkyl group, a haloalkyl group, a cycloalkyl group which may have a substituent, an alkoxy group, an amino group, a substituted amino group, a heterocyclic group which may have a substituent, a cyano group, a halogen atom, an alkylthio group, an arylthio group which may have a substituent, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aralkyl group which may have a substituent, an aralkoxy group which may have a substituent, an aryloxy group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, a thiol group, an alkoxyalkylthio group, a haloalkylthio group, or a cycloalkylthio group which may have a substituent; c represents an integer of 0 to 4; When c is 2 to 4, multiple R ５ may be the same or different from each other, c is 2 to 4, and adjacent R ５ If there is a ５ Together they ５ may form a ring together with the carbon atom bonded to it which may contain an oxygen atom, a sulfur atom, or a nitrogen atom, and the ring may further have a substituent, R ６ and R ７ each independently represents a group bonded to a long-chain group having a number average molecular weight of 300 to 10,000, or a hydrogen atom, a hydroxy 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 which may have a substituent, an aralkoxy group which may have a substituent, an aryloxy group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent; R ６ and R ７ may combine together with the carbon atom at position 13 to which they are bonded to form an aliphatic ring having 3 to 20 ring carbon atoms, a condensed polycyclic ring in which an aromatic ring or an aromatic heterocycle is condensed to the aliphatic ring, a heterocycle having 3 to 20 ring atoms, or a condensed polycyclic ring in which an aromatic ring or an aromatic heterocycle is condensed to the heterocycle, R ２ , R ３ , R ４ , R ５ , R ６ , and R ７ At least one of the groups is a group bonded to a long-chain group having a number average molecular weight of 300 to 10,000. The photochromic curable composition according to claim 1, wherein the indenonaphthopyran is represented by the formula:

3. In the indenonaphthopyran represented by the formula (2), R ６ and R ７ and (b) are bonded together with the carbon atom at position 13 to form an aliphatic ring having 3 to 20 ring carbon atoms, a condensed polycycle in which an aromatic ring or an aromatic heterocycle is condensed to the aliphatic ring, a heterocycle having 3 to 20 ring atoms, or a condensed polycycle in which an aromatic ring or an aromatic heterocycle is condensed to the heterocycle, and the ring optionally has a substituent.

4. In the indenonaphthopyran represented by the formula (2), the aliphatic ring having 3 to 20 ring carbon atoms is a ring selected from a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cycloundecane ring, a cyclododecane ring, and a spirodicyclohexane ring; The photochromic curable composition according to claim 3, wherein the aliphatic ring may have 1 to 10 alkyl groups having 1 to 3 carbon atoms or cycloalkyl groups having 5 to 7 carbon atoms as substituents, or may be condensed with cycloalkyl groups having 5 to 7 carbon atoms.

5. A photochromic optical article obtained by polymerizing the photochromic curable composition according to any one of claims 1 to 4.

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