Photochromic curable composition and photochromic optical article

Abstract

(A) a (meth)acrylate composition having a content of 24 to 100 mass% of a polyfunctional (meth)acrylate having three or more (meth)acryloyl groups in the molecule, (B) a photochromic curable composition comprising a photochromic compound in which at least one specific naphthopyran is bonded to a long chain having a number average molecular weight of 300 to 10000, and a photochromic optical article formed by polymerizing the photochromic curable composition.

Description

Technology Field

[0001] The present invention relates to a photochromic curable composition and a photochromic optical article. Background Technology

[0002] Photochromic compounds, such as naphthopyran compounds, fulgide compounds, and spirooxazine compounds, are compounds that can reversibly take on two isomers with different absorption spectra by irradiating them with light containing ultraviolet rays, such as sunlight or light from mercury. Photochromic compounds have the characteristic (hereinafter referred to as "photochromic properties") that when ultraviolet rays are irradiated onto a compound that is generally in a colorless, colorless state, it rapidly isomerizes (color reaction) into a colored state, and returns to its original color when the irradiation is stopped and the compound is placed in a dark place. Taking advantage of this characteristic, they are used for various purposes, particularly as optical materials.

[0003] For example, photochromic eyeglass lenses, which are imparted photochromic properties through the use of photochromic compounds, rapidly tint to function as sunglasses when exposed to light containing ultraviolet rays such as sunlight outside of buildings, and fade to function as transparent ordinary eyeglasses when exposed to light inside buildings where such light is absent; as such, demand for them has been increasing recently.

[0004] In order to impart photochromic properties to optical articles, photochromic compounds and plastic materials are generally used in combination, and specifically, the following methods are known.

[0005] (a) A method of forming an optical article, such as a lens, directly by mixing a photochromic compound with a polymerizable monomer and polymerizing it.

[0006] (b) A method of forming a resin layer in which a photochromic compound is dispersed on the surface of a plastic molded article, such as a lens, by coating or mold polymerization.

[0007] (c) A method of bonding two optical sheets by an adhesive layer formed by a resin composition in which a photochromic compound is dispersed.

[0008] Among these, in particular, as shown 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 photocured to form a photochromic coating layer is an effective means in that it is applicable to various existing lenses.

[0009] However, among photochromic compounds used in photochromic optical articles, those that not only block light of a specific wavelength during isomerization (fading reaction) from a colored state to a decolored state but also return to their original colorless state upon heat are called T-type photochromic compounds. T-type photochromic compounds are frequently studied as materials for photochromic lenses. Generally, the following characteristics are required for T-type photochromic compounds.

[0010] (1) The degree of coloration in the visible light region before irradiation with ultraviolet light (hereinafter referred to as “initial coloration”) is small.

[0011] (2) The speed at which the color intensity reaches saturation after the start of irradiation with ultraviolet light is fast (i.e., the color sensitivity is high).

[0012] (3) The speed at which it returns to its original state after stopping the irradiation with ultraviolet rays (hereinafter referred to as the “fading speed”) is fast.

[0013] (4) The reversible reaction has good durability.

[0014] (5) So that the dispersibility of the host material used is increased, it is dissolved in a high concentration in the monomer composition that becomes the host material after curing.

[0015] Chromene compounds have been widely studied as photochromic compounds that satisfy these characteristics. Recently, the demands for photochromic glasses have become more sophisticated, and, for example, there is a demand to reduce temperature dependence.

[0016] It is generally known that T-type photochromic compounds have a trade-off relationship between the fading rate and the color intensity. Therefore, it is known that they are susceptible to the influence of the ambient temperature (high temperature dependence), such as when used under high temperatures, for example, during the summer when sunlight is strong, the fading reaction becomes more likely and the color intensity decreases. Therefore, there has been a particular demand for the development of photochromic lenses that have high color intensity even under high temperatures, such as during the summer (hereinafter, the characteristic of having high color intensity even under high temperatures is sometimes referred to as having "low temperature dependence").

[0017] Generally, in order to obtain a high color intensity at high temperatures, it was necessary to improve the thermal stability of the photochromic compound in the color-developing state, that is, to make it a photochromic compound with a slow fading rate. Therefore, it is generally difficult to achieve the same characteristics as (3) above and the characteristic of having low temperature dependence. The inventors have proposed a chromene compound with reduced temperature dependence by having a substituent at a specific position (see Patent Document 2). In this compound, the temperature dependence can be made relatively small, but since it is a compound having a substituent at a specific position, the color tone is limited, and there is also room for further improvement in the fading rate in the solid matrix.

[0018] In a solid matrix, structural changes resulting from the isomerization of photochromic compounds are limited, so the fading rate tends to decrease. Therefore, to improve the fading rate, one might consider lowering the glass transition temperature of the solid matrix (polymer) to soften the substrate or expanding the free space within the matrix. However, while it is possible to create an environment where structural changes of photochromic compounds 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 becomes insufficient. Consequently, the temperature dependence of the solid matrix increases, and as a result, the temperature dependence of the photochromic properties increases, making it impossible to satisfy the high photochromic properties required recently. Furthermore, the strength and hardness as a photochromic lens become insufficient; when photochromic properties are imparted by a coating method, the photochromic compound leaches out when a hard coating layer is formed over the photochromic coating layer, indicating that there is still room for improvement.

[0019] Other methods to improve the fading rate in a solid matrix include using photochromic compounds having oligomeric chains (see Patent Documents 3 to 5). However, there was room for improvement, such as the compatibility of oligomeric chain photochromic compounds with the solid matrix being used being important, and if compatibility is low, cloudiness occurs, which limits the solid matrix being used. Furthermore, when photochromic properties are expressed through a thin film using a coating method, it is necessary to add the photochromic compound at a high concentration, but because the concentration of the photochromic compound in the molecule is lowered due to the oligomeric chains, it is necessary to add it at an even higher concentration, and as a result, there were problems such as the hardness of the photochromic coating layer being significantly reduced. Prior art literature

[0020] Patent Document 1: International Publication No. 2011 / 125956 Patent Document 2: Japanese Patent 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 The problem to be solved

[0021] As described above, to meet the recently required high photochromic properties (particularly, the reduction of temperature dependence), additional improvements are necessary, while additional improvements are also required in terms of the strength and hardness of host materials such as resins.

[0022] Accordingly, the present invention aims to provide a photochromic curable composition that achieves sufficient strength and hardness while simultaneously achieving high photochromic properties, and a photochromic optical article using the photochromic curable composition. means of solving the problem

[0023] The inventors of the present invention have diligently conducted repeated investigations to solve the above problem. As a result, they discovered that the above problem can be solved not only by using a photochromic compound having an oligomeric chain, but also by using a specific host material, and thus completed the present invention.

[0024] That is, the photochromic curable composition according to the present invention comprises: (A) a (meth)acrylate composition having a content of 24 to 100 mass% of a polyfunctional (meth)acrylate having three or more (meth)acryloyl groups in the molecule; and,

[0025] (B) A photochromic compound formed by bonding at least one naphthopyran represented by the following formula (1) to a long chain having a number average molecular weight of 300 to 10,000;

[0026] It contains

[0027] [Chemical Formula 1]

[0028]

[0029] (during the meal,

[0030] R 1 and R 2 Each represents, independently, a group bonded to a long chain having a number average molecular weight of 300 to 10,000, or a hydroxyl group, an alkyl group, a haloalkyl group, a cycloalkyl group that may have a substituent, an alkoxy group, an amino group, a substituted amino group, a heterocyclic group that may have a substituent, a cyano group, a halogen atom, an alkylthio group, an arylthio group that may have a substituent, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aralkyl group that may have a substituent, an aralkoxy group that may have a substituent, an aryloxy group that may have a substituent, an aryl group that may have a substituent, a heteroaryl group that may have a substituent, a thiol group, an alkoxyalkylthio group, a haloalkylthio group, or a cycloalkylthio group that may have a substituent.

[0031] a represents an integer from 0 to 2, and b represents an integer from 0 to 4,

[0032] If a is 2, then multiple R 1 They may be identical or different from each other,

[0033] a is 2, and adjacent R 1 In the case where this exists, the two adjacent Rs 1 Becoming one, they R 1 It may form a ring that may include an oxygen atom, a sulfur atom, or a nitrogen atom together with a carbon atom bonded to it, and furthermore, said ring may have a substituent, and

[0034] If b is 2 to 4, multiple R 2 They may be identical or different from each other,

[0035] b is 2 to 4, and adjacent R 2If exists, the two adjacent Rs 2 They become one and R 2 It may form a ring that may include an oxygen atom, a sulfur atom, or a nitrogen atom together with a carbon atom bonded to it, and furthermore, said ring may have a substituent, and

[0036] If a and b are not both 0, then at least 1 R 1 and at least one R 2 A may become one to form a ring, and also the ring may have a substituent,

[0037] R 3 and R 4 Each represents, independently, a group bonded to a long chain having a number average molecular weight of 300 to 10,000, or an aryl group that may have a substituent or a heteroaryl group that may have a substituent, and

[0038] R 1 , R 2 , R 3 , and R 4 At least one of them is a group that combines with a long chain group having a number average molecular weight of 300 to 10,000.)

[0039] In addition, the photochromic optical article according to the present invention is formed by polymerizing the photochromic curable composition according to the present invention. Effects of the invention

[0040] According to the present invention, a photochromic curable composition that achieves sufficient strength and hardness while simultaneously achieving high photochromic properties, and a photochromic optical article using the photochromic curable composition can be provided. Brief explanation of the drawing

[0041] Figure 1 is a diagram showing the relationship between temperature dependence and fading half-life in the compounds of the example and the compounds of the comparative example. Specific details for implementing the invention

[0042] <<Photochromic Curable Composition>>

[0043] The photochromic curable composition according to the present embodiment comprises (A) a (meth)acrylate composition having a content of 24 to 100 mass% of a polyfunctional (meth)acrylate having three or more (meth)acryloyl groups in the molecule (hereinafter also referred to as "Component A"), and (B) a photochromic compound formed by bonding at least one specific naphthopyran to a long chain having a number average molecular weight of 300 to 10,000 (hereinafter also referred to as "Component B"). According to this photochromic curable composition, a photochromic optical article having high photochromic properties while possessing sufficient strength and hardness can be obtained. The inventors have considered the reasons for obtaining such effects as follows.

[0044] That is, sufficient strength and hardness can be realized in a solid matrix by polymerizing a host material containing a (meth)acrylate composition having a content of 24 to 100 mass% of a polyfunctional (meth)acrylate having three or more (meth)acryloyl groups within the molecule. Typically, since free space is not sufficiently formed in such a solid matrix, it becomes difficult to express photochromic properties. However, in the case of a photochromic compound in which at least one naphthopyran is bonded to a long chain with a number average molecular weight of 300 to 10,000, it is believed that sufficient strength and hardness can be realized while maintaining an environment where structural changes are likely to occur only near the long chain. Furthermore, since the crosslinking density of the obtained solid matrix is ​​high, the temperature dependence of the solid matrix is ​​reduced, thereby maintaining the temperature dependence of the photochromic properties at a low level. Thus, it is possible to produce a photochromic optical article with a high color intensity even under high temperatures such as those in summer.

[0045] Furthermore, the term "(meth)acryloyl group" refers to both "acryloyl group" and "methacryloyl group." The same applies to other terms such as "(meth)acrylate."

[0046] <(A) (Meth)acrylate composition>

[0047] As for the (meth)acrylate composition of component A, a known polyfunctional (meth)acrylate may be used alone without particular limitation, 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 difunctional (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 used. Various compounds used as component A will be described in detail below.

[0048] [A1 component]

[0049] As the A1 component, polyfunctional (meth)acrylates having three or more (meth)acryloyl groups in the molecule, polyfunctional (meth)acrylates having urethane bonds, and polyfunctional (meth)acrylates not corresponding to the above are preferably used.

[0050] ((A1-1) Polyfunctional (meth)acrylate represented by the following formula (3))

[0051] [Chemical Formula 2]

[0052]

[0053] During the meal, R 10 Representing silver, a hydrogen atom, or a methyl group, R 11 Representing silver, a hydrogen atom, or an alkyl group having 1 to 2 carbon atoms, R12 represents a 3 to 6-valent organic group having 1 to 10 carbon atoms, e represents a number from 0 to 3 as an average value, and f represents an integer from 3 to 6. R 11 As for the alkyl group having 1 to 2 carbon atoms represented by, a methyl group is preferred. R 12 Examples of organic groups represented by [the name] include groups derived from polyols, 3 to 6-valent hydrocarbon groups, and organic groups including 3 to 6-valent urethane bonds.

[0054] Specific examples of the polyfunctional (meth)acrylate expressed by the above formula (3) include, for example, 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, dipentaerythritol hexaacrylate, etc.

[0055] ((A1-2) Polyfunctional (meth)acrylate having urethane bonds)

[0056] (A1-2) A polyfunctional (meth)acrylate having urethane bonds is obtained by reacting a polyisocyanate compound having two or more isocyanate groups in the molecule, a polyol compound having two or more hydroxyl groups in the molecule, and a hydroxyl group-containing (meth)acrylate, and has three or more (meth)acryloyl groups in the molecule.

[0057] Specific examples of polyisocyanate compounds having two or more isocyanate groups in the molecule include, for example, hexamethylene diisocyanate, isophorone diisocyanate, lysine isocyanate, 2,2,4-hexamethylene diisocyanate, dimer acid diisocyanate, isopropylidene bis-4-cyclohexyl isocyanate, dicyclohexylmethane diisocyanate, norbornene diisocyanate, methylcyclohexane diisocyanate, etc.

[0058] Specific examples of polyol compounds having two or more hydroxyl groups within the molecule include, for example, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, etc.

[0059] Commercially available products may be used as polyfunctional (meth)acrylates having urethane bonds. Examples of commercially available products include U-4 HA (molecular weight: 596, number of functional groups: 4), U-6 HA (molecular weight: 1019, number of functional groups: 6), U-6 LPA (molecular weight: 818, number of functional groups: 6), and U-15 HA (molecular weight: 2300, number of functional groups: 15), manufactured by Shin-Nakamura Kagaku Kogyo Co., Ltd.

[0060] ((A1-3) Polyfunctional (meth)acrylates not corresponding to the above)

[0061] (A1-3) Polyfunctional (meth)acrylates not corresponding to the above may include, for example, compounds in which the terminals of a polyester compound are modified with (meth)acryloyl groups. Various polyester (meth)acrylate compounds are commercially available depending on the molecular weight of the raw polyester compound or the amount of modification of the (meth)acryloyl groups, and these commercially available products may be used. Specific examples of polyester (meth)acrylate compounds include, for example, tetrafunctional polyester oligomers (molecular weight: 2500 to 3500, manufactured by Daicel All Nex Co., Ltd., EB80, etc.), hexafunctional polyester oligomers (molecular weight: 6000 to 8000, manufactured by Daicel All Nex Co., Ltd., EB450, etc.), hexafunctional polyester oligomers (molecular weight: 45000 to 55000, manufactured by Daicel All Nex Co., Ltd., EB1830, etc.), tetrafunctional polyester oligomers (molecular weight: 10000, manufactured by Daiichi Kokyose Iyaku Co., Ltd., GX8488B, etc.).

[0062] By using the A1 component exemplified above, strength and hardness can be improved while maintaining photochromic properties.

[0063] For each of the above A1 components, one type may be used alone or two or more types may be used in combination. Additionally, the individually described components may be used in combination with each other. When multiple types of A1 components are used in combination, the mass that serves as the standard for the A1 components is the total amount thereof.

[0064] Among the A1 components described above, trimethylolpropane trimethacrylate, ditrimethylolpropane tetramethacrylate, and dipentaerythritol hexaacrylate are preferred.

[0065] [A2 component]

[0066] As for the A2 component, it is not particularly limited to a difunctional (meth)acrylate, and a difunctional (meth)acrylate represented by the following formulas (4), (5), or (6), a difunctional (meth)acrylate having a urethane bond, and a difunctional (meth)acrylate not corresponding to the above are preferably used.

[0067] ((A2-1) A difunctional (meth)acrylate represented by the following formula (4))

[0068] [Chemical Formula 3]

[0069]

[0070] During the meal, R 13 and R 14 Each represents a hydrogen atom or a methyl group independently, g and h each represent an integer greater than or equal to 0 independently, and g + h is an integer greater than or equal to 2. Furthermore, the difunctional (meth)acrylate represented by the above formula (4) is often obtained as a mixture during manufacturing. Therefore, g + h is a number greater than or equal to 2 as an average value, and preferably a number between 2 and 50 as an average value.

[0071] Specific examples of the difunctional (meth)acrylate represented by the above formula (4) include, for example, 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 composed of a mixture of polypropylene glycol and polyethylene glycol (having two repeating units of polyethylene and two repeating units of polypropylene), polyethylene glycol dimethacrylate (particularly, g=4, h=0, average molecular weight: 330), polyethylene glycol dimethacrylate (particularly, g=9, h=0, average molecular weight: 536), Examples include 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), etc.

[0072] ((A2-2) A difunctional (meth)acrylate represented by the following formula (5))

[0073] [Chemical Formula 4]

[0074]

[0075] During the meal, 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)(C6H5)-. i and j each independently represent an integer greater than or equal to 1, and i+j is an average value of 2 to 30. Furthermore, the difunctional (meth)acrylate expressed by the above formula (5) can typically be obtained in the form of a mixture of molecules with different molecular weights. Therefore, i+j is expressed as an average value.

[0076] Specific examples of the difunctional (meth)acrylates represented by the above formula (5) include, for example, 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: 672), 2,2-bis[3,5-dibromo-4-(methacryloyloxyethoxy)phenyl]propane (i+j=2, average molecular weight: 768), and 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-(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 Examples include 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.

[0077] ((A2-3) A difunctional (meth)acrylate represented by the following formula (6))

[0078] [Chemical Formula 5]

[0079]

[0080] During the meal, R 20 and R 21Each represents independently a hydrogen atom or a methyl group, k represents a number from 1 to 20 as an average value, and B and B' each represent independently a straight-chain or branched-chain alkylene group having 2 to 15 carbon atoms. If multiple B are present, each of the multiple B may be the same group or different groups.

[0081] The difunctional (meth)acrylate represented by the above formula (6) can be prepared by reacting polycarbonate diol with (meth)acrylic acid.

[0082] Specific examples of polycarbonate diols include, for example, polycarbonate diol obtained by phosgenation of trimethylene glycol (average molecular weight: 500 to 2000), polycarbonate diol obtained by phosgenation of tetramethylene glycol (average molecular weight: 500 to 2000), polycarbonate diol obtained by phosgenation of pentamethylene glycol (average molecular weight: 500 to 2000), polycarbonate diol obtained by phosgenation of hexamethylene glycol (average molecular weight: 500 to 2000), polycarbonate diol obtained by phosgenation of octamethylene glycol (average molecular weight: 500 to 2000), polycarbonate diol obtained by phosgenation of nonamethylene glycol (average molecular weight: 500 to 2000), and polycarbonate diol obtained by phosgenation of triethylene glycol and tetramethylene glycol (average Examples include polycarbonate diol obtained by phosgenation of tetramethylene glycol and hexamethylene diglycol (average molecular weight: 500 to 2000), polycarbonediol obtained by phosgenation of pentamethylene glycol and hexamethylene glycol (average molecular weight: 500 to 2000), polycarbonediol obtained by phosgenation of tetramethylene glycol and octamethylene glycol (average molecular weight: 500 to 2000), polycarbonate diol obtained by phosgenation of hexamethylene glycol and octamethylene glycol (average molecular weight: 500 to 2000), and polycarbonate diol obtained by phosgenation of 1-methyltrimethylene glycol (average molecular weight: 500 to 2000).

[0083] ((A2-4) Difunctional (meth)acrylate having urethane bonds)

[0084] (A2-4) As a difunctional (meth)acrylate having urethane bonds, it is preferable to obtain it by reacting a polyisocyanate compound having two or more isocyanate groups in the molecule, a polyol compound having two or more hydroxyl groups in the molecule, and a hydroxyl group-containing (meth)acrylate.

[0085] Specific examples of polyisocyanate compounds having two or more isocyanate groups in the molecule include, for example, hexamethylene diisocyanate, isophorone diisocyanate, lysine isocyanate, 2,2,4-hexamethylene diisocyanate, dimer acid diisocyanate, isopropylidene bis-4-cyclohexyl isocyanate, dicyclohexylmethane diisocyanate, norbornene diisocyanate, methylcyclohexane diisocyanate, etc.

[0086] Specific examples of polyol compounds having two or more hydroxyl groups within the molecule include, for example, polyalkyleneglucol 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, trimethylolpropane; etc.

[0087] In addition, as a difunctional (meth)acrylate having urethane bonds, a reaction mixture obtained by reacting a urethane prepolymer having isocyanate groups at the molecular ends, which is obtained by reacting the polyisocyanate compound and the polyol compound, with 2-hydroxy(meth)acrylate, or a urethane(meth)acrylate obtained by directly reacting the A1 component with 2-hydroxy(meth)acrylate, etc., may also be used.

[0088] Specific examples of hydroxyl group-containing (meth)acrylates include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate.

[0089] Commercially available products may be used as difunctional (meth)acrylates having urethane bonds. Examples of commercially available products include U-2 PPA (molecular weight: 482), UA-122 P (molecular weight: 1100), U-122 P (molecular weight: 1100) manufactured by Shin-Nakamura Kagaku Kogyo Co., Ltd., and EB4858 (molecular weight: 454) manufactured by Daicel Allnex Co., Ltd.

[0090] ((A2-5) Difunctional (meth)acrylates not corresponding to the above)

[0091] (A2-5) Examples of difunctional (meth)acrylates not corresponding to the above include compounds having (meth)acryloyl groups at both ends of an alkylene group that may have a substituent. Among these, it is preferable to have an alkylene group having 6 to 20 carbon atoms. Specifically, examples include 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol diacrylate, 1,10-decanediol dimethacrylate, etc.

[0092] In addition, difunctional (meth)acrylates that do not fall under the above may include difunctional (meth)acrylates containing sulfur atoms. It is preferable that the sulfur atom forms part of the molecular chain as a sulfide group. Specifically, 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, 1,2-bis(acryloyloxyisopropylthioisopropyl)sulfide, etc.

[0093] For each of the above A2 components, one type may be used alone or two or more types may be used in combination. Additionally, the components described individually may be used in combination with each other. When multiple types of A2 components are used in combination, the mass that serves as the standard for the A2 components is the total amount thereof.

[0094] Among the A2 components described above, polyethylene glycol dimethacrylate (specifically, g=4, h=0, average molecular weight: 330), polyethylene glycol dimethacrylate (specifically, g=9, h=0, average molecular weight: 536), polyethylene glycol dimethacrylate (specifically, 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), and 2,2-bis[4-(acryloyloxypolyethoxy)phenyl]propane (i+j=20, average molecular weight 1216) are preferred.

[0095] [A3 component]

[0096] As for the A3 component, it is not particularly limited to monofunctional (meth)acrylate, and a monofunctional (meth)acrylate represented by the following formula (7) is preferably used.

[0097] [Chemical Formula 6]

[0098]

[0099] During the meal, R 22 represents a hydrogen atom or a methyl group, and R 23It represents a hydrogen atom, a methyl dimethoxysilyl group, a trimethoxysilyl group, or a glycidyl group, where l represents an integer from 0 to 10, and m represents an integer from 0 to 20.

[0100] Specific examples of monofunctional (meth)acrylates 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, glycidyl methacrylate, etc.

[0101] Among the A3 components described above, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and glycidyl methacrylate are preferred.

[0102] [A4 ingredient]

[0103] As for the A4 component, other radical polymerizable monomers are not particularly limited, and radical polymerizable polyrotaxanes, radical polymerizable silsesquioxane compounds, allyl compounds, and vinyl compounds are preferably used.

[0104] ((A4-1) Radical Polymerizable Polyrotaxane)

[0105] (A4-1) A radical polymerizable polyrotaxane has a complex molecular structure comprising a axial molecule and a plurality of cyclic molecules that enclose the axial molecule, and a side chain having a hydroxyl group is introduced into the cyclic molecule. In this polyrotaxane, the hydroxyl group of the side chain is modified by 1 mol% or more and less than 100 mol% with a radical polymerizable compound to have a radical polymerizable group. In addition, in this specification, the reaction of reacting the hydroxyl group of the side chain with another compound to introduce a structure derived from the other compound is also referred to as "modification."

[0106] Polyrotaxanes have a complex molecular structure formed of chain-like axial molecules and cyclic molecules. That is, multiple cyclic molecules enclose the axial molecules, and the axial molecules penetrate the interior of the rings of the cyclic molecules. Although the cyclic molecules can freely slide along the axial molecules, bulky terminal groups are formed at both ends of the axial molecules, preventing the cyclic molecules from detaching from the axial molecules.

[0107] Various types of axial molecules are known for polyrotaxanes. For example, as axial molecules, they can be straight or branched as long as they can penetrate the ring of the cyclic molecule; generally, straight or branched polymers are used.

[0108] Specific examples of polymers forming axial molecules include, for example, polyvinyl alcohol, polyvinylpyrrolidone, cellulose-based resins (carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, 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-based resins (poly(meth)acrylic acid, polymethyl methacrylate, polymethyl acrylate, acrylonitrile-methyl acrylate copolymer resin, etc.), polycarbonate, polyurethane, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral, polyisobutylene, Examples include polytetrahydrofuran, polyaniline, acrylonitrile-butadiene-styrene ternary polymer resin (ABS resin), polyamide (nylon, etc.), polyimide, polydiene (polyisoprene, polybutadiene, etc.), polysiloxane (polydimethylsiloxane, etc.), polysulfone, polyimine, polyacetic anhydride, polyurea, polysulfide, polyphosphazene, polyketone-polyphenylene, polyhaloolefin, etc. These polymers may be appropriately copolymerized or modified.

[0109] Among these, polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, polypropylene, polyvinyl alcohol, and polyvinylmethyl ether are preferred, and polyethylene glycol is more preferred.

[0110] The bulky groups formed at both ends of the axis molecule are not particularly limited as long as they prevent the cyclic molecule from leaving the axis molecule, but in terms of bulk, adamantyl groups, trityl groups, fluoresceinyl groups, dinitrophenyl groups, and pyrenyl groups are preferred, and in terms of ease of introduction, adamantyl groups are more preferred.

[0111] The mass 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, etc.) tends to be poor, and if it is too small, the mobility of the cyclic molecule decreases, and photochromic properties tend to decrease. In this regard, 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. Furthermore, this mass average molecular weight is a value measured by the GPC measurement method described in the examples to be described later.

[0112] A cyclic molecule is one having a ring of a size capable of encapsulating an axial molecule. Examples of such rings include a cyclodextrin ring, a crown ether ring, a benzocrown ring, a dibenzocrown ring, a dicyclohexanocrown ring, etc., and a cyclodextrin ring is preferred. Cyclodextrin rings include α-types (ring inner diameter: 0.45 to 0.6 nm), β-types (ring inner diameter: 0.6 to 0.8 nm), and γ-types (ring inner diameter: 0.8 to 0.95 nm), and α-cyclodextrin rings and γ-cyclodextrin rings are preferred, and α-cyclodextrin rings are more preferred.

[0113] Typically, a plurality of cyclic molecules are encapsulated in a single axial molecule. When the maximum number of cyclic molecules that can be encapsulated per axial molecule is set to 1.0, the number of cyclic molecules encapsulated 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.

[0114] The maximum number of inclusions of a cyclic molecule for a single axial molecule can be calculated from the length of the axial molecule and the thickness of the cyclic molecule. For example, if 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 [-CH2-CH2O-] of polyethylene glycol are approximately equal to 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 can be obtained as the maximum number of inclusions of the cyclic molecule. By setting this maximum number of inclusions to 1.0, the number of inclusions of the cyclic molecule is adjusted to the range described above.

[0115] Polyrotaxane having a radical polymerizable group is prepared using a polyrotaxane in which a side chain having a hydroxyl group is introduced into the aforementioned cyclic molecule (hereinafter also referred to as "side chain hydroxyl group containing polyrotaxane"). By introducing these side chains into the ring, a suitable space can be more reliably formed between adjacent axis molecules. Therefore, a gap capable of allowing the reversible reaction of photochromic compound molecules can be reliably secured, thereby enabling the expression of excellent photochromic properties. Furthermore, these side chains form a pseudo-crosslinked structure in polyrotaxanes, which can thereby improve the photochromic properties of the photochromic resin layer.

[0116] As for the side chain, it is preferable that it be formed by the repetition of an organic chain having a hydroxyl group and having a carbon number in the range of 3 to 20. The average molecular weight of such 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 securing a gap capable of allowing the reversible reaction of the photochromic compound molecule tends to become insufficient. On the other hand, if the side chain is too large, it becomes difficult to tightly mix the photochromic compound described later with the polyrotaxane, and it tends to be difficult to fully utilize the space secured by the polyrotaxane. Furthermore, the average molecular weight of the side chain can be adjusted by the amount used when introducing the side chain and, in addition to being calculated 1 It can also be obtained from H-NMR measurements.

[0117] The above-mentioned side chains can be introduced by utilizing the functional groups of the cyclic molecule and modifying these functional groups. For example, an α-cyclodextrin ring has 18 hydroxyl groups as functional groups, and side chains can be introduced through these hydroxyl groups. That is, up to 18 side chains can be introduced for a single α-cyclodextrin ring. In order to fully exert the function of the above-mentioned side chains, it is desirable that at least 6%, and particularly at least 30%, of the total number of functional groups of the ring are modified as side chains.

[0118] In addition, the functional groups of the cyclic molecule may affect compatibility with other components, and in particular, if the functional groups are hydroxyl groups, they have a significant effect on compatibility with other components. Therefore, the ratio of the functional groups modified (degree of modification) is preferably 6 to 80%, and more preferably 30 to 70%. Since the functional groups of the cyclic molecule have lower reactivity than the hydroxyl groups of the side chains, problems such as reduced compatibility or bleed-out do not easily occur even with a low degree of modification. Therefore, a superior effect is achieved when the degree of modification is within the above range. Furthermore, when side chains are attached to 9 of the 18 hydroxyl groups of the α-cyclodextrin ring, the degree of modification becomes 50%.

[0119] The above side chain may be a straight chain or a branched chain if it is an organic chain having a hydroxyl group. An organic chain having a desired hydroxyl group may be introduced as a side chain by reacting a compound capable of introducing a hydroxyl group to the functional group of a cyclic molecule using ring-opening polymerization; radical polymerization; cationic polymerization; anionic polymerization; 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 modification of the hydroxyl group into a compound having a radical polymerizable group, it is preferable to adopt a method of introducing a side chain derived from a cyclic compound by ring-opening polymerization. Furthermore, it is preferable to introduce a side chain having a hydroxyl group at the terminal end.

[0120] For ring-opening polymerization, it is preferable to use cyclic ethers or lactone-based compounds, considering that they are readily available, highly reactive, and easy to adjust in size (molecular weight). By using cyclic ethers or lactone-based compounds, hydroxyl groups can be introduced to the ends of the side chains. Specific examples of these preferred cyclic ethers or lactone-based compounds are as follows.

[0121] Specific examples of cyclic ethers include, for example, ethylene oxide, 1,2-propylene oxide, epichlorohydrin, epibromohydrin, 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide, oxetane, 3-methyl oxetane, 3,3-dimethyl oxetane, tetrahydrofuran, 2-methyl tetrahydrofuran, 3-methyl tetrahydrofuran, etc.

[0122] Specific examples of lactone compounds include, for example, tetracyclic 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, D-erythronolactone, α-methyl-γ-butyrolactone, γ-nonanolactone, DL-pantolactone, γ-phenyl-γ-butyrolactone, γ-undecanolactone, γ-valerolactone, 2,2-pentamethylene-1,3-dioxolan-4-one, 5-membered ring lactones such as α-bromo-γ-butyrolactone, γ-crotonolactone, α-methylene-γ-butyrolactone, α-methacryloyloxy-γ-butyrolactone, β-methacryloyloxy-γ-butyrolactone; 6-membered lactones such as δ-valerolactone, δ-hexanolactone, δ-octanolactone, δ-nonanolactone, 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-dioxane-2-one, 1,5-dioxephan-2-one, etc.; nonalkyl-ε-caprolactone, dialkyl-ε-caprolactone, monomethyl-ε-caprolactone, monoethyl-ε-caprolactone, monohexyl-ε-caprolactone, Examples include seven-membered lactones such as 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-oxephane-2-one, 4,4,6-trimethyl-oxephane-2-one, 4,6,6-trimethyl-oxephane-2-one, and 5-hydroxymethyl-oxephane-2-one; eight-membered lactones such as ζ-enantholactone; and other lactones such as lactone, lactide, dilacide, tetramethylglycoside, 1,5-dioxephane-2-one, and t-butylcaprolactone.The above cyclic compounds may be used as a single type or in combination of two or more types.

[0123] Among these cyclic compounds, lactone-based compounds such as ε-caprolactone, α-acetyl-γ-butyrolactone, α-methyl-γ-butyrolactone, γ-valerolactone, and γ-butyrolactone are preferred, and ε-caprolactone is more preferred.

[0124] In addition, when introducing a side chain by reacting a cyclic compound through ring-opening polymerization, the functional group (e.g., hydroxyl group) attached to the cyclic molecule may lack reactivity, and it may be difficult to directly react the large molecule due to steric hindrance or other factors. In such cases, a method may be employed in which a small molecular weight compound, such as propylene oxide, is reacted with the functional group attached to the cyclic molecule to perform hydroxypropylation, thereby introducing a highly reactive functional group (hydroxyl group), and then introducing a side chain through ring-opening polymerization using the aforementioned cyclic compound. In this case, the hydroxypropylated portion can also be considered as a side chain.

[0125] When a side chain is introduced by reacting a cyclic compound through ring-opening polymerization, the side chain introduced by the cyclic compound is described as a side chain modified by the cyclic compound. For example, a side chain obtained by introducing a lactone-based compound is described as a side chain modified by the lactone-based compound. In the present embodiment, it is preferable that the side chain introduced into the polyrotaxane containing a side chain hydroxyl group is a side chain modified by the lactone-based compound.

[0126] Polyrotaxane having a radical polymerizable group is prepared by reacting a hydroxyl group on the side chain of a polyrotaxane containing a side chain hydroxyl group with a compound having a radical polymerizable group, thereby introducing a radical polymerizable group into the side chain of the polyrotaxane containing a side chain hydroxyl group. Known reaction conditions may be employed for the reaction between the hydroxyl group on the side chain of the polyrotaxane containing a side chain hydroxyl group and the compound having a radical polymerizable group.

[0127] It can be assumed that by introducing a radical polymerizable group capable of polymerizing with the aforementioned polymerizable monomer into the side chain of the cyclic molecule, compatibility can be increased, and furthermore, the photochromic compound can be maintained homogeneously in a dispersed state within the pores formed by the polyrotaxane. As a result, the resulting photochromic resin layer can continuously exhibit excellent photochromic properties, and furthermore, it can be assumed that the mechanical strength is increased.

[0128] As for the compound having a radical polymerizable group, it is not particularly limited to a compound having both a functional group capable of reacting with a hydroxyl group of a side chain and a radical polymerizable group in one molecule, and considering compatibility with other components, it is preferable to have a compound that does not have a hydroxyl group in the molecule.

[0129] Functional groups capable of reacting with hydroxyl groups include, for example, isocyanate groups (-NCO), carboxyl groups (-COOH), acid chloride groups (-COCl), etc. By reacting a compound having an isocyanate group, a radical polymerizable group is introduced through a urethane bond. In addition, by reacting a compound having a carboxyl group, acid chloride group, etc., a radical polymerizable group is introduced through an ester bond.

[0130] Specific examples of compounds having an isocyanate group and a radical polymerizable group include, for example, 2-isocyanate ethyl methacrylate, 2-isocyanate ethyl acrylate, 1,1-(bisacryloyloxymethyl)ethyl isocyanate. Specific examples of compounds having a carboxyl group and a radical polymerizable group include, for example, 2-methacryloyloxyethyl sacrylate, β-carboxyethyl acrylate. Compounds having an acid chloride group and a radical polymerizable group can be synthesized by reacting a compound having a carboxyl group and a radical polymerizable group with a chlorinating agent such as thionyl chloride.

[0131] Radical polymerizable polyrotaxanes are not particularly limited as long as they have radical polymerizable groups in the molecule, but the modification ratio of the radical polymerizable groups to the hydroxyl groups of the side chains, that is, the reaction ratio of the compound having radical polymerizable groups to the total number of hydroxyl groups of the side chains, is preferably 1 mol% or more and less than 100 mol%. The modification ratio can be calculated as (number of moles of radical polymerizable groups introduced) / (number of moles of the total hydroxyl groups of the side chains) × 100. Furthermore, from the perspective of adhesion, mechanical strength of the resulting cured body, and photochromic properties, the modification ratio is preferably 10 to 95 mol%.

[0132] ((A4-2) Radical Polymerizable Silsesquioxane Compounds)

[0133] Radical polymerizable silsesquioxane compounds take on various molecular structures, such as cage, ladder, and random types, and possess radical polymerizable groups such as (meth)acryloyl groups.

[0134] Examples of such radical polymerizable silsesquioxane compounds include those represented by the following formula (8).

[0135] [Chemical Formula 7]

[0136]

[0137] In the formula, n is the degree of polymerization and represents an integer from 3 to 100. Multiple R 24 represents 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, which may be identical or different from each other. provided that at least one R 24 is a radical polymerization group, or an organic group containing a radical polymerization group.

[0138] Here, R 24Examples of radical polymerization groups, or organic groups containing radical polymerization groups, include (meth)acryloyl groups; organic groups having (meth)acryloyl groups such as (meth)acryloyloxypropyl groups, (3-(meth)acryloyloxypropyl)dimethylsiloxy groups; allyl groups; organic groups having allyl groups such as allylpropyl groups, allylpropyldimethylsiloxy groups; vinyl groups; organic groups having vinyl groups such as vinylpropyl groups, vinyldimethylsiloxy groups; etc.

[0139] ((A4-3) Allyl compounds)

[0140] Specific examples of allyl compounds include, for example, diethylene glycol bis-allyl carbonate, methoxypolyethylene glycol allyl ether (especially, average molecular weight: 550), methoxypolyethylene glycol allyl ether (especially, average molecular weight: 350), methoxypolyethylene glycol allyl ether (especially, average molecular weight: 1500), polyethylene glycol allyl ether (especially, average molecular weight: 450), methoxypolyethylene glycol-polypropylene glycol allyl ether (especially, average molecular weight: 750), butoxypolyethylene glycol-polypropylene glycol allyl ether (especially, average molecular weight: 1600), methacryloyloxypolyethylene glycol-polypropylene glycol allyl ether (especially, average molecular weight: 560), phenoxypolyethylene glycol allyl ether (especially, average molecular weight: 600), methacryloyloxypolyethylene glycol allyl ether (especially, average molecular weight: 430), and acryloyloxypolyethylene glycol allyl ether (especially, average Examples include vinyloxypolyethylene glycol allyl ether (especially, average molecular weight: 560), styryloxypolyethylene glycol allyl ether (especially, average molecular weight: 650), methoxypolyethylene thioglycol allylthioether (especially, average molecular weight: 730), etc.

[0141] ((A4-4) Vinyl compounds)

[0142] Specific examples of vinyl compounds include, for instance, methyl vinyl ketone, ethyl vinyl ketone, ethyl vinyl ether, styrene, vinyl cyclohexane, butadiene, 1,4-pentadiene, divinyl sulfide, divinyl sulfone, 1,2-divinylbenzene, 1,3-divinyl-1,1,3,3-tetramethylpropanedisiloxane, diethylene glycol divinyl ether, divinyl adipice, divinyl sebacate, ethylene glycol divinyl ether, divinyl sulfoxide, divinyl persulfide, dimethyl divinylsilane, 1,2,4-trivinylcyclohexane, methyltrivinylsilane, α-methylstyrene, α-methylstyrene dimer, etc.

[0143] (Desirable Component A and Mixing Ratio)

[0144] Among the A1, A2, and A3 components described above, 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 A combination using 2,2-bis[4-(acryloyloxypolyethoxy)phenyl]propane (i+j=10, average molecular weight: 776) and glycidyl methacrylate as the A3 component is preferred.

[0145] In addition, the mixing ratios of the above-described components A1, A2, A3, and A4 are not particularly limited as long as the mixing ratio of component A1 is 24 to 100 mass%; however, considering photochromic properties such as the color intensity and fading speed of the resulting photochromic optical article, it is preferable to have 24 to 100 mass% of component A1, 0 to 76 mass% of component A2, 0 to 76 mass% of component A3, and 0 to 76 mass% of component A4; it is more preferable to have 24 to 75 mass% of component A1, 25 to 65 mass% of component A2, 0 to 5 mass% of component A3, and 0 to 10 mass% of component A4; or 24 to 60 mass% of component A1, 40 to 76 mass% of component A2, 0 to 3 mass% of component A3, and 0 to 7 mass% of component A4. It is more desirable to have 25% to 50 mass% of component A1, 50 to 75 mass% of component A2, 0 to 2 mass% of component A3, and 0 to 5 mass% of component A4.

[0146] The total content of component A is preferably 80.0 to 99.9 mass% with respect to the total amount of the photochromic curable composition according to the present embodiment, and more preferably 88.5 to 99.9 mass%.

[0147] <(B) Photochromic Compounds>

[0148] The photochromic compound of component B is a compound formed by bonding at least one naphthopyran represented by the following formula (1) to a long chain with a number average molecular weight of 300 to 10,000. By using such a photochromic compound, high color intensity and a fast fading rate can be exhibited even in a solid matrix with a high crosslinking density like component A, and the temperature dependence tends to be reduced. In addition, because the number average molecular weight of the long chain used is 300 to 10,000, it has excellent compatibility with the solid matrix of component A, and cloudiness tends to be suppressed.

[0149] [Chemical Formula 8]

[0150]

[0151] During the meal, R 1 and R 2 Each represents, independently, a group bonded to a long chain having a number average molecular weight of 300 to 10000, or a hydroxyl group, an alkyl group, a haloalkyl group, a cycloalkyl group that may have a substituent, an alkoxy group, an amino group, a substituted amino group, a heterocyclic group that may have a substituent, a cyano group, a halogen atom, an alkylthio group, an arylthio group that may have a substituent, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aralkyl group that may have a substituent, an aralkoxy group that may have a substituent, an aryloxy group that may have a substituent, an aryl group that may have a substituent, a heteroaryl group that may have a substituent, a thiol group, an alkoxyalkylthio group, a haloalkylthio group, or a cycloalkylthio group that may have a substituent. a represents an integer from 0 to 2, and b represents an integer from 0 to 4. When a is 2, multiple R 1 may be identical or different, a is 2, and adjacent R 1 In the case where this exists, the two adjacent Rs 1 Becoming one, they R 1 It may form a ring that may include an oxygen atom, a sulfur atom, or a nitrogen atom together with the carbon atom bonded to it, and furthermore, said ring may have a substituent. When b is 2 to 4, a plurality of R 2 may be identical or different from each other, b is 2 to 4, and adjacent R 2 If exists, the two adjacent Rs 2 They become one and R 2It may form a ring that may include an oxygen atom, a sulfur atom, or a nitrogen atom together with the carbon atom bonded to it, and furthermore, said ring may have a substituent. If a and b are not both zero, at least one R 1 and at least one R 2 A may become one to form a ring, and additionally, the ring may have a substituent. R 3 and R 4 Each represents, independently, a group bonded to a long chain having a number average molecular weight of 300 to 10,000, or an aryl group that may have a substituent or a heteroaryl group that may have a substituent. provided that R 1 , R 2 , R 3 , and R 4 At least one of them is a group that combines with a long chain having a number average molecular weight of 300 to 10,000. And, "combines with a long chain having a number average molecular weight of 300 to 10,000" means that it is directly connected to the long chain.

[0152] In this way, by using a photochromic compound in which at least one naphthopyran is bonded to a long chain with a number average molecular weight of 300 to 10,000, the naphthopyran itself can form an environment where structural changes are likely to occur, thereby obtaining a photochromic curable composition with excellent photochromic properties.

[0153] In order to produce the above-mentioned effects, the naphthopyran expressed by the above formula (1) comprises two adjacent Rs 1 It is preferable that this be an indenonaphtopyran that forms a ring, and it is more preferable that it be an indenonaphtopyran expressed by the following formula (2).

[0154] [Chemical Formula 9]

[0155]

[0156] During the meal, R2 , R 3 , R 4 , and b are the same as in the above equation (1). R 5 represents a group bonded to a long chain having a number average molecular weight of 300 to 10,000, or a hydroxyl group, an alkyl group, a haloalkyl group, a cycloalkyl group that may have a substituent, an alkoxy group, an amino group, a substituted amino group, a heterocyclic group that may have a substituent, a cyano group, a halogen atom, an alkylthio group, an arylthio group that may have a substituent, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aralkyl group that may have a substituent, an aralkoxy group that may have a substituent, an aryloxy group that may have a substituent, an aryl group that may have a substituent, a heteroaryl group that may have a substituent, a thiol group, an alkoxyalkylthio group, a haloalkylthio group, or a cycloalkylthio group that may have a substituent. c represents an integer from 0 to 4. If c is 2 to 4, multiple R 5 may be identical or different from each other, c is 2 to 4, and adjacent R 5 If exists, the two adjacent Rs 5 They become one and R 5 Along with the carbon atom bonded to, it may form a ring that may contain an oxygen atom, a sulfur atom, or a nitrogen atom, and furthermore, said ring may have a substituent. R 6 and R 7Each represents, independently, a group bonded to a long chain having a number average molecular weight of 300 to 10,000, or a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a halogen atom, an aralkyl group that may have a substituent, an aralkoxy group that may have a substituent, an aryloxy group that may have a substituent, an aryl group that may have a substituent, or a heterocyclic group that may have a substituent, and R 6 and R 7 These may become one, and together with the carbon atom at the 13th position to which they bond, may form an aliphatic ring having 3 to 20 carbon atoms, a condensed polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is condensed onto the aliphatic ring, a heterocyclic ring having 3 to 20 atoms, or a condensed polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is condensed onto the heterocyclic ring. However, R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 At least one of them is a group that combines with a long chain group having a number average molecular weight of 300 to 10,000.

[0157] For each of the examples 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 alkyl carbonyl 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.

[0158] Among them, R 2 , R 3 , R 4 , and R 5 It is preferable that at least one of them is a group that combines with a long chain group having a number average molecular weight of 300 to 10,000.

[0159] R 2 It is preferable that the group is a group bonded to a long chain 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 that may have a substituent, an alkylthio group, an arylthio group that may have a substituent, or an aryl group having 6 to 12 carbon atoms that may have a substituent. Among these, it is more preferable that these groups are present at the 6th and / or 7th positions of indeno[2,1-f]naphtho[1,2-b]pyran. Additionally, R at the 6th and 7th positions of indeno[2,1-f]naphtho[1,2-b]pyran 2 There exists, and 2 R 2It is also desirable to form an aliphatic ring (which may further have substituents) that may contain an oxygen atom, a nitrogen atom, or a sulfur atom. In this case, it is desirable that the number of atoms of the aliphatic ring containing the oxygen atom, a nitrogen atom, or a sulfur atom (the number of atoms including heteroatoms and carbon atoms located at the 6th and 7th positions) be 5 to 8. Additionally, the aliphatic ring may have substituents, and it is desirable that these substituents be alkyl groups having 1 to 6 carbon atoms.

[0160] R 5 Preferably, the group bonded to the long chain having a number average molecular weight of 300 to 10,000, a hydrogen atom (where 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 that may have a substituent, or an arylthio group. Among these, it is more preferable that these groups are present at the 11th position of indeno[2,1-f]naphtho[1,2-b]pyran.

[0161] R 3 and R 4 It is preferable that each of them independently be an aryl group that may have a substituent or a heteroaryl group that may have a substituent, or a group that may have a long chain having a number average molecular weight of 300 to 10000.

[0162] R 6 and R 7 Considering the reduction of temperature dependence, it is preferable that each be an alkyl group having 1 to 12 carbon atoms, or R 6 and R 7It is preferable that this becomes one, together with the carbon atom at the 13th position to which they bond, a ring selected from an aliphatic ring having 3 to 20 reduced carbon atoms, a condensed polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is condensed onto the aliphatic ring, a heterocyclic ring having 3 to 20 reduced atoms, or a condensed polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is condensed onto the heterocyclic ring, that is, a ring having a spiro structure with the carbon at the 13th position located in the pentatonic ring of indenonaphtopyran. Among these, R 6 and R 7 It is preferable that this becomes an aliphatic ring having 3 to 20 carbon atoms, and specifically, it is more preferable that it be a ring selected from cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cyclododecane, cyclododecane, and spirodicyclohexane. Furthermore, the ring having a spiro structure may have 1 to 10 substituents, such as alkyl groups having 1 to 3 carbon atoms or cycloalkyl groups having 5 to 7 carbon atoms, or may have condensed cycloalkyl groups having 5 to 7 carbon atoms. An example of a more preferable group is a group expressed by the following formula.

[0163] [Chemical Formula 10]

[0164]

[0165] As long chain groups having a number average molecular weight of 300 to 10,000, known long chain groups may be used without particular limitation, and examples include polyalkylene groups, polyalkyleneoxy groups, polyfluoroalkylene groups, polyfluoroalkylenyloxy groups, polydialkylsilyl groups, polydialkylsilyloxy groups, polyester groups, etc. The long chain groups may be groups having these alone or groups formed through other groups. For example, R 3 and / or R 4In the case where a group is bonded to a long chain with a number average molecular weight of 300 to 10,000, the long chain with a number average molecular weight of 300 to 10,000 bonded to is preferably an aryl group or a heteroaryl group to which the long chain is bonded. Furthermore, a group containing an ether group, an ester group, etc. may be interposed between the long chain and the aryl group or the heteroaryl group.

[0166] Among these long chain groups, long chain groups consisting of polyalkylene groups, polyalkylene oxygen groups, polydialkylsilyl oxygen groups, polyester groups, and combinations thereof are preferred, long chain groups consisting of polyalkylene oxygen groups, polydialkylsilyl oxygen groups, polyester groups, and combinations thereof are more preferred, polyalkylene oxygen groups and polydialkylsilyl oxygen groups are even more preferred, and polyalkylene oxygen groups are particularly preferred.

[0167] The number of naphtopyrans bound to a long chain having a number average molecular weight of 300 to 10,000 is not particularly limited and at least one is required. For example, not only is there an embodiment in which two or more naphtopyrans are bound to one long chain, but also an embodiment in which multiple long chains are bound to one naphtopyran. In these embodiments, the number of naphtopyrans is preferably 0.1 to 4, and more preferably 0.2 to 2. Furthermore, the number of naphtopyrans being 1 or less is the case of a photochromic compound formed by binding multiple long chains to one naphtopyran. For example, when the number of naphtopyrans is 0.25, it refers to four long chains having a number average molecular weight of 300 to 10,000 being bound to one naphtopyran. And, in the case where there are multiple long chains with a number average molecular weight of 300 to 10000, the long chains with a number average molecular weight of 300 to 10000 may be the same group or different groups.

[0168] The number average molecular weight of these long chains is preferably 400 to 7500, and more preferably 450 to 5000.

[0169] The naphtopyran used in the photochromic compound of component B is not particularly limited as long as it has the structure described above, and examples include the naphtopyran described in Patent Documents 3 to 5 and the naphtopyran appropriately selected from the combination described above.

[0170] An example of a photochromic compound that is component B is shown below, but is not limited thereto. In the example below, n should be appropriately set so that the number-average molecular weight of the long chain is 300 to 10,000, and is typically selected from 1 to 250 (typically, since the long chain has multiple molecular weights, it is expressed as the number-average molecular weight. Therefore, n can take values ​​other than integer values). Me represents a methyl group.

[0171] [Chemical Formula 11]

[0172]

[0173] As for the naphthopyran used in the photochromic compound of component B, a single type may be used alone, or multiple types of naphthopyran may be combined according to the desired color tone to obtain various color tones required for a photochromic lens. In addition, within a range that does not impair the effects of the present invention, it may be combined with other photochromic compounds that do not have long chains and have a number average molecular weight of 300 to 10,000, depending on the intended use. As for the other photochromic compounds to be combined, known compounds such as fulgid, fulgimide, spirooxazine, and chromene may be used without any limitation.

[0174] In the photochromic curable composition according to the present embodiment, the content of component B is preferably 0.01 to 15 parts by mass and more preferably 0.1 to 10 parts by mass with respect to photochromic properties such as the color intensity and fading speed of the resulting photochromic optical article.

[0175] <Other Ingredients>

[0176] The photochromic curable composition according to the present embodiment may contain various compounding agents known in itself, to the extent that the effects of the present invention are not impaired. Examples of compounding agents include polymerization initiators, ultraviolet absorbers, infrared absorbers, ultraviolet stabilizers, antioxidants, anti-coloring agents, antistatic agents, dyes, pigments, fragrances, solvents, leveling agents, etc.

[0177] Examples of polymerization initiators among the above formulations include thermal polymerization initiators and photopolymerization initiators.

[0178] Examples of thermal polymerization initiators include diacyl peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide, and acetyl peroxide; peroxyesters such as t-butyl peroxy-2-ethylhexanate, t-butyl peroxyneodecanate, cumyl peroxyneodecanate, and t-butyl peroxybenzoate; percarbonates such as diisopropyl peroxydicarbonate and di-sec-butyl peroxydicarbonate; and azo compounds such as azobisisobutyronitrile.

[0179] Examples of photopolymerization initiators include acetophenone compounds such as 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, and 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one; α-dicarbonyl compounds such as 1,2-diphenylethanedione and methylphenylglycoxylate; and acylphosphine oxide compounds such as 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine methyl ester, 2,6-dichlorobenzoyldiphenylphosphine oxide, and 2,6-dimethoxybenzoyldiphenylphosphine oxide.

[0180] In addition, when using a photopolymerization initiator, known polymerization curing accelerators such as tertiary amines may be used in combination.

[0181] The content of other components in the photochromic curable composition according to the present embodiment is typically 0.001 to 10 parts by mass per 100 parts by mass of component A, and preferably 0.01 to 3 parts by mass.

[0182] <Method for preparing a photochromic curable composition>

[0183] The photochromic curable composition according to the present embodiment can be prepared by mixing the above-described component A, component B, and other components as needed by a known method.

[0184] <<Photochromic Optical Products>>

[0185] The photochromic optical article according to the present embodiment is formed by polymerizing the above-described photochromic curable composition. Polymerization for manufacturing 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, depending on the type of component A or polymerization initiator used and the form of the photochromic optical article formed, an appropriate polymerization means may be employed.

[0186] When thermally polymerizing a photochromic curable composition, the temperature conditions, in particular, affect the properties and state of the resulting photochromic optical article. Since these temperature conditions are influenced by the type and amount of the thermal polymerization initiator and the type of component A, they cannot be limited to a single value; however, generally, it is preferable to start the polymerization at a relatively low temperature and gradually increase the temperature. Since the polymerization time also varies depending on various factors, just like the temperature, it is desirable to determine the optimal time according to these conditions in advance; however, generally, it is preferable to select conditions such that the polymerization is completed within 2 to 48 hours.

[0187] Furthermore, when photopolymerizing a photochromic curable composition, the illuminance condition among the polymerization conditions, in particular, affects the properties and state of the resulting photochromic optical article. Since this illuminance condition is influenced by the type and amount of the photopolymerization initiator or the type of component A, it cannot be limited to a single value; however, generally, it is 50 to 500 mW / cm² at a wavelength of 365 nm. 2 It is preferable to select conditions to irradiate with UV light for 0.5 to 5 minutes.

[0188] When manufacturing a photochromic lens using a photochromic optical article, a known method described below may be adopted as long as a method that obtains uniform light-emitting performance.

[0189] For example, when manufacturing a photochromic lens by the paste method, a photochromic curable composition is injected between glass molds held by an elastomer gasket or spacer, and a photochromic optical article molded into the shape of a lens or the like can be obtained by mold polymerization. During polymerization, depending on the type of component A or polymerization initiator, heating in air or irradiation with active energy rays such as ultraviolet rays may be employed.

[0190] In addition, when manufacturing a photochromic lens by a lamination method, a photochromic curable composition is appropriately dissolved in an organic solvent to prepare a coating solution, and the coating solution is applied to the surface of an optical substrate, such as a lens substrate, by spin coating, dipping, etc., and the organic solvent is removed by drying, and then polymerization is performed 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).

[0191] In addition, a photochromic optical article can be obtained by mold polymerization using an inner mold, wherein an optical substrate such as a lens substrate is placed in a glass mold to form a predetermined void, a photochromic curable composition is injected into the void, and polymerization is performed in this state by UV irradiation or heating, etc. (mold polymerization method).

[0192] When forming a photochromic layer on the surface of an optical substrate by the lamination method (coating method and mold polymerization method) as described above, the adhesion between the photochromic layer and the optical substrate can be enhanced by performing chemical treatment with an alkaline solution, acidic solution, etc., or physical treatment by corona discharge, plasma discharge, polishing, etc., on the surface of the optical substrate in advance. Of course, it is also possible to provide a transparent adhesive resin layer on the surface of the optical substrate.

[0193] In addition, when manufacturing a photochromic lens by the binder method, a photochromic sheet is first produced by sheet molding using a photochromic curable composition, and by placing this between two transparent sheets (optical sheets) and performing polymerization, a photochromic laminate in which the photochromic layer is an adhesive layer can be obtained. For the production of the photochromic sheet, a coating method using a coating solution in which the photochromic curable composition is dissolved in an organic solvent may also be employed.

[0194] By mounting the photochromic laminate produced in this manner into a mold and injection molding a thermoplastic resin (such as polycarbonate) for optical substrates such as lenses, a photochromic optical article, such as a lens of a predetermined shape, in which the photochromic laminate is laminated can be obtained. Additionally, a photochromic optical article can be obtained by bonding the photochromic laminate to the surface of an optical substrate using an adhesive or the like.

[0195] In addition, depending on the application, photochromic optical articles may be subjected to post-processing such as dyeing using dyes such as disperse dyes; making a hard coating film using a hard coating agent with a silane coupling agent or a colloidal solution of silicon, zirconium, antimony, aluminum, tin, tungsten as the main component; forming a thin film by depositing metal oxides such as SiO2, TiO2, ZrO2; or anti-reflective or antistatic treatment by forming a thin film by applying an organic polymer.

[0196] Examples

[0197] 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 examples and comparative examples, the methods for evaluating each component and photochromic properties, etc., are as follows.

[0198] <(A) (Meth)acrylate composition>

[0199] (A1) Polyfunctional (meth)acrylate having three or more (meth)acryloyl groups in the molecule

[0200] TMPT: Trimethylolpropane triacrylate

[0201] DTMP: Ditrimethylolpropane tetramethacrylate

[0202] (A2) Difunctional (meth)acrylate

[0203] PEG14: Polyethylene glycol dimethacrylate (Average molecular weight: 736)

[0204] BPA10: 2,2-bis[4-(methacryloyloxypolyethoxy)phenyl]propane (average molecular weight: 804)

[0205] PEG9: Polyethylene glycol dimethacrylate (Average molecular weight: 536)

[0206] PEG9A: Polyethylene glycol diacrylate (Average molecular weight: 508)

[0207] C4PCDA: A reaction product of polycarbonate diol obtained by the phosgenation of tetramethylene glycol and acrylic acid

[0208] BPE-500: Ethoxylated bisphenol A dimethacrylate (Product of Shinnakamura Kagaku Kogyo Co., Ltd.)

[0209] (A3) Monofunctional (meth)acrylate

[0210] GMA: Glycidyl methacrylate

[0211] (A4) Polymerizable monomers other than (A1) to (A3)

[0212] PR1: Polyrotaxane having (meth)acryloyl groups prepared according to Preparation Example 1 below

[0213] PS1: Silsesquioxane having a (meth)acryloyl group prepared according to Preparation Example 2 below

[0214] <(B) Photochromic Compounds>

[0215] (B1) A photochromic compound having a polypropylene glycol monobutyl ether chain with a number average molecular weight of 1000, expressed by the following formula (n=17.2)

[0216] [Chemical Formula 12]

[0217]

[0218] (B2) A photochromic compound having a polyethylene glycol chain with a number average molecular weight of 3000, expressed by the following formula (n=68.2)

[0219] [Chemical Formula 13]

[0220]

[0221] (B3) A photochromic compound having a polydimethylsiloxane chain with a number average molecular weight of 1100, expressed by the following formula (n=12)

[0222] [Chemical Formula 14]

[0223]

[0224] (BR1, BR2) Photochromic compounds used in comparative examples

[0225] [Chemical Formula 15]

[0226]

[0227] <Other Ingredients>

[0228] PI1: Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide

[0229] HA: Bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate

[0230] HP: Ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate]

[0231] <Manufacturing Example 1: Method for manufacturing PR1>

[0232] (1) Preparation of the axial molecule (PEG-COOH)

[0233] Linear polyethylene glycol (PEG) with a molecular weight of 20,000 was prepared as the axial molecule compound. 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. To this solution, 5 mL of a commercially available aqueous sodium hypochlorite solution (effective chlorine concentration 5%) was added and stirred at room temperature for 10 minutes. Afterward, ethanol was added in a range of up to 5 mL, and the reaction was terminated. Then, extraction was performed using 50 mL of methylene chloride, after which the methylene chloride was removed by distillation and dissolved in 250 mL of ethanol. The mixture was then reprecipitated at -4°C for 12 hours to recover PEG-COOH as the axial molecule, and the mixture was dried.

[0234] (2) Preparation of polyrotaxane without side chain introduction

[0235] PEG-COOH (3 g) and α-cyclodextrin (α-CD) (12 g) prepared above were each dissolved in 50 mL of hot water at 70°C, and the resulting solutions were mixed and shaken well. Then, this mixed solution was reprecipitated at 4°C for 12 hours, and the precipitated inclusion complex was recovered by freeze-drying. Subsequently, adamantanamine (0.13 g) was dissolved in 50 mL of dimethylformamide (DMF) at room temperature, the above inclusion complex was added, and the mixture was quickly shaken well. Next, a solution of BOP reagent (benzotriazole 1-yl-oxy-tris(dimethylamino)phosphonium hexafluorophosphate) (0.38 g) dissolved in DMF was additionally added and shaken well. Additionally, a solution of diisopropylethylamine (0.14 mL) dissolved in DMF was added and shaken well to obtain a slurry-like reagent. The slurry-type reagent obtained above was left to stand at 4°C for 12 hours. Afterward, 50 mL of a DMF / methanol mixed solvent (volume ratio: 1 / 1) was added and mixed, and centrifugation was performed to discard the supernatant. Additionally, after washing with the above DMF / methanol mixed solution, the mixture was washed with methanol and centrifuged to obtain a precipitate. The obtained precipitate was vacuum dried, dissolved in 50 mL of DMSO, and the resulting clear solution was dropped into 700 mL of water to precipitate the branch-free polyrotaxane. The precipitated branch-free polyrotaxane was recovered by centrifugation and vacuum dried. Furthermore, it was dissolved in DMSO, precipitated in water, recovered, and dried to obtain purified branch-free polyrotaxane. The inclusion amount of α-CD at this time was 0.25.

[0236] Here, the inclusion amount is obtained by dissolving a side-chain unintroduced polyrotaxane in DMSO-d6, and 1It was measured using an H-NMR measuring device (JNM-LA500 manufactured by Nihon Denshi Co., Ltd.) and calculated by the method below. Here, X, Y, and X / (YX) represent the following meanings.

[0237] X: Integral value of hydroxyl group-derived protons in cyclodextrin at 4 to 6 ppm

[0238] Y: Integral value of methylene group-derived protons in cyclodextrin and PEG at 3 to 4 ppm

[0239] X / (YX): Proton ratio of cyclodextrin to PEG

[0240] First, X / (YX) was calculated in advance when the maximum inclusion amount was theoretically 1.0, and the inclusion amount was calculated by comparing this value with X / (YX) calculated from the analysis value of the actual compound.

[0241] (3) Introduction of side chains to polyrotaxanes without side chains

[0242] The above-described purified polyrotaxane without side chain introduction (500 mg) was dissolved in 50 mL of a 1 mol / L NaOH aqueous solution, propylene oxide (3.83 g, 66 mmol) was added, and the mixture was stirred for 12 hours at room temperature under an argon atmosphere. Then, the above solution was neutralized with a 1 mol / L HCl aqueous solution to a pH of 7 to 8, dialyzed in a dialysis tube, and freeze-dried to obtain hydroxypropylated polyrotaxane. The degree of modification of the hydroxyl group of the cyclic molecule by the hydroxypropyl group was 50%. The obtained hydroxypropylated polyrotaxane (5 g) was dissolved in ε-caprolactone (30 g) at 80°C to prepare a mixture. This mixture was stirred at 110°C for 1 hour while blowing dry nitrogen, then 50 mass% xylene solution (0.16 g) of 2-ethylhexanoate tin (II) was added and stirred at 130°C for 6 hours. After that, xylene was added to obtain a polycaprolactone modified polyrotaxane xylene solution with a non-volatile concentration of about 35 mass% and a side chain.

[0243] The polycaprolactone-modified polyrotaxane xylene solution prepared above was added dropwise into hexane, recovered, and dried to obtain a polycaprolactone-modified polyrotaxane containing side-chain hydroxyl groups. The obtained polycaprolactone-modified polyrotaxane is, 1 It was identified by H-NMR and GPC and confirmed to be a polyrotaxane containing side chain hydroxyl groups having the desired structure. This polycaprolactone-modified polyrotaxane had a degree of modification of the side chain of 50%, a (average) molecular weight of the side chain of about 500, and a mass average molecular weight (Mw) measured by GPC of 700,000.

[0244] (4) Introduction of acryloyl groups to polyrotaxanes containing side-chain hydroxyl groups

[0245] Polycaprolactone-modified polyrotaxane (10.0 g), which is a polyrotaxane containing a side chain hydroxyl group prepared in (3) above, was dissolved in 50 mL of methyl ethyl ketone, and 5 mg of dibutylhydroxytoluene (polymerization inhibitor) was added, followed by the addition of 2-acryloyloxyethyl isocyanate (1.94 g). 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 having (meth)acryloyl groups, in which an acryloyl group was introduced to the hydroxyl group at the end of the polycaprolactone. This solution was added dropwise in hexane, the precipitated solid was recovered, and by drying, a polyrotaxane having (meth)acryloyl groups (PR1) was obtained. This polyrotaxane (PR1) having (meth)acryloyl groups had a (average) molecular weight of the side chains of about 600, a mass average molecular weight (Mw) measured by GPC of 880,000, a modification rate of the acryloyl groups of 85 mol%, and a ratio of hydroxyl groups remaining in the side chains of 15 mol%.

[0246] <Manufacturing Example 2: Method for manufacturing PS1>

[0247] Ethanol (248 mL) and water (54 g, 3.0 mol) were added to 3-trimethoxysilylpropyl methacrylate (248 g, 1.0 mol), sodium hydroxide (0.20 g, 0.005 mol) was added as a catalyst, and the mixture was reacted at 30°C for 3 hours. After confirming the loss of the raw material, the mixture was neutralized with dilute hydrochloric acid, toluene (174 mL), heptane (174 mL), and water (174 g) were added, and the aqueous layer was removed. Subsequently, the organic layer was washed with water until the aqueous layer became neutral, and the solvent was concentrated to obtain silsesquioxane (PS1) having (meth)acryloyl groups. Then, 1 From H-NMR, it was confirmed that the raw material was completely consumed. In addition, 29From Si-NMR, it was confirmed that the obtained PS1 is a mixture of cage-type, ladder-type, and random-type structures. The acid value of the obtained PS1 was 1.1 mgKOH / g, and the mass average molecular weight (Mw) was 4800.

[0248] <Evaluation Method>

[0249] A obtained photochromic optical article was used as a sample, and a xenon lamp L-2480 (300 W) SHL-100 manufactured by Hamamatsu Photonics Co., Ltd. was applied to it through an aeromass filter (manufactured by Corning) at 23°C and 35°C, with a beam intensity at the surface of the photochromic optical article of 365 nm = 2.4 mW / cm² 2 , 245 nm = 24 μW / cm² 2 The photochromic properties of the photochromic optical article were measured by irradiating it for 300 seconds to induce color development. Each photochromic property, Vickers hardness, and the leaching ability of the photochromic compound were evaluated using the following methods.

[0250] (1) Photochromic

[0251] · Maximum absorption wavelength (λmax): This is the maximum absorption wavelength after color development, obtained using a spectrophotometer (Instantaneous Multi-Channel Photodetector - MCPD1000) manufactured by Otsuka Denshi Kogyo Co., Ltd. The above maximum absorption wavelength is related to the hue at the time of color development.

[0252] ·23℃ Color intensity {ε(300)-ε(0)}: The difference between the absorbance {ε(300)} after irradiating for 300 seconds at the maximum absorption wavelength and the absorbance ε(0) before irradiation. The higher this value, the better the photochromic properties.

[0253] ·23℃ fading rate [t1 / 2(sec.)]: The time required for the absorbance at the maximum absorption wavelength of the sample to decrease to 1 / 2 of {ε(300)-ε(0)} when the light irradiation is stopped after 300 seconds of light irradiation. The shorter this time, the better the photochromic properties.

[0254] · Temperature dependence: This is the ratio of the color development concentration at 35°C to the color development concentration at 23°C. The higher this value, the smaller the temperature dependence, and the better the result.

[0255] (2) Vickers hardness (Hv)

[0256] Vickers hardness was measured using a hardness tester equipped with an automatic measurement (reading) device (PMT-X7A, manufactured by Matsuzawa, Inc.). 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 serves as an indicator of whether scratches occur during the lens manufacturing process. As a standard, if the Vickers hardness exceeds 4.5, scratches do not occur easily, while if it is 4.5 or lower, scratches occur easily.

[0257] (3) Leachability

[0258] 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. Then, ultraviolet light was irradiated to visually check for the presence or absence of color development, and evaluated according to the following evaluation criteria.

[0259] -metewand-

[0260] 4: Does not develop color at all

[0261] 3: You can see a very slight color development.

[0262] 2: Light color development

[0263] 1: Develop color

[0264] <Example 1>

[0265] For component A and other components shown in Table 1, a photochromic compound was added at a concentration of 26 mmol per 100 g of component A to obtain a photochromic curable composition. The numbers in parentheses in Table 1 represent parts by mass. Using the photochromic curable composition obtained in this way, a photochromic optical article was obtained by the following method.

[0266] 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. Then, this thiourethane-based plastic lens was subjected to alkaline etching at 50°C for 5 minutes using a 10% sodium hydroxide aqueous solution, and then thoroughly cleaned with distilled water.

[0267] Using a spin coater (1 H-DX2, manufactured by Mikasa Co., Ltd.), a moisture-curing primer (product name: TR-SC-P, manufactured by Tokuyama Co., Ltd.) was coated on the surface of the plastic lens above 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 film thickness of the photochromic curable composition became 40 μm.

[0268] A lens having a photochromic curable composition coated on its surface in this manner, under a nitrogen gas atmosphere at an output of 200 mW / cm² 2 The photochromic curable composition was polymerized by irradiating light for 90 seconds using a metal halide lamp. Afterward, a photochromic optical product having a photochromic layer was produced by heating at 110°C for 1 hour. The evaluation results are shown in Table 2.

[0269] <Examples 2 to 5, Comparative Examples 1 to 3>

[0270] A photochromic optical article was produced by performing the same operation as in Example 1, except that component A, the photochromic compound, and other components were changed as described in Table 1. The evaluation results are shown in Table 2.

[0271] [Table 1]

[0272]

[0273] [Table 2]

[0274]

[0275] Figure 1 shows the results of the temperature dependence of Examples 1, 3, 5 and Comparative Examples 1 to 3 and the results of the fading half-life at 23°C.

[0276] As can be seen from FIG. 1, in the photochromic optical article of the comparative example using a photochromic compound not bonded to a long chain with a number average molecular weight of 300 to 10,000, the temperature dependence and the fading half-life at 23°C are in an almost linear relationship. That is, the faster the fading rate of the compound, the greater the temperature dependence. In addition, Comparative Example 1 is an example with a low content of a polyfunctional (meth)acrylate having three or more (meth)acryloyl groups in the molecule, and Comparative Examples 2 and 3 are examples using a photochromic compound not having a long chain with a number average molecular weight of 300 to 10,000.

[0277] Meanwhile, in a photochromic optical article using a (meth)acrylate composition having a content of 24 to 100 mass% of a polyfunctional (meth)acrylate having three or more (meth)acryloyl groups in the molecule as in the example, and also using a photochromic compound having a long chain with a number average molecular weight of 300 to 10000, the temperature dependence value is improved compared to the comparative example when compared with the same fading half-life at 23°C.

[0278] To summarize the results, a photochromic optical article using a (meth)acrylate composition having a content of 24 to 100 mass% of a polyfunctional (meth)acrylate having three or more (meth)acryloyl groups in the molecule, and a photochromic compound having long chains with a number average molecular weight of 300 to 10,000, has sufficient hardness while possessing excellent photochromic properties. That is, by having long chains with a number average molecular weight of 300 to 10,000, the fading rate is significantly improved, and by increasing the content of a polyfunctional acrylate having three or more (meth)acryloyl groups in the molecule, the crosslinking density is improved, so the temperature dependence of the photochromic optical article does not deteriorate significantly. As a result, a photochromic optical article satisfying both conditions has improved temperature dependence compared to a photochromic optical article that does not satisfy at least one of the conditions.

[0279] <Examples 6 to 11>

[0280] A photochromic optical article was produced by performing the same operation as in Example 1, except that component A, the photochromic compound, and other components were changed as described in Table 3. The evaluation results are shown in Table 4.

[0281] [Table 3]

[0282]

[0283] [Table 4]

[0284]

Claims

Claim 1 (A) a (meth)acrylate composition comprising a polyfunctional (meth)acrylate having three or more (meth)acryloyl groups in the molecule in a content of 50 to 100 mass%; and (B) a photochromic compound comprising a naphthopyran having a long chain having a number average molecular weight of 300 to 10000, represented by the following formula (1); wherein the long chain having a number average molecular weight of 300 to 10000 is a polyalkylene group, a polyalkyleneoxy group, a polyfluoroalkylene group, a polyfluoroalkyllenyloxy group, a polydialkylsilyl group, a polydialkylsilyloxy group, or a combination thereof. (In the food, R 1 and R 2 Each represents, independently, a group bonded to a long chain having a number average molecular weight of 300 to 10,000, or a hydroxyl group, an alkyl group, a haloalkyl group, a cycloalkyl group that may have a substituent, an alkoxy group, an amino group, a substituted amino group, a heterocyclic group that may have a substituent, a cyano group, a halogen atom, an alkylthio group, an arylthio group that may have a substituent, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aralkyl group that may have a substituent, an aralkoxy group that may have a substituent, an aryloxy group that may have a substituent, an aryl group that may have a substituent, a heteroaryl group that may have a substituent, a thiol group, an alkoxyalkylthio group, a haloalkylthio group, or a cycloalkylthio group that may have a substituent, where a represents an integer from 0 to 2, and b represents 0 Represents an integer from 4 to 4, and if a is 2, multiple R 1 may be identical or different, a is 2, and adjacent R 1 In the case where this exists, the two adjacent Rs 1 Becoming one, they R 1 It may form a ring that may include at least one heteroatom selected from the group consisting of oxygen, sulfur, and nitrogen atoms, together with a carbon atom bonded to it, and furthermore, said ring may have substituents, and when b is 2 to 4, a plurality of R 2 may be identical or different from each other, b is 2 to 4, and adjacent R 2 If exists, the two adjacent Rs 2 They become one and R 2 It may form a ring that may include at least one heteroatom selected from the group consisting of oxygen, sulfur, and nitrogen atoms, together with a carbon atom bonded to it, and furthermore, said ring may have a substituent, and if a and b are not both zero, at least one R 1 and at least one R 2 A may become one to form a ring, and furthermore, the ring may have a substituent, R 3 and R 4 Each represents, independently, a group bonded to a long chain having a number average molecular weight of 300 to 10,000, or an aryl group that may have a substituent or a heteroaryl group that may have a substituent, and R 1 , R 2 , R 3 , and R 4 At least one of them is a group that combines with a long chain group having a number average molecular weight of 300 to 10,000.) Claim 2 A photochromic curable composition according to claim 1, wherein the naphtopyran represented by the above formula (1) is an indenonaphtopyran represented by the following formula (2). (In the food, R 2 , R 3 , R 4 , and b are the same as in the above equation (1), and R 5 ...represents a group bonded to a long chain having a number average molecular weight of 300 to 10,000, or a hydroxyl group, an alkyl group, a haloalkyl group, a cycloalkyl group that may have a substituent, an alkoxy group, an amino group, a substituted amino group, a heterocyclic group that may have a substituent, a cyano group, a halogen atom, an alkylthio group, an arylthio group that may have a substituent, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aralkyl group that may have a substituent, an aralkoxy group that may have a substituent, an aryloxy group that may have a substituent, an aryl group that may have a substituent, a heteroaryl group that may have a substituent, a thiol group, an alkoxyalkylthio group, a haloalkylthio group, or a cycloalkylthio group that may have a substituent, wherein c represents an integer from 0 to 4, and c is 2 to In the case of 4, multiple R 5 may be identical or different from each other, c is 2 to 4, and adjacent R 5 If exists, the two adjacent Rs 5 They become one and R 5 It may form a ring that may include at least one heteroatom selected from the group consisting of oxygen, sulfur, and nitrogen atoms, together with a carbon atom bonded to it, and furthermore, said ring may have a substituent, and R 6 and R 7 Each represents, independently, a group bonded to a long chain having a number average molecular weight of 300 to 10,000, or a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a halogen atom, an aralkyl group that may have a substituent, an aralkoxy group that may have a substituent, an aryloxy group that may have a substituent, an aryl group that may have a substituent, or a heterocyclic group that may have a substituent, and R 6 and R 7 This may become one, and together with the carbon atom at the 13th position to which they bond, may form an aliphatic ring having 3 to 20 reduced carbon atoms, a condensed polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is condensed on the aliphatic ring, a heterocyclic ring having 3 to 20 reduced atoms, or a condensed polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is condensed on the heterocyclic ring, and R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 At least one of them is a group that combines with a long chain group having a number average molecular weight of 300 to 10,000.) Claim 3 In paragraph 2, in the indenonaphtopyran represented by the above formula (2), R 6 and R 7 A photochromic curable composition in which, together with the carbon atom at the 13th position to which they bond, they form an aliphatic ring having 3 to 20 reduced 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 reduced atoms, or a condensed polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is condensed to the heterocyclic ring, wherein the ring may have a substituent. Claim 4 A photochromic curable composition according to claim 3, wherein in the indenonaphtopyran represented by the above formula (2), the reducing aliphatic ring having 3 to 20 carbon atoms is a ring selected from cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cyclododecane ring, and spirodicyclohexane ring, and the aliphatic ring may have 1 to 10 substituents of an alkyl group having 1 to 3 carbon atoms or a cycloalkyl group having 5 to 7 carbon atoms, or may have a cycloalkyl group having 5 to 7 carbon atoms condensed therein. Claim 5 A photochromic curable composition according to any one of claims 1 to 4, wherein the polyfunctional (meth)acrylate comprises at least one compound selected from the group consisting of trimethylolpropane triacrylate and ditrimethylolpropane tetramethacrylate. Claim 6 A photochromic curable composition according to any one of claims 1 to 4, wherein the (meth)acrylate composition further comprises a difunctional (meth)acrylate having two (meth)acrylate groups in the molecule in a content of 19 to 50 mass%. Claim 7 In claim 6, the photochromic curable composition comprises a compound represented by the following chemical formula (6), wherein the difunctional (meth)acrylate is a compound. (during food, R 20 and R 21 Each represents independently a hydrogen atom or a methyl group, k represents a number from 1 to 20 as an average value, B and B' each represent independently a straight-chain or branched-chain alkylene group having 2 to 15 carbon atoms, and if B is present in multiples, the multiple B may each be the same group or different groups.) Claim 8 In claim 7, the photochromic curable composition further comprises polyethylene glycol dimethacrylate as the difunctional (meth)acrylate. Claim 9 A photochromic curable composition according to any one of claims 1 to 4, wherein the (meth)acrylate composition further comprises glycidyl (meth)acrylate in a content of 1 to 5 weight%. Claim 10 A photochromic optical article formed by polymerizing a photochromic curable composition according to any one of claims 1 to 4. Claim 11 A lens comprising a photochromic optical article according to paragraph 10.

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