Photochromic hydroxyurethane compounds

Abstract

A photochromic hydroxyurethane compound according to the present invention is characterized by having a hydroxyurethane constituent unit represented by formula (1) on condition of having at least one photochromic site, which is a photochromic minimum unit, within a molecule. (1) ꟷXꟷOꟷCOꟷNHꟷ In the formula, X is an oxygen-containing chain organic group having a hydroxyl group as a substituent, or the hydrogen atom of the hydroxyl group is substituted by any of: (A) a photochromic group having the photochromic site; (B) a polymerization reactive group having a polymerizable substituent; (C) a C1-10 alkyl group; (D) a C3-10 cycloalkyl group; and (E) a C6-14 aryl group. (Each of (C) to (E) may be bonded to a hydrogen atom derived from the hydroxyl group via the oxygen-containing chain organic group.)

Description

[Technical Field]

[0001] The present invention relates to a novel photochromic compound, and further to a photochromic curable composition containing the photochromic compound and a photochromic cured product comprising the curable composition. [Background technology]

[0002] Photochromic compounds, such as chromene compounds, fulgide compounds, and spirooxazine compounds, possess the property (photochromicity) of rapidly changing color when exposed to ultraviolet light, such as sunlight or mercury lamp light, and returning to their original color when exposed to darkness. This property is utilized in a variety of applications, particularly in optical materials.

[0003] For example, photochromic eyeglass lenses, molded from plastic materials containing photochromic compounds, quickly color up outdoors when exposed to light containing ultraviolet rays, such as sunlight, functioning as sunglasses. Indoors, where such light is absent, they fade and function as clear, ordinary eyeglasses. Demand for such lenses has been increasing in recent years.

[0004] In order to impart photochromic properties to optical materials, photochromic compounds are generally used in combination with plastic materials, and the following methods are known: (a) A method of directly forming optical materials such as lenses by dissolving a photochromic compound in a compound and polymerizing it. This method is called the compounding method. (b) A method for forming a resin layer containing a photochromic compound on the surface of a plastic molded product such as a lens, by coating or casting polymerization. This method is called lamination. (c) A method of joining two optical sheets using an adhesive layer formed from an adhesive resin in which a photochromic compound is dispersed. This method is called the binder method.

[0005] Optical materials, such as optical articles that have been given photochromic properties, are further required to have the following characteristics: (I) The degree of coloration in the visible light region before irradiation with ultraviolet light (initial coloration) is low. (II) The degree of coloration (color intensity) when exposed to ultraviolet light is high. (III) The rate at which the color returns to its original state after exposure to ultraviolet light is stopped (fading rate) is fast. (IV) Good durability of repeated reversible color development and fading. (V) High storage stability. (VI) It is easy to mold into various shapes.

[0006] While various photochromic compounds have been reported to date, it has been observed that even photochromic compounds that exhibit good photoresponsiveness in liquid matrices tend to exhibit poor photoresponsiveness and longer fading half-lives in solid matrices. This is thought to be because the free space in solid matrices is overwhelmingly smaller compared to liquid matrices, thus restricting the structural changes of photochromic compounds.

[0007] To solve this problem, various molecular designs of photochromic compounds themselves are being investigated. For example, Patent Documents 1 and 2 propose photochromic compounds (hereinafter referred to as polymer photochromic compounds) having oligomeric chain groups such as polyalkylene oxyoligomeric chain groups and polysiloxane oligomeric chain groups. It is presumed that such polymer photochromic compounds can be encapsulated in a solid matrix because the oligomeric chain groups cover the photochromic moiety. When such photochromic moiety is encapsulated in a matrix, the matrix dependence decreases, and it is thought that the compound exhibits excellent photoresponsiveness even in a solid matrix.

[0008] The polymer photochromic compounds described above are a technology that has attracted attention in recent years. However, even the polymer photochromic compounds described in Patent Documents 1 and 2 require further improvement. Specifically, our research has shown that cured products containing polymer photochromic compounds tend to become cloudy. We believe that this cloudiness is probably caused by the aggregation of the polymer photochromic compounds during curing. On the other hand, low-molecular-weight photochromic compounds that do not have oligomeric chain groups tend to aggregate less in solid matrices, resulting in relatively transparent photochromic cured products. However, low-molecular-weight photochromic compounds are highly matrix-dependent, and issues such as fading rates can arise in solid matrices. Furthermore, chromene compounds, for example, are highly crystalline and may be difficult to dissolve in other polymerizable compounds (polymerizable monomers). Therefore, it can be difficult to disperse them at high concentrations in photochromic cured products, or the process may become complicated to achieve high dispersion, indicating room for improvement in this respect as well. [Prior art documents] [Patent Documents]

[0009] [Patent Document 1] International Publication No. 2004 / 041961 [Patent Document 2] International Publication No. 2000 / 015630 [Overview of the project] [Problems that the invention aims to solve]

[0010] The object of the present invention is to provide a novel photochromic compound that has high dispersion stability with respect to a solid matrix and reduced matrix dependence of photochromicity. Another object of the present invention is to provide a polymeric photochromic compound that is readily soluble in other polymerizable compounds and easy to handle. A further object of the present invention is to provide a photochromic cured product containing the above-mentioned photochromic compound, and a photochromic curable composition capable of obtaining such a product. [Means for solving the problem]

[0011] The inventors diligently conducted research to solve the above problems. They investigated various structures of polymer photochromic compounds that exhibit excellent photochromic properties in a solid matrix and can be highly dispersed in the matrix. In particular, they investigated photochromic compounds with structures that are well-suited to the matrix (structures that can be finely dispersed in the matrix). As a result, they found that a photochromic compound that utilizes hydroxyurethane in its molecule, specifically a hydroxyurethane bond (-XO-CO-NH-; X is a group having a hydroxyl group), in which at least a portion of the hydroxyl group is substituted with a photochromic moiety, is useful for solving the above problems. That is, they found that a photochromic compound having a hydroxyurethane chain as its main chain and a photochromic moiety in the chain maintains photochromic properties in a solid matrix, suppresses aggregation during curing, and exhibits excellent solubility with other polymerizable compounds, thus completing the present invention.

[0012] According to the present invention, a photochromic hydroxyurethane compound is characterized by having a hydroxyurethane structural unit represented by the following formula (1), provided that it has at least one photochromic moiety within the molecule, which is a photochromic minimum unit selected from the group consisting of a naphthopyran skeleton, a spirooxazine skeleton, a spiropyran skeleton, a fulgid skeleton, a fulgimid skeleton, and a diarylethene skeleton; -XO-CO-NH- (1) During the ceremony, X is an oxygen-containing chain organic group having a hydroxyl group as a substituent, or an oxygen-containing chain organic group in which the hydrogen atom of the hydroxyl group is substituted with any of the following groups (A) to (E); (A) Photochromic group having the photochromic moiety, (B) Polymerizable substituents, (C) Alkyl alkyl group having 1 to 10 carbon atoms, (D) Cycloalkyl groups having 3 to 10 carbon atoms, (E) Aryl groups having 6 to 14 carbon atoms, However, each of the above groups (C) to (E) may be bonded to an oxygen atom derived from the hydroxyl group via an oxygen-containing chain organic group. That is, each of the groups (C) to (E) having a predetermined number of carbon atoms may be located at the end of an oxygen-containing chain organic group.

[0013] The photochromic hydroxyurethane compound of the present invention preferably has the following structure.

[0014] (1) The hydroxyurethane constituent units are multiple in number, and all of the photochromic parts are located within the hydroxy constituent units.

[0015] (2) It must be represented by the following formula (2). [ka] During the ceremony, n is an integer between 1 and 100. R 100 This includes a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or an aryl group having 6 to 14 carbon atoms. R 200 These are hydroxyl groups, alkyl groups with 1 to 30 carbon atoms, alkoxy groups with 1 to 30 carbon atoms, or aryl groups with 6 to 14 carbon atoms. -X 1 -R 1 -X 2 - is a group corresponding to the group X in formula (1) above, X 1 and X 2 These are each divalent groups represented by one of the following formulas (2a) to (2d):

[0016] [ka] In formulas (2a) to (2d), R 3 is a hydrogen atom or any one of the groups (A) to (E), and among the plural Rs present in formula (2), 3 at least one is a photochromic group. R 4 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R 1 and R[[ID=1十八]] 2 are each a divalent group represented by the following formula (3).

[0017]

Chemical formula

[0018] (3) The photochromic site is an indeno[2,1-f]naphtho[1,2-b]pyran skeleton.

[0019] (4) The polymerizable substituent is at least one group selected from the group consisting of an acrylic group, a methacrylic group, an allyl group, a vinyl group, a 4-vinylphenyl group, an epoxy group, an episulfide group, a thietanyl group, a carboxyl group, a hydroxyl group, a thiol group, an amino group, an isocyanate group, and a thiocyanate group.

[0020] (5) The photochromic group is represented by the following formula (4). [ka] During the ceremony, d and e are integers between 0 and 50, PC is a group that has a photochromic site. R 8 This is an alkylene group having 1 to 30 carbon atoms. R 9 This is an alkylene group having 1 to 30 carbon atoms, or an alkylene group having 1 to 30 carbon atoms with an ether bond. Z 1 is an oxygen atom, a sulfur atom, or NH, L is a divalent group in which one of the bonds is bonded to the photochromic site, and is represented by the following formula (5).

[0021] [ka] During the ceremony, R 10 These are alkylene groups with 1 to 30 carbon atoms, cycloalkylene groups with 3 to 12 carbon atoms, or arylene groups with 6 to 12 carbon atoms. R 11 This is an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, or a dialkylsilylene group having an alkyl group having 1 to 20 carbon atoms. R 12a These are alkylene groups with 1 to 20 carbon atoms, cycloalkylene groups with 3 to 12 carbon atoms, or arylene groups with 6 to 12 carbon atoms. Z 2and Z 3 These are, respectively, a direct bond, O, CO, or NH. f and g are integers between 0 and 50, h is an integer, either 0 or 1.

[0022] (6) The polymerization reactive group is represented by the following formula (6). [ka] During the ceremony, PG is a polymerizable substituent, d1 and e1 are numbers between 0 and 50, R 81 This is an alkylene group having 1 to 30 carbon atoms. R 91 This is an alkylene group having 1 to 30 carbon atoms, or an alkylene group having 1 to 30 carbon atoms with an ether bond. Z 11 is an oxygen atom, a sulfur atom, or an NH group, L' is expressed by the following equation (7).

[0023] [ka] During the ceremony, R 101 These are direct bonds, alkylene groups with 1 to 30 carbon atoms, cycloalkylene groups with 3 to 12 carbon atoms, or arylene groups with 6 to 12 carbon atoms. R 111 This is an alkylene group having 1 to 20 carbon atoms; a cycloalkylene group having 3 to 12 carbon atoms; an arylene group having 6 to 12 carbon atoms; or a dialkylsilylene group having an alkyl group with 1 to 20 carbon atoms. R 121 These are alkylene groups with 1 to 20 carbon atoms, cycloalkylene groups with 3 to 12 carbon atoms, or arylene groups with 6 to 12 carbon atoms. Z 21 and Z 31 These are, respectively, a direct bond, O, CO, or NH. f1 and g1 are integers between 0 and 50, h1 is an integer, either 0 or 1.

[0024] The present invention also provides a curable composition comprising the above-mentioned photochromic hydroxyurethane compound and other polymerizable compounds.

[0025] In the curable composition of the present invention, (1) The other polymerizable compound has at least one polymerizable substituent selected from the group consisting of a carboxyl group, a hydroxyl group, a thiol group, an amino group, an isocyanate group, and a thiocyanate group. (2) The other polymerizable compound has at least one radical polymerizable group selected from the group consisting of acrylic group, methacrylic group, allyl group, vinyl group, and 4-vinylphenyl group as a polymerizable substituent. Or, (3) The other polymerizable compound is a compound having at least one polymerizable substituent selected from the group consisting of epoxy groups, episulfide groups, and thietanyl groups. It is preferable.

[0026] The present invention further provides a photochromic cured body obtained by curing the above-mentioned curable composition, a polymer molded body in which the above-mentioned photochromic hydroxyurethane is dispersed, and an optical article coated with a polymer film in which the above-mentioned photochromic hydroxyurethane is dispersed. [Effects of the Invention]

[0027] The hydroxyurethane compound of the present invention has a hydroxyurethane structural unit represented by formula (1) described above, and has the structural characteristic of having at least one photochromic moiety in or linked to the structural unit. Because it has such a structure, the hydroxyurethane compound of the present invention exhibits excellent photochromic properties in a polymer matrix. Furthermore, this hydroxyurethane compound is not prone to aggregation, and when cured in a polymer matrix, turbidity is effectively suppressed, and a transparent photochromic cured product can be obtained. Moreover, the hydroxyurethane compound of the present invention can be easily dissolved in other polymerizable compounds. [Modes for carrying out the invention]

[0028] <Photochromic hydroxyurethane compound> The photochromic hydroxyurethane compound of the present invention has at least one photochromic site in its molecule, as well as a hydroxyurethane structural unit.

[0029] 1. Regarding photochromic sites and photochromic groups; The photochromic moiety of the hydroxyurethane compound of the present invention refers to a photochromic skeleton that represents the smallest photochromic unit, such as a naphthopyran skeleton, a spirooxazine skeleton, a spiropyran skeleton, a fulgid skeleton, a fulgimid skeleton, or a diarylethene skeleton. Because the molecule has at least one such photochromic moiety, photochromicity (reversible phototautomorphism) is exhibited.

[0030] In the present invention, among the various structures described above, the indenonaphthopyran skeleton, and especially the indeno[2,1-f]naphtho[1,2-b]pyran skeleton, is particularly preferred as the photochromic site because it can exhibit excellent photochromicity in terms of color intensity and fading rate.

[0031] The photochromic moieties described above exist in molecules in the form of photochromic groups in which substituents are introduced into each basic skeleton. These photochromic groups all have a photochromic moiety (photochromic skeleton), and as long as photochromicity is exhibited, they are all photochromic groups. However, in this invention, a photochromic basic structural group is defined as a photochromic skeleton with certain substituents introduced into it, and both this basic structural group and groups in which a chain-like group, described later, is bonded to this basic structural group are treated as photochromic groups. This chain-like group is introduced in order to incorporate the photochromic structural group into the molecule.

[0032] As mentioned above, in the present invention, the naphthopyran skeleton, particularly the indeno[2,1-f]naphtho[1,2-b]pyran skeleton, is preferred as the photochromic moiety, and a photochromic basic structural group having such a basic skeleton is represented by the following formula (8).

[0033] [ka]

[0034] The above-mentioned photochromic basic structural groups may be introduced directly into the molecule as photochromic groups, but it is preferable that they be introduced into the hydroxyurethane structural unit or to a site other than the structural unit via the chain-like groups described later.

[0035] In equation (8), base R 12 ~R 17 The structure with the photochromic elements removed reveals the photochromic region, which is the basic photochromic framework.

[0036] In formula (8), the group R 12 i, which represents the number, is an integer from 0 to 4, and the base R 13 The value j, which represents the number, is an integer between 0 and 4. R 12 and R 13 When i or j is multiple, there will be multiple instances of each, but there will be multiple instances of R 12 Or R13 These may be the same group or different groups.

[0037] Such R 12 and R 13 These terms each represent a bond (hereinafter simply referred to as a direct bond) in which this photochromic basic structural group is bonded to another group, or the following atoms or groups. Hydrogen atom (i or j=0) Hydroxyl group; Alkyl alkyl groups having 1 to 6 carbon atoms; Cycloalkyl groups having 3 to 8 carbon atoms; Alkoxy groups having 1 to 6 carbon atoms; Amino group (including primary and secondary amines); A heterocyclic group having a ring-member nitrogen atom and to which a carbon atom is bonded via the nitrogen atom; Cyano group; Nitro group; Formyl group; Hydroxycarbonyl group; Alkylcarbonyl groups having 2 to 7 carbon atoms; Alkoxycarbonyl groups having 2 to 7 carbon atoms; halogen atom; Aralkyl groups with 7 to 11 member carbon atoms; Aralcooxy group with 7 to 11 ring members; Aryloxy groups with 6 to 12 carbon atoms; Aryl groups with 6 to 12 carbon atoms; Alkylthio groups having 1 to 6 carbon atoms; Cycloalkylthio groups having 3 to 8 carbon atoms; Arylthio groups with 6 to 12 carbon atoms;

[0038] Each of the groups described above may have substituents such as halogen atoms, as long as such substituents can be attached to them and do not inhibit photochromicity. Furthermore, linear groups such as alkyl groups may be linear or branched.

[0039] Unless otherwise specified, groups or rings that can have substituents that do not inhibit photochromicity are not limited to the above groups, and chain-like groups may have such substituents. Also, R 12 and R 13 Although each exists independently, two adjacent atoms may come together to form an aliphatic ring (which may contain oxygen, nitrogen, and sulfur atoms).

[0040] R 14 and R 15 Each of these represents either a direct bond or one of the atoms or groups listed below. hydrogen atom; Hydroxyl group; Alkyl alkyl groups having 1 to 6 carbon atoms; Cycloalkyl groups having 3 to 8 carbon atoms; Alkoxy groups having 1 to 6 carbon atoms; Alkoxyalkyl groups having 1 to 6 carbon atoms; Formyl group; Hydroxycarbonyl group; Alkylcarbonyl groups having 2 to 7 carbon atoms; Alkoxycarbonyl groups having 2 to 7 carbon atoms; halogen atom; Aralkyl groups with 7 to 11 member carbon atoms; Aralcooxy group with 7 to 11 ring members; Aryloxy groups with 6 to 12 carbon atoms; Aryl groups with 6 to 12 carbon atoms;

[0041] Also, R 14 and R 15 These are groups that exist independently of each other, but together they can form the following ring with the carbon atom at position 13 to which they are bonded. Aliphatic rings with 3 to 20 carbon atoms; A fused polycyclic ring in which an aromatic ring or aromatic heterocyclic ring is fused to the aforementioned aliphatic ring; Heterocyclic rings with 3 to 20 member atoms; A polycyclic ring formed by the fusion of an aromatic ring or an aromatic heterocycle with the aforementioned heterocyclic ring;

[0042] Also, R 16 and R 17 These are aryl groups with 6 to 20 carbon atoms and heteroaryl groups with 6 to 20 ring member carbon atoms, respectively.

[0043] In equation (8) above, R 12 ~R 17 Preferably, at least one of these is an aryl group or a heteroaryl group, and a chain-like group for introducing this photochromic group into a hydroxyurethane structural unit or other part is bonded to this aryl group or heteroaryl group.

[0044] Furthermore, R 12 ~R 17 If the group indicated by has further substituents, these substituents are mainly introduced to control the color and tone. Examples of such substituents, provided they are within the carbon number limit, include the following groups. Alkyl alkyl groups having 1 to 6 carbon atoms; Alkoxy groups having 1 to 6 carbon atoms; Amino group (including primary and secondary amines); A heterocyclic group having a ring-membered nitrogen atom and bonded to a carbon atom via the nitrogen atom; Arylthio groups with 6 to 12 carbon atoms; Aryloxy groups with 6 to 12 carbon atoms; Aryl groups with 6 to 12 carbon atoms; Alkylthio groups having 1 to 6 carbon atoms;

[0045] In the photochromic group represented by formula (8) above, in order to exhibit excellent photochromic properties, R 12 ~R 17 It is preferable that the following groups are present.

[0046] <Recommended 12 > Alkyl alkyl groups having 1 to 6 carbon atoms; Alkoxy groups having 1 to 6 carbon atoms; Amino group (including primary and secondary amines); A heterocyclic group having a ring-membered nitrogen atom and bonded to a carbon atom via the nitrogen atom; Arylthio groups with 6 to 12 carbon atoms; Aryl groups with 6 to 12 carbon atoms; Alkylthio groups having 1 to 6 carbon atoms; In particular, it is more preferable that the above-mentioned group is located at position 6 and / or position 7. Furthermore, suitable R for positions 6 and 7 of indeno[2,1-f]naphtho[1,2-b]pyran, respectively. 12 There exist two R 12 Most preferably, these atoms come together to form an aliphatic ring (which may include oxygen, nitrogen, and sulfur atoms). In particular, it is preferable that the number of atoms in this aliphatic ring (including heteroatoms and the number of carbon atoms bonded at positions 6 and 7) be 5 to 7. Furthermore, alkyl groups having 1 to 6 carbon atoms are preferred as substituents that the aliphatic ring may have.

[0047] <Recommended 13 > Alkyl alkyl groups having 1 to 6 carbon atoms; Alkoxy groups having 1 to 6 carbon atoms; Hydrogen atom (when j=0)

[0048] <Recommended 14 and R 15 > Alkyl alkyl groups having 1 to 6 carbon atoms; direct bond; Furthermore, R 14 and R 15 A configuration in which these atoms are bonded to each other and, together with the carbon atom at position 13 to which they are bonded, forms the following ring is also preferred. Aliphatic rings with 3 to 20 carbon atoms; A fused polycyclic ring in which an aromatic ring or aromatic heterocycle is fused to the above-mentioned aliphatic ring; A heterocycle having 3 to 20 member atoms; A polycyclic ring formed by the fusion of an aromatic ring or an aromatic heterocycle with the above-mentioned heterocyclic ring; Specific examples of the above ring include the following:

[0049] R 14 and R 15 A preferred ring formed by: Cyclopentane ring; Cyclohexane ring; Cycloheptane ring; Cyclooctane ring; Cyclononane ring; Cyclodecane ring; Cycloundecane ring; Cyclododecane ring; Spirodicyclohexane ring; Furthermore, the spiro ring may also have 1 to 10 substituents of C1-C6 alkyl groups or C5-C7 cycloalkyl groups, and it may also be preferable that the spiro ring is fused with a C5-C7 cycloalkyl group. Among the rings mentioned above, a more suitable one is exemplified by the following formula.

[0050] [ka]

[0051] <Recommended 16 and R 17 > Aryl groups with 6 to 12 carbon atoms; The following are examples of preferred substituents that the above aryl group may have. Alkyl alkyl groups having 1 to 6 carbon atoms; Alkoxy groups having 1 to 6 carbon atoms; dimethylamino group; Diphenylamino group; A heterocyclic group having a ring-membered nitrogen atom and bonded to a carbon atom via the nitrogen atom;

[0052] The photochromic basic structural group having the indeno[2,1-f]naphtho[1,2-b]pyran skeleton described above is known in itself, and various other types are also known. For example, see International Publication No. 1996 / 014596, International Publication No. 2001 / 019813, International Publication No. 2001 / 060811, International Publication No. 2005 / 028465, International Publication No. 2006 / 110221, International Publication No. 2007 / 073462, International Publication No. 2007 / 140071, International Publication No. 2008 / 054942, and International Publication No. 2010 / 06539. This is also described in Brochure No. 3, International Publication No. 2011 / 10744, International Publication No. 2011 / 016582, International Publication No. 2011 / 025056, International Publication No. 2011 / 034202, International Publication No. 2011 / 078030, International Publication No. 2012 / 102409, International Publication No. 2012 / 102410, International Publication No. 2012 / 121414, etc. The present invention may also use materials having such basic structural groups. In this invention, the photochromic basic structural group of formula (8) described above is bonded to a chain-like group and exists in the molecule as a photochromic group represented by the following formula (4).

[0053] [ka]

[0054] In the above formula (4), PC is the aforementioned photochromic basic structural group, and this basic structural group is also a photochromic group. As can be understood from this formula (4), R bonded to PC 8 ,R 9 , Z 1 The chain portion containing L is a chain group that introduces the basic structural group into the molecule.

[0055] R 8R is an alkylene group having 1 to 30 carbon atoms, and typical substituents that this alkylene group may have are halogen atoms. 8 Preferred groups are ethyl, propyl, isopropyl, or butyl groups. R 9 This is an alkylene group having 1 to 30 carbon atoms, or an alkylene group having 1 to 30 carbon atoms with an ether bond. 9 Suitable groups are butylene, pentylene, or hexylene. Z 1 This is an oxygen atom, a sulfur atom, or an NH group.

[0056] Furthermore, d is an integer between 0 and 50, preferably between 0 and 10, and particularly preferably between 0 and 2. e is an integer between 0 and 50, with 0 to 10 being preferred. When d or e is 2 or greater, R 8 , or R 9 and Z 1 There will be multiple instances of this, and they may be the same or different. Furthermore, when d=e=0, this chain-like group consists only of L bonded to PC.

[0057] Furthermore, L is a divalent group represented by the following formula (5). [ka]

[0058] In equation (5) above, f and g are integers between 0 and 50. In equation (5) as well, there will be multiple R values ​​depending on the value of f or g. 10 ,R 11 ,Z 2 ,Z 3 The bases of the elements may be the same or different. Furthermore, h is an integer of either 0 or 1. As understood from formula (5), when f = g = h = 0, L becomes a direct bond. Therefore, when f = g = h = 0 and d and e in formula (4) are 0, this chain group does not exist and becomes a direct bond, and the photochromic group (basic structural group) directly binds to other groups.

[0059] In formula (5), R 10 represents an alkylene group having 1 to 30 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms, or an arylene group having 6 to 12 carbon atoms. R 10 Preferred groups as R are an ethylene group, a propylene group, and a cyclohexylene group, and an ethylene group is particularly preferred.

[0060] R 11 is an alkylene group having 1 to 20 carbon atoms; a cycloalkylene group having 3 to 12 carbon atoms; an arylene group having 6 to 12 carbon atoms; or a dialkylsilylene group having an alkyl group having 1 to 20 carbon atoms. R 11 Preferred groups as R are an ethylene group, a propylene group, a butylene group, or a dimethylsilylene group, and an ethylene group, a propylene group, and a dimethylsilylene group are particularly preferred.

[0061] R 12a represents an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms, or an arylene group having 6 to 12 carbon atoms. R 12a Preferred groups as R are an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a cyclohexene group, a phenylene group, and a naphthylene group.

[0062] Z 2 , Z 3 are each a direct bond, O, CO or NH, and preferably a direct bond, O or CO.

[0063] As L represented by formula (5) as described above, particularly preferred ones are represented by the following formula.

[0064] [ka]

[0065] In formula (4) having L as described above, the following groups are particularly preferred, considering the productivity of the hydroxyurethane compound and the effects of encapsulation function by the oligomer chain (suppression of matrix dependence) and anti-aggregation.

[0066] [ka]

[0067] 2. Hydroxyurethane constituent units; The hydroxyurethane compound of the present invention contains at least one photochromic group (which may also be a photochromic basic structural group) containing the aforementioned photochromic moiety in the molecule, and is defined by the following formula (1): -XO-CO-NH- (1) It has a hydroxyurethane constituent unit represented by [the formula shown]. In other words, the molecular structure either has a photochromic group having the aforementioned photochromic moiety introduced into this structural unit, or has a photochromic group introduced into a part outside this structural unit. That is, the hydroxyurethane compound of the present invention reflects the properties of the hydroxyurethane structural unit represented by formula (1) along with its photochromicity. As a result, it is thought that compatibility and dispersibility in solid matrices are improved, and turbidity due to aggregation in the matrix and a decrease in photochromic properties in the matrix are suppressed. Furthermore, since such a photochromic hydroxyurethane compound is obtained in an oily state with reduced crystallinity, its solubility in other polymerizable compounds is improved.

[0068] In formula (1) above, X is an oxygen-containing chain-like organic group having a hydroxyl group as a substituent. This oxygen-containing chain-like organic group (a group having an oxygen atom in the chain, and may also contain nitrogen atoms, sulfur atoms, etc.) coats the photochromic moiety in the solid matrix as an oligomer chain (microencapsulation), reducing matrix dependence and ensuring excellent photoresponsiveness.

[0069] The hydroxyl group of the above-mentioned oxygen-containing chain organic group may have a substituent on its hydrogen atom. If this substituent is represented by R, the oxygen-containing chain organic group X will have either an -OH group or a group represented by -OR. Such substituent R is one of the following groups (A) to (E). (A) A photochromic group having the photochromic moiety. (B) A polymerization-reactive group having a polymerizable substituent. (C) Alkyl alkyl group having 1 to 10 carbon atoms. (D) Cycloalkyl groups with 3 to 10 carbon atoms. (E) Aryl groups with 6 to 14 carbon atoms.

[0070] Substituent (A); This substituent (A) is a photochromic group, a group having a photochromic moiety. For example, formula (4) mentioned above; [ka] It is a base represented by .

[0071] Polymerization reactive group (B); The polymerization-reactive group imparts polymerizability to this hydroxyurethane compound. By polymerizing and curing this compound alone or in combination with other polymerizable compounds described later, it can be immobilized on the resulting solid matrix, and a photochromic cured product with improved dispersibility in the solid matrix can be obtained.

[0072] This polymerization-reactive group has a polymerizable substituent, and there are various types of polymerizable substituents depending on the polymerization mode. In the present invention, examples of polymerizable substituents include at least one group selected from the group consisting of acrylic group, methacrylic group, allyl group, vinyl group, 4-vinylphenyl group, epoxy group, episulfide group, thietanyl group, carboxyl group, hydroxyl group, thiol group, amino group, isocyanate group, and thiocyanate group. These groups may individually substitute for the hydrogen atoms of the hydroxyl group, but they usually have a chain-like linking group, similar to the photochromic group PC mentioned above, and the polymerizable substituents are located at the ends of this chain-like group from the viewpoint of polymerization reactivity.

[0073] A polymerization-reactive group having such a polymerizable substituent is represented by the following formula (6). [ka]

[0074] In the above formula, PG is the polymerizable substituent described above, and any of the groups exemplified above is preferred.

[0075] d1 is an integer between 0 and 50, with 0 to 10 being particularly preferred, and 0 to 2 being especially preferred. Furthermore, e1 is an integer between 0 and 50, preferably between 0 and 10. Furthermore, when d1 and e1 are 2 or more, there are multiple R 81 , R 91 Or Z 11 The groups may be the same or different. Furthermore, when d1=e1=0, L' in equation (6) directly bonds to the hydroxyl group (oxygen atom).

[0076] In formula (6), R 81 The alkylene group has 1 to 30 carbon atoms, and preferred groups include ethylene, propylene, isopropylene, and butylene. A halogen atom is a suitable substituent that the alkylene group may have.

[0077] R 91 is an alkylene group having 1 to 30 carbon atoms or an alkylene group having 1 to 30 carbon atoms with an ether bond. Preferred groups include a butylene group, a pentylene group, and a hexylene group. Further, as a substituent that the alkylene group may have, a halogen atom is suitable.

[0078] Z 11 is an oxygen atom, a sulfur atom, or an NH group.

[0079] Furthermore, L' in formula (6) is an oxygen-containing chain organic group represented by the following formula (7).

Chemical formula

[0080] In formula (7), f1 and g1 are each an integer from 0 to 50. When f1 and g1 are numbers of 2 or more, R 101 、R 111 、Z 21 and Z 31 each exist in plural, but in this case, the plural groups may be the same or different. Also, h1 is an integer of 0 or 1. In addition, when f1 = g1 = h1 = 0, L' becomes a direct bond, and the polymerizable substituent PG directly binds to the group Z 11 in formula (6). Further, when d1 = e1 = f1 = g1 = h1 = 0, the polymerizable substituent PG directly binds to the hydroxyl group (oxygen atom). <00​​​​​

[0082] R 111 These are alkylene groups having 1 to 20 carbon atoms; cycloalkylene groups having 3 to 12 carbon atoms; arylene groups having 6 to 12 carbon atoms; and dialkylsilylene groups having an alkyl group having 1 to 20 carbon atoms. Preferred groups include ethylene, propylene, butylene, and dimethylsilylene groups, with ethylene, propylene, and dimethylsilylene groups being particularly preferred.

[0083] R 121 The group is an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms, or an arylene group having 6 to 12 carbon atoms. Preferred groups include ethylene, propylene, butylene, pentylene, hexylene, cyclohexene, phenylene, and naphthylene groups.

[0084] Also, Z 21 and Z 31 Each of these is a direct bond, O, CO, or NH, preferably a direct bond, O, or CO.

[0085] In equation (6) described above, the L' that is particularly preferred is expressed by the following equation.

[0086] [ka]

[0087] In the polymerization reactive group represented by formula (6) described above, the oxygen-containing chain group to which the polymerizable substituent PG is attached is particularly preferred from the viewpoint of productivity of urethane hydroxy compounds and dispersibility in a solid matrix, as shown below.

[0088] [ka]

[0089] Alkyl groups (C), cycloalkyl groups (D), and aryl groups (E); These groups, which substitute for hydrogen atoms in the hydroxyl groups of oxygen-containing chain-like organic groups X, secure free space around the photochromic groups, enhancing photochromic properties such as color intensity and fading rate, while also increasing the solubility of the hydroxyurethane compound and improving its dispersibility and curability within the solid matrix. The number of carbon atoms in these groups is restricted from the standpoint of synthesizability and photochromic properties. For example, the alkyl group has 1 to 10 carbon atoms, and preferred groups include methyl, ethyl, propyl, isopropyl, n-butyl, and sec-butyl groups. Furthermore, the number of carbon atoms in the cycloalkyl group is 3 to 10, and preferred groups include cyclopentyl, cyclohexyl, and cycloheptyl groups. The aryl group has 6 to 14 carbon atoms, and suitable groups include phenyl, naphthyl, anthracenyl, and fluorenyl groups. Furthermore, these groups (C) to (E), like polymerizable substituents, may be bonded to oxygen atoms derived from the hydroxyl group via oxygen-containing chain organic groups. These oxygen-containing chain organic groups can be represented, for example, by formula (7) described above.

[0090] <Suitable hydroxyurethane compounds> The photochromic hydroxyurethane compound of the present invention has at least one photochromic group containing the aforementioned photochromic moiety, and also contains a hydroxyurethane structural unit represented by formula (1). However, from the viewpoint of ease of synthesis, dispersibility in a polymer matrix, and high photochromic properties, it is preferable that at least the hydroxyurethane structural unit contains a photochromic group. In the present invention, preferred hydroxyurethane compounds are represented, for example, by the following formula (2).

[0091] [ka]

[0092] In formula (2) above, n represents the number of repeating units and is an integer between 1 and 100. It is particularly desirable that n be an integer of 2 or more, from the viewpoint that the chain to which the photochromic site is attached becomes longer. When n is multiple, X 1 ,X 2 ,R 1 and R 2 Although multiple of these groups will exist within the molecule, these multiple groups may be the same group or different groups.

[0093] Furthermore, in equation (2), the R bonded to NH 100 The carbon atoms are hydrogen atoms, C1-C30 alkyl groups, C1-C30 alkoxy groups, or C6-C14 aryl groups. Specifically, preferred C1-C30 alkyl groups include methyl, ethyl, butyl, hexyl, octyl, nonyl, decyl, 2-ethylhexyl, hexadecyl, octadecyl, eicosyl, tetracosyl, and oleyl groups. Preferred C1-C30 alkoxy groups include methoxy, ethoxy, propoxy, butoxy, hexyloxy, and octadecyloxy groups. Preferred C6-C14 aryl groups include phenyl, naphthyl, phenanthryl, and anthracenyl groups. Furthermore, R is bonded to CO. 200 The group is a hydroxyl group, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or an aryl group having 6 to 14 carbon atoms. Specifically, preferred alkyl groups having 1 to 30 carbon atoms include methyl, ethyl, butyl, hexyl, octyl, nonyl, decyl, 2-ethylhexyl, hexadecyl, octadecyl, eicosyl, tetracosyl, and oleyl groups. Preferred alkoxy groups having 1 to 30 carbon atoms include methoxy, ethoxy, propoxy, butoxy, hexyloxy, and octadecyloxy groups. Preferred aryl groups having 6 to 14 carbon atoms include phenyl, naphthyl, phenanthryl, and anthracenyl groups.

[0094] -X in equation (2) 1 -R1 -X 2 - is a group corresponding to the group X in formula (1) above, and X 1 and X 2 Each of these is expressed by one of the following equations (2a) to (2d) It is a divalent group represented.

[0095] [ka]

[0096] In the above equations (2a) to (2d), R 3 R is a hydrogen atom or any of the groups (A) to (E) above, but there are multiple R in formula (2). 3 Of these, at least one is the photochromic group of (A). That is, this hydroxyurethane constituent unit always contains a photochromic group. Also, R 3 When is a hydrogen atom or one of the groups (B) to (E), the solubility of this hydroxyurethane compound can be further improved. Furthermore, when polymerizing and curing in combination with other polymerizable compounds, the polymerizability can be controlled, and the desired photochromic cured product can be easily obtained. Also, the groups (C) to (E), like the group (B), may be bonded to the oxygen atom derived from the hydroxyl group via an oxygen-containing chain organic group, and as mentioned above, this oxygen-containing chain organic group can be represented by formula (7). In the present invention, X 1 and X 2 Preferably, the group is represented by the above formula (2a) or (2b).

[0097] Also, R 4 This is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably a hydrogen atom, a methyl group, or an ethyl group.

[0098] Also, in equation (2), R 1 and R 2 These are, respectively, divalent oxygen-containing chain groups represented by the following formula (3). [ka]

[0099] In equation (3), a, b, and c are integers between 0 and 100, provided that none of them are zero. Also, when a, b, or c are multiple, Y 1 , R 5 , Y 2 , R 6 Or R 7 Although multiple of these groups will exist within the molecule, these multiple groups may be the same group or different groups.

[0100] Also, in equation (3), R 5 This group is an alkylene group having 1 to 30 carbon atoms, a cycloalkylene group having 3 to 30 carbon atoms, or an arylene group having 6 to 30 carbon atoms. Furthermore, halogen atoms are preferred substituents that the alkylene group may have.

[0101] R 6 This is a silylene group having one to 30 carbon atoms as an alkylene group, three to 30 carbon atoms as a cycloalkylene group, six to 30 carbon atoms as an arylene group, or any of the following groups as a substituent. substituents on a silylene group; Alkyl alkyl groups having 1 to 30 carbon atoms, Alkoxy groups having 1 to 30 carbon atoms, and Aryl groups with 6 to 30 carbon atoms, Preferred C1-C30 alkyl groups as substituents include, specifically, methyl, ethyl, butyl, hexyl, octyl, nonyl, decyl, 2-ethylhexyl, hexadecyl, and octadecyl groups. Among these, C1-C10 alkyl groups are preferred, specifically, methyl, ethyl, propyl, butyl, and 2-ethylhexyl groups. Preferred C1-C30 alkoxy groups as substituents include methoxy, ethoxy, propoxy, butoxy, hexyloxy, and octadecyloxy groups. Among these, C1-C10 alkoxy groups are preferred, specifically, methoxy, ethoxy, and propoxy groups. Preferred C6-C30 aryl groups as substituents are preferably C6-C14 aryl groups, specifically, phenyl, naphthyl, phenanthryl, and anthracenyl groups.

[0102] R 7 These are alkylene groups with 1 to 30 carbon atoms, cycloalkylene groups with 3 to 30 carbon atoms, or arylene groups with 6 to 30 carbon atoms.

[0103] Y 1 and Y 2 These are, respectively, a direct bond, an oxygen atom, a sulfur atom, CO, SO, or NH.

[0104] In the hydroxyurethane compound represented by formula (2) described above, it is particularly preferable that it has the following structure, as it can exhibit better photochromic properties while also having dispersibility in a solid matrix.

[0105] base R 1 and base R 2Regarding this, it is preferable that at least one of them is an alkylene group, a polyoxyalkylene group, or a polyoxysilylene group. Among these groups, it is more preferable that the alkylene group has 1 to 30 carbon atoms; the polyoxyalkylene group has 1 to 30 carbon atoms; and the polyoxysilylene group has at least one substituent selected from an alkyl group with 1 to 30 carbon atoms, an alkoxy group with 1 to 30 carbon atoms, and an aryl group with 6 to 30 carbon atoms. Even more preferable is that the alkylene group has 1 to 15 carbon atoms, the poly(oxyethylene) group has 2 to 200 carbon atoms, the poly(oxypropylene) group has 3 to 300 carbon atoms, or the poly(oxydimethylsilylene) group.

[0106] Furthermore, among the hydroxyurethane compounds having the above structure, X 1 and X 2 The photochromic groups (represented by formula (4)) containing photochromic moieties exhibit particularly excellent effects when they are present in the following number proportions.

[0107] X 1 and X 2 The total R in 3 This is expressed as the average value of the proportion (number of atoms) occupied by hydrogen atoms, etc. The proportion of hydrogen atoms is 0-99%, especially 1-50%; The proportion of photochromic groups is 1-100%, especially 50-99%; The proportion of polymerization-reactive groups (groups of formula (6)) is 0-99%, particularly 0-50%; The proportion of groups with other groups is 0-50%;

[0108] Naturally, a hydrogen atom ratio of 100% is not found in all groups R 3 This indicates that the group is -OH, and the sum of the ratios of hydrogen atoms, photochromic groups, polymerization reactive groups, and other groups is 100%.

[0109] In the present invention, the weight-average molecular weight (Mw) of the hydroxyurethane (non-photochromic hydroxyurethane before the introduction of the photochromic group) in the portion excluding the photochromic group having a photochromic moiety (the group represented by formula (4)) is not particularly limited. However, if the molecular weight becomes too high, the solubility of the photochromic hydroxyurethane compound of the present invention tends to decrease, and its viscosity tends to increase, making it difficult to handle. On the other hand, if the molecular weight is too low, the photochromic properties tend to decrease. From this viewpoint, the weight-average molecular weight (Mw) of the above-mentioned non-photochromic hydroxyurethane is preferably 300 to 100,000, particularly preferably 500 to 50,000, and even more preferably 1,000 to 30,000.

[0110] Furthermore, for each photochromic group, the weight-average molecular weight (Mw) of the non-photochromic hydroxyurethane is preferably 300 to 50,000, particularly 500 to 30,000, and most preferably 700 to 15,000. The weight-average molecular weights and other parameters were determined by the method described in the examples below. First, the weight-average molecular weight (Mw) of the non-photochromic hydroxyurethane before the introduction of photochromic groups was measured by gel permeation chromatography (GPC). Then, by dividing this weight-average molecular weight (Mw) by the number of introduced photochromic groups, the weight-average molecular weight (Mw) of the non-photochromic hydroxyurethane per photochromic group could be determined.

[0111] <Production of photochromic hydroxyurethane compounds> The photochromic hydroxyurethane compound of the present invention is produced by reacting a pre-synthesized hydroxyurethane having an OH group (non-photochromic hydroxyurethane) with a separately synthesized photochromic compound having an OH-reactive functional group (starting photochromic compound). The OH-reactive functional group described above is located at the end of the oxygen-containing chain organic group (the portion bonded to the group PC) in the photochromic group represented by formula (4), and is preferably located at the end of the divalent group L represented by formula (5).

[0112] If we represent the chain portion containing the OH-reactive functional group as, for example, Q, this reaction can be simply represented by the following equation. -X-OH+α-Q-PC→-XOQ-PC In the above, X is an oxygen-containing chain-like organic group found in the non-photochromic hydroxyurethane, and α is a detached portion (such as a hydrogen atom or chlorine atom) bonded to Q. Furthermore, the photochromic group PC and the OH group may react directly. In this case, the chain-like group (or L) represented by Q becomes a direct bond. Also, when an OH-reactive functional group is present at the end of L, the above Q is L.

[0113] The above reaction utilizes the reaction between an OH group and an OH-reactive functional group, and various groups are known as OH-reactive functional groups. For example, carboxylic acid groups, carboxylic acid halides, acid anhydride groups, isocyanate groups, etc. In this invention, any of these functional groups can be used to react with OH.

[0114] For example, the above-mentioned functional group can be introduced to a photochromic group PC by a known method, and then reacted with the OH group of the hydroxyurethane.

[0115] When the OH-reactive functional group is a carboxylic acid group, the reaction with OH is an esterification reaction. This esterification reaction can be carried out by stirring in a solvent such as toluene, with heating as needed, in the presence of a mineral acid such as sulfuric acid or hydrochloric acid, an organic acid such as aromatic sulfonic acid, or a Lewis acid such as boron fluoride ether, and removing the resulting water by azeotrope. In the esterification reaction, methods for removing water include removing water with a drying agent such as anhydrous magnesium sulfate or molecular sieves, or removing water in the presence of a dehydrating agent such as dicyclohexylcarbodiimide.

[0116] Even when the OH-reactive functional group is a carboxylic acid halide, the reaction with OH is an esterification reaction. This esterification reaction can be carried out in the presence of a base such as pyridine or dimethylaniline, in an ether-based solvent such as tetrahydrofuran, stirring with heating as needed, and removing the generated hydrogen halide.

[0117] Even when the functional group is an acid anhydride group, it is still an esterification reaction, and methods such as stirring with heating as needed in a solvent such as toluene in the presence of a catalyst such as sodium acetate or pyridine can be employed.

[0118] Furthermore, if the functional group is an NCO group, the reaction with OH results in a urethane reaction. This reaction can be carried out in the presence of an amine-based catalyst such as triethylenediamine or a tin-based catalyst such as dibutyltin dilaurate, in a solvent-free or solvent such as toluene, and stirred while heating as necessary.

[0119] Furthermore, the same method as described above can be used to introduce polymerization-reactive groups and other groups.

[0120] Manufacturing of non-photochromic hydroxyurethanes; Non-photochromic hydroxyurethanes, which are reacted with photochromic compounds, are produced by reacting a compound having at least one cyclic carbonate group in its molecule (hereinafter simply referred to as a cyclic carbonate compound) with a compound having at least one amino group in its molecule (hereinafter simply referred to as an amino compound). The compound obtained by the above reaction has an oxygen-containing chain organic group X containing a hydroxyl group as a substituent. For example, R present in formula (2) 3 All of them are hydrogen atoms.

[0121] The above reaction can be carried out by heating and stirring in a solvent, either in the presence or absence of a catalyst. While not particularly limited, the solvent can be 1,4-dioxane, ethyl acetate, propylene glycol monomethyl ether acetate, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, acetonitrile, etc.

[0122] The following compounds can be used as catalysts. Tertiary amines; Triethylamine, tributylamine, DBU (diazabicycloundecene), DABCO (diazabicyclooctane), pyridine, etc. Alkali metal salts; Lithium chloride, lithium bromide, lithium fluoride, sodium chloride, etc. Alkaline earth metal salts; Calcium chloride, etc. Quaternary ammonium salts; Examples include tetrabutylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, and benzyltrimethylammonium chloride. Carbonates; Potassium carbonate, sodium carbonate, etc. Metal acetates; Zinc acetate, lead acetate, copper acetate, iron acetate, etc. Metal hydrides; Calcium hydride, etc. Metal oxides; Calcium oxide, magnesium oxide, zinc oxide, etc. Phosphonium salts; Tetrabutylphosphonium chloride, etc. Sulfonium salts; Benzyltetrahydrothiophenium chloride, etc. Tin compounds; Tetrabutyltin, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin oxide, etc.

[0123] From the viewpoint of effectively promoting the reaction, the amount of the catalyst used is 0.01 to 0.5 mol, preferably 0.03 to 0.3 mol, and more preferably 0.05 to 0.2 mol per 1 mol of the cyclic carbonate compound. The reaction temperature is 30 to 150 °C, preferably 40 to 120 °C, and more preferably 50 to 100 °C.

[0124] Regarding the usage ratio of the cyclic carbonate compound and the amino compound, there is no particular limitation. However, from the viewpoint of effectively promoting the reaction, the amount of the amino compound used is 0.7 to 1.2 mol, particularly 0.9 to 1.1 mol, more preferably 0.95 to 1.05, and most preferably 1.00 per 1 mol of the cyclic carbonate compound (the number of moles of the cyclic carbonate group).

[0125] In addition, the cyclic carbonate group of the cyclic carbonate compound and the amino group of the amino compound only need to have at least one in the molecule. However, considering the solubility of the non-photochromic hydroxyurethane, ease of handling, and the photochromic property of the photochromic hydroxyurethane compound as the final target product, it is preferably less than 4, more preferably 2 or less, and particularly preferably 2.

[0126] Cyclic carbonate compounds; Carbonate compounds having at least one cyclic carbonate group in their molecule are not particularly limited as long as they can react with an amino compound to form a hydroxyurethane structure, but compounds having a five-membered carbonate ring are preferred in terms of reactivity with amino compounds. Such compounds having a five-membered cyclic carbonate group can be produced by reacting an epoxy group-containing compound with carbon dioxide at atmospheric pressure or slightly above atmospheric pressure at a temperature of 40°C to 150°C in the presence of a catalyst.

[0127] In the above reaction, a solvent is used as needed. Examples of such solvents include 1,4-dioxane, ethyl acetate, propylene glycol monomethyl ether acetate, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, and acetonitrile.

[0128] Examples of catalysts for the production of cyclic carbonate compounds include tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, benzyltrimethylammonium bromide, benzyltrimethylammonium chloride, lithium iodide, and lithium bromide. From the viewpoint of effectively promoting the reaction, the amount of catalyst used is 0.01 to 0.5 moles, particularly 0.03 to 0.3 moles, and more preferably 0.05 to 0.2 moles per mole of epoxy compound.

[0129] Furthermore, cyclic carbonate compounds include the following types, depending on the type of epoxy compound used in the reaction. Aliphatic cyclic carbonate compounds obtained by reacting an aliphatic epoxy compound with carbon dioxide; Aromatic cyclic carbonate compounds obtained by reacting aromatic epoxy compounds with carbon dioxide; Alicyclic cyclic carbonate compounds obtained by reacting alicyclic epoxy compounds with carbon dioxide; Polyalkylene glycol-based cyclic carbonate compounds obtained by reacting a polyalkylene glycol having an epoxy group with carbon dioxide; Polysiloxane-based cyclic carbonate compounds obtained by reacting a polysiloxane compound having an epoxy group with carbon dioxide; A polyester polyether-based cyclic carbonate compound obtained by reacting a polyester polyether having epoxy groups with carbon dioxide; A polycyclic carbonate compound having three or more carbonate rings, obtained by reacting a polyepoxy compound with carbon dioxide;

[0130] Of the cyclic carbonate compounds mentioned above, aliphatic cyclic carbonate compounds, polyalkylene glycol-based cyclic carbonate compounds, polysiloxane-based cyclic carbonate compounds, and polyester polyether-based cyclic carbonate compounds are preferred when considering photochromicity and dispersibility in a solid matrix, as the final target product is a hydroxyurethane compound.

[0131] Amino compounds; The amino compound to be reacted with the above-mentioned cyclic carbonate compound is not particularly limited, as long as it has a primary or secondary amino group and is reactive with the above-mentioned cyclic carbonate compound. Among these, a compound having a primary amino group is preferred, considering its reactivity with the cyclic carbonate compound. Examples of amino compounds having a primary amino group include aliphatic amino compounds, aromatic amino compounds, alicyclic amino compounds, polyalkylene glycol compounds having an amino group, and polysiloxane compounds having an amino group. Furthermore, these amino compounds may also have a secondary amino group or a tertiary amino group in addition to the primary amino group.

[0132] Of these, considering the photochromic properties and dispersibility in a solid matrix of the final target hydroxyurethane compound, aliphatic amino compounds, polyalkylene glycol-based amino compounds, and polysiloxane-based amino compounds are preferred.

[0133] <Photochromic curable composition> The photochromic hydroxyurethane compound of the present invention, produced by the method described above, can be cured alone to form a photochromic cured product, but it can also be used as a photochromic curable composition by combining it with other polymerizable compounds. Examples of such polymerizable compounds include urethane or urea-based polymerizable compounds capable of forming urethane bonds or urea bonds, radical polymerizable compounds, and epoxy polymerizable compounds. These polymerizable compounds are not particularly limited, but for example, polymerizable compounds described in International Publication WO2018-235771 can be suitably used. Among these, the polymerizable compounds listed below are particularly suitably used.

[0134] Iso(thio)cyanate compounds; Iso(thio)cyanate compounds are compounds having an isocyanate group or an isothiocyanate group, and may contain both an isocyanate group and an isothiocyanate group. These compounds are preferably used in combination with compounds containing active hydrogen, as described later.

[0135] Examples of such isocyanate compounds, though not limited to these, include the following: Polyiso(thio)cyanates having at least two iso(thio)cyanate groups in one molecule; Aromatic polyiso(thio)cyanates having an aromatic ring, such as m-xylene diisocyanate and 4,4'-diphenylmethane diisocyanate; Aliphatic polyiso(thio)cyanates such as norbornane diisocyanate and dicyclohexylmethane-4,4'-diisocyanate;

[0136] Compounds containing active hydrogen; Examples of the compound having active hydrogen include, but are not limited to, compounds having a hydroxyl group and / or a thiol group, and particularly preferred are polyfunctional compounds having two or more active hydrogens in one molecule. Specific examples of the compound having active hydrogen include polyfunctional thiol compounds such as pentaerythritol tetrakis(3-mercaptopropionate) and 4-mercaptomethyl-3,6-dithiaoctanedithiol; polyfunctional alcohols such as trimethylolpropane and pentaerythritol.

[0137] Radical polymerizable compound; The radical polymerizable compound can be classified into polyfunctional radical polymerizable compounds and monofunctional radical polymerizable compounds, and each can be used alone or in combination of a plurality. Examples of the radical polymerizable substituent include a group having an unsaturated double bond, that is, a vinyl group (including a styryl group, a (meth)acrylic group, an allyl group, etc.).

[0138] The polyfunctional radical polymerizable compound is a compound having two or more radical polymerizable substituents in the molecule. This polyfunctional radical polymerizable compound can be divided into a first polyfunctional radical polymerizable compound having 2 to 10 radical polymerizable substituents and a second polyfunctional radical polymerizable compound having more than 10 radical polymerizable substituents.

[0139] The first radical polymerizable compound is not particularly limited, but it is more preferable that the number of radical polymerizable substituents is 2 to 6. Specific examples are as follows. Polyfunctional (meth)acrylate compound; Ethylene glycol di(meth)acrylate Diethylene glycol di(meth)acrylate Triethylene glycol di(meth)acrylate Tetraethylene glycol di(meth)acrylate Ethylene glycol bisglycidyl (meth)acrylate Bisphenol A di(meth)acrylate 2,2-Bis(4-(meth)acryloyloxyethoxyphenyl)propane 2,2-Bis(3,5-dibromo-4-(meth)acryloyloxyethoxyphenyl)propane Polyfunctional allyl compounds; diallylphthalate diallyl terephthalate diallyl isophthalate diallyl tartrate diallyl epoxy succinate diallyl fumarate Diallyl chloride Diallyl hexaphthalate diallyl carbonate Allyl diglycol carbonate Trimethylolpropane triallyl carbonate Polyfunctional thio(meth)acrylic acid ester compounds; 1,2-Bis(methacryloylthio)ethanebis(2-acryloylthioethyl)ether 1,4-Bis(methacryloylthiomethyl)benzene vinyl compound; Divinylbenzene

[0140] Examples of second polyfunctional radical polymerizable compounds with more than 10 radical polymerizable substituents include relatively large molecular weight compounds such as silsesquioxane compounds with radical polymerizable substituents and polyrotaxane compounds with radical polymerizable substituents.

[0141] Furthermore, monofunctional radical polymerizable compounds are compounds that have one radical polymerizable substituent in their molecule. Specific examples, though not limited to these, include the following compounds.

[0142] Unsaturated carboxylic acid; Acrylic acid Methacrylic acid maleic anhydride (meth)acrylic acid ester; Methyl (meth)acrylate Benzyl methacrylate Phenyl methacrylate 2-hydroxyethyl methacrylate Glycidyl (meth)acrylate β-methylglycidyl (meth)acrylate Bisphenol A-monoglycidyl ether-methacrylate 4-Glycidyloxymethacrylate 3-(glycidyl-2-oxyethoxy)-2-hydroxypropyl methacrylate 3-(glycidyloxy-1-isopropyloxy)-2-hydroxypropyl acrylate 3-(glycidyloxy-2-hydroxypropyloxy)-2-hydroxypropyl acrylate fumarate ester; Diethyl fumarate Diphenyl fumarate Thio(meth)acrylic acid; Methylthioacrylate benzylthioacrylate benzylthiomethacrylate Vinyl compounds; styrene Chlorophylloid Methylstyrene Vinyl naphthalene α-methylstyrene dimer Bromostyrene

[0143] Radical polymerizable compounds can be used alone or as a mixture of multiple types. In this case, it is preferable to use 80 to 100 parts by mass of polyfunctional radical polymerizable compounds and 0 to 20 parts by mass of monofunctional radical polymerizable compounds per 100 parts by mass of total radical polymerizable compounds, and more preferably 90 to 100 parts by mass of polyfunctional radical polymerizable compounds and 0 to 10 parts by mass of monofunctional radical polymerizable compounds. Furthermore, it is preferable to use 80 to 100 parts by mass of first polyfunctional radical polymerizable compounds, 0 to 20 parts by mass of second radical polymerizable compounds and 0 to 20 parts by mass of monofunctional radical polymerizable compounds per 100 parts by mass of total radical polymerizable compounds, and even more preferably 85 to 100 parts by mass of first polyfunctional radical polymerizable compounds, 0 to 10 parts by mass of second polyfunctional radical polymerizable compounds and 0 to 10 parts by mass of monofunctional radical polymerizable compounds.

[0144] Various compounding agents; The curable composition containing the photochromic hydroxyurethane compound of the present invention may contain various known compounding agents, such as mold release agents, ultraviolet absorbers, infrared absorbers, ultraviolet stabilizers, antioxidants, color inhibitors, antistatic agents, fluorescent dyes, dyes, pigments, fragrances, and other stabilizers, as long as they do not impair the effects of the present invention. Solvents and leveling agents may also be added, and thiols such as t-dodecyl mercaptan may be added as polymerization modifiers as needed.

[0145] Among the above-mentioned formulations, UV stabilizers are preferred because they can improve the durability of the photochromic portion. Examples of such UV stabilizers include hindered amine light stabilizers, hindered phenol antioxidants, and sulfur-based antioxidants. Particularly preferred UV stabilizers are as follows: Bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate; Adeka stubs LA-52, LA-57, LA-62, LA-63, LA-67, LA-77, LA-82, LA-87, manufactured by Asahi Denka Kogyo Co., Ltd. 2,6-di-tert-butyl-4-methylphenol; Ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate]; IRGANOX® 1010, 1035, 1075, 1098, 1135, 1141, 1222, 1330, 1425, 1520, 259, 3114, 3790, 5057, 565, manufactured by Ciba Specialty Chemicals.

[0146] The amount of UV stabilizer used is not particularly limited as long as it does not impair the effects of the present invention, but is usually in the range of 0.001 to 10 parts by mass, particularly 0.01 to 1 part by mass, per 100 parts by mass of the photochromic hydroxyurethane compound of the present invention. In particular, when a hindered amine light stabilizer is used, the effect of improving durability differs depending on the type of photochromic moiety, and as a result, color shifts occur in the adjusted color tone. To suppress such color shifts, it is preferable to use a blending amount of 0.5 to 30 moles, more preferably 1 to 20 moles, and even more preferably 2 to 15 moles per mole of photochromic moiety.

[0147] In addition, other photochromic compounds besides the photochromic hydroxyurethane compounds of the present invention may be incorporated as long as they do not impair the effects of the present invention.

[0148] <Preferred composition of curable composition> In a curable composition containing the polymerizable compounds described above, the photochromic hydroxyurethane compound of the present invention can be either one having a polymerizable substituent or one without a polymerizable substituent. In any case, in order to obtain a sufficient color intensity, it is preferable that the amount of the hydroxyurethane compound of the present invention be set so that when the total amount of compounding agents other than the photochromic compound is 100 parts by mass, the mass corresponding to the photochromic portion (photochromic skeleton) is 0.001 to 10 parts by mass.

[0149] Furthermore, the more preferable amount of the photochromic compound, which is identified by the mass corresponding to the photochromic moiety, also varies depending on the method of exhibiting photochromicity. For example, when photochromicity is exhibited by the kneading method, the amount of the photochromic moiety is in the range of 0.001 to 2 parts by mass, particularly 0.001 to 1 part by mass, while when photochromicity is exhibited by the lamination method and the binder method, the amount of the photochromic moiety is in the range of 0.1 to 10 parts by mass, particularly 1 to 7 parts by mass.

[0150] Furthermore, the blending ratio of the hydroxyurethane compound of the present invention to other polymerizable compounds also varies depending on how many groups having photochromic moieties (photochromic skeletons) are contained in one molecule of the hydroxyurethane compound used. For example, if the blending amounts are defined based on a two-component standard of a hydroxyurethane compound and other polymerizable compounds, when the average number of photochromic groups contained in one molecule is 1 to 30, it is preferable to blend the hydroxyurethane compound in a ratio of 0.5 to 80% by mass and the total amount of other polymerizable compounds in a ratio of 20 to 99.5% by mass. Furthermore, when the average number of photochromic groups contained in one molecule is 30 to 300, it is preferable to blend the hydroxyurethane compound in a ratio of 0.1 to 50% by mass and the total amount of other polymerizable compounds in a ratio of 50 to 99.9% by mass.

[0151] Furthermore, in the present invention, in order to maximize the photochromicity-enhancing effect of the photochromic hydroxyurethane compound, it is preferable to select the type of polymerizable compound used in combination with the molecular structure of the hydroxyurethane compound.

[0152] For example, if the polymerizable substituent introduced into the hydroxyurethane compound is an acrylic group and / or a methacrylic group, it is preferable to select a radical polymerizable compound as the other polymerizable compound.

[0153] Furthermore, when the polymerizable substituent introduced into the hydroxyurethane compound is an OH group, it is preferable to use polyols, polythiols, polyamines, polyisocyanates, and polyisothiocyanates in combination such that urethane bonds, thiourethane bonds, urea bonds, or thiourea bonds (especially urethane bonds or thiourethane bonds) are formed.

[0154] <Use of curable compositions> When a photochromic hydroxyurethane compound of the present invention is introduced with a polymerizable substituent group, this hydroxyurethane compound can be used alone without being used in combination with other polymerizable compounds.

[0155] For example, a photochromic sheet (photochromic cured product) can be produced by forming a sheet using a curable composition that does not contain other polymerizable compounds. Alternatively, a coating solution can be prepared by dispersing or dissolving this curable composition in an organic solvent, and this coating solution can be applied to a transparent optical sheet or optical film and dried to form a photochromic coating layer (photochromic cured product), thereby exhibiting photochromic properties.

[0156] However, it is preferable that the curable composition of the present invention generally contains polymerizable compounds and other compounding agents in addition to the photochromic hydroxyurethane compound. For example, it is desirable to prepare a photochromic curable composition by melt-kneading each component, produce a photochromic cured body by polymerizing and curing this composition, and exhibit photochromic properties with this cured body. The following describes an example of a curable composition containing a polymerizable compound being used to produce a photochromic cured product. However, the same method as for curing the curable composition can be used when using only a photochromic hydroxyurethane compound into which a polymerizable substituent group has been introduced. Furthermore, the photochromic hydroxyurethane compound contained in the curable composition may or may not have a polymerizable substituent.

[0157] Polymerization curing for producing photochromic cured products is carried out by radical polymerization, ring-opening polymerization, anionic polymerization, or condensation polymerization using irradiation with active energy rays such as ultraviolet rays, alpha rays, beta rays, and gamma rays, heat, or a combination of both. In other words, an appropriate polymerization method should be adopted depending on the type of polymerizable compound and polymerization accelerator and the form of the photochromic cured product that is formed.

[0158] When thermally polymerizing the curable composition of the present invention, which contains polymerizable compounds, the polymerization temperature is particularly affected, as it influences the properties of the photochromic cured product. While these temperature conditions cannot be generalized as they are influenced by the type and amount of thermal polymerization initiator and the type of polymerizable compound, it is generally preferable to start polymerization at a relatively low temperature and slowly increase the temperature. Furthermore, while the polymerization time, like the temperature, is preferably determined according to various factors, it is generally preferable to select conditions such that polymerization is completed in 2 to 48 hours. In particular, when obtaining a photochromic laminated sheet, it is preferable to polymerize at a temperature at which the reaction between polymerizable functional groups proceeds, and to determine the optimal temperature and time at that time so that the desired molecular weight is achieved.

[0159] Furthermore, when photopolymerizing the curable composition of the present invention, UV intensity in particular affects the properties of the resulting photochromic cured product. While these illumination conditions cannot be generalized as they are influenced by the type and amount of photopolymerization initiator and the type of polymerizable monomer, they are generally rated at a wavelength of 365 nm and 50-500 mW / cm². 2 It is preferable to select conditions that allow UV light to be irradiated for a period of 0.5 to 5 minutes.

[0160] When photochromic properties are to be achieved by the mixing method utilizing polymerization curing as described above, the curable composition is injected between glass molds held by an elastomer gasket or spacer, and a photochromic cured body molded into the form of an optical material such as a lens can be obtained by casting polymerization using heating in an air furnace or irradiation with active energy rays such as ultraviolet light, depending on the type of polymerizable compound and polymerization curing accelerator. According to this method, eyeglass lenses and the like with photochromic properties can be obtained directly.

[0161] When photochromic properties are achieved by a lamination method, a coating solution is prepared by dissolving a curable composition in an appropriate organic solvent. This coating solution is then applied to the surface of an optical substrate, such as a lens substrate, by spin coating or dipping, dried to remove the organic solvent, and then polymerized and cured by UV irradiation or heating in an inert gas such as nitrogen. This forms a photochromic layer consisting of a photochromic cured material on the surface of the optical substrate (coating method).

[0162] Furthermore, a photochromic layer made of a photochromic cured material can also be formed on the surface of an optical substrate by casting polymerization using an inner mold, in which an optical substrate such as a lens substrate is placed facing a glass mold so that a predetermined void is formed, a curable composition is injected into this void, and polymerization curing is performed by UV irradiation or heating in this state (casting polymerization method).

[0163] When forming a photochromic layer on the surface of an optical substrate using the lamination methods described above (coating method and casting polymerization method), the adhesion between the photochromic layer and the optical substrate can be improved by pre-treating the surface of the optical substrate with chemical treatments such as alkaline solutions and acid solutions, or with physical treatments such as corona discharge, plasma discharge, and polishing. Of course, it is also possible to provide a transparent adhesive resin layer on the surface of the optical substrate.

[0164] Furthermore, when photochromic properties are to be achieved by the binder method, a photochromic sheet is prepared by sheet molding using a curable composition, and this is sandwiched between two transparent sheets (optical sheets). By performing the aforementioned polymerization curing, a photochromic laminate is obtained in which the photochromic layer is the adhesive layer. In this case, a method of coating using a coating solution in which a curable composition is dissolved in an organic solvent can also be employed to create the photochromic sheet.

[0165] The photochromic laminate produced in this manner can be, for example, placed in a mold, and then an optical substrate such as a lens with a predetermined shape and photochromic properties can be obtained by injection molding a thermoplastic resin (e.g., polycarbonate) for optical substrates. Furthermore, this photochromic laminate can also be bonded to the surface of an optical substrate using an adhesive, thereby obtaining a photochromic lens.

[0166] When producing a photochromic laminate as described above, it is preferable to use a urethane or urea-based polymerizable compound, particularly a urethane-based polymerizable compound, as the polymerizable compound, especially in terms of high adhesion to the optical substrate, and to prepare it so that polyurethane is formed.

[0167] The curable composition of the present invention described above can exhibit excellent photochromic properties in terms of color intensity and fading rate, and moreover, it does not reduce properties such as mechanical strength, and can be effectively used in the production of photochromic optical substrates, such as photochromic lenses.

[0168] Furthermore, the photochromic layer and photochromic cured body formed by the curable composition of the present invention can be subjected to post-processing such as dyeing with disperse dyes or other dyes, hard coat film creation using silane coupling agents or hard coat agents mainly composed of sols such as silicon, zirconium, antimony, aluminum, tin, and tungsten, thin film formation by deposition of metal oxides such as SiO2, TiO2, and ZrO2, and anti-reflective treatment and anti-static treatment by coating with organic polymers, depending on the application. [Examples]

[0169] The present invention will be explained by the following examples. The molecular weight of the compounds in the following experiment was measured as follows.

[0170] (molecular weight measurement) The molecular weight was determined by gel permeation chromatography (GPC) using a liquid chromatograph (Waters Corporation Japan), and converted to the weight-average molecular weight by comparison with polyethylene, under the following conditions. A differential refractometer was used as the detector. column: Depending on the molecular weight of the sample to be analyzed, we used the KF series of Shodex® GPC manufactured by Showa Denko K.K. KF-802 (exclusion limit molecular weight: 5,000) KF-802.5 (exclusion limit molecular weight: 20,000) KF-803 (exclusion limit molecular weight: 70,000) KF-804 (exclusion limit molecular weight: 400,000) KF-805 (exclusion limit molecular weight: 2,000,000) Developing agent: Dimethylformamide (DMF) Flow rate: 1ml / min Temperature: 40℃ Standard sample: Polyethylene

[0171] <Example 1> First step in the synthesis of photochromic hydroxyurethane compound (PHU1D1) (Synthesis of polysiloxane-type five-membered cyclic carbonates); An epoxy compound represented by the following formula (9) (average weight molecular weight 1996) was prepared.

[0172] [ka]

[0173] 10g (5.0 mmol) of the above epoxy compound Tetrabutylammonium bromide 0.24g (0.7 mmol) N-methylpyrrolidone 25mL The mixture was heated at 100°C for 56 hours under a carbon dioxide atmosphere. 1 The reaction was tracked by 1H-NMR to confirm that the starting epoxy compound had been consumed, and then the mixture was cooled to room temperature. Next, 50 mL of water and 100 mL of toluene were added, and liquid-liquid extraction was performed. Liquid-liquid extraction was repeated twice, and the solvent of the resulting organic layer was concentrated to obtain 9.9 g (96.5% yield) of a slightly yellowish, oily polydimethylpolysiloxane-type cyclic carbonate represented by the following formula (10).

[0174] [ka]

[0175] 2nd process (Synthesis of hydroxyurethane compounds (PHU1)); 4.2 g (2.0 mmol) of cyclic carbonate obtained in the first step. Dodecamethylenediamine 0.4g (2.0mmol) Tetrabutylammonium bromide 0.06g (0.2 mmol) Propylene glycol methyl ether acetate 2 mL The mixture was carried out at 100°C under a nitrogen atmosphere for 24 hours, and then cooled to room temperature. Next, 50 mL of water and 100 mL of toluene were added, and liquid-liquid extraction was performed. Liquid-liquid extraction was repeated twice, and the solvent of the resulting organic layer was concentrated to obtain 3.9 g of yellow, oily hydroxyurethane (PHU1), represented by the following formula. This hydroxyurethane (PHU1) has a polydimethylsilicone chain. Furthermore, it does not contain any photochromic groups and is therefore non-photochromic. Furthermore, the ratio of hydroxyl groups directly bonded to the main chain of the linear group to those bonded to the side chains extending from the linear chain is random.

[0176] [ka]

[0177] When the obtained PHU1 was analyzed by GPC, the weight-average molecular weight Mw(GPC) was found to be 6000 (number of repeats: 2.6). Furthermore, when the obtained PHU1 was analyzed by FT-IR, C=O stretching vibration (1703cm) originating from urethane bonding -1 ) generation and NH stretching vibration (3373cm -1 The generation of ) was confirmed.

[0178] 3rd process (Synthesis of compounds containing photochromic moieties); We prepared a compound represented by formula (11) and a compound represented by formula (12) below.

[0179] [ka]

[0180] [ka]

[0181] Compound represented by formula (11): 1.8 g (5.0 mmol) Compound represented by formula (12): 2.7 g (7.6 mmol) 0.13g (0.5 mmol) of pyridinium p-toluenesulfonate Toluene 50mL The mixture was heated and stirred at 75°C for 2 hours. After cooling to room temperature, it was washed three times with 50 mL of water, and the organic layer was removed by distillation under reduced pressure. The resulting residue was purified by silica gel column chromatography to obtain 2.4 g of the photochromic compound shown in formula (13) below. The yield was 70%.

[0182] [ka]

[0183] To the photochromic compound of formula (13) obtained above, Succinic anhydride 0.5g (5.0 mmol) Triethylamine 0.6g (6.0mmol) Dichloromethane 25 mL The mixture was added and stirred at room temperature for 12 hours. After the reaction, the dichloromethane was removed by distillation under reduced pressure, and the resulting residue was purified by silica gel chromatography to obtain 2.5 g (3.2 mmol) of the photochromic compound represented by formula (14) below, in which a carboxyl group was introduced at the terminal end. The yield was 90%.

[0184] [ka]

[0185] 4th step (Synthesis of photochromic hydroxyurethane (PHU1D1)); 0.6g (0.1 mmol) of PHU1 obtained in the second step. 0.16 g (0.2 mmol) of the photochromic compound of the terminal carboxyl group of formula (14) obtained in the third step. Dichloromethane 10ml After mixing and stirring, WSC(water-soluble carbodiimide) 192mg DMAP (Dimethylaminopyridine) 63mg The mixture was added and stirred for 12 hours under light shielding. After confirming the disappearance of the starting material by TLC (Thin-layer Chromatography), water was added to stop the reaction. After extraction with toluene, the mixture was concentrated in an evaporator and purified by silica gel chromatography to obtain 0.5 g of photochromic hydroxyurethane (PHU1D1) having a photochromic group represented by the following formula (15). The yield was 65%. In formula (15), the dashed line indicates the bond with hydroxyurethane (PHU1).

[0186] [ka]

[0187] Furthermore, regarding the compounds obtained above, 1 ¹H-NMR confirmed that the number of photochromic sites (photochromic basic frameworks) per repeating unit of PHU1 (hydroxyurethane) is approximately 2.0 (approximately 5.2 per molecule). The number of photochromic sites corresponds to the number in equation (15) above. The structural formula of the obtained photochromic hydroxyurethane (PHU1D1) is as follows. The numerical values ​​in the formula are average values.

[0188] [ka]

[0189] The above structural formula can be compared with each group in formula (2) as follows: [ka]

[0190] base R 3 Analysis of the following; Hydrogen atom ratio: 0% Photochromic area ratio: 100% Ratio of polymerization reactive groups: 0% Other base ratio: 0% Furthermore, the weight-average molecular weight (Mw) of the hydroxyurethane portion per photochromic group was 1154.

[0191] <Example 2> Synthesis of photochromic hydroxyurethane (PHU1D2); In the fourth step of Example 1, the amount of PHU1 (non-photochromic hydroxyurethane having a polydimethylsilicone chain) obtained in the second step was changed to 1.2 g (0.2 mmol), and the amount of the photochromic compound of the terminal carboxyl group of formula (14) was changed to 0.26 g (0.32 mmol). Otherwise, the same procedure as in Example 1 was performed to obtain 0.88 g (60% yield) of the photochromic hydroxyurethane compound (PHU1D2).

[0192] 1 ¹H-NMR confirmed that the number of photochromic sites (photochromic basic frameworks) per repeat of PHU1 (hydroxyurethane) is approximately 1.57 (approximately 4.1 per molecule).

[0193] The molecular structure of the obtained photochromic hydroxyurethane compound (PHU1D2) was analyzed in the same manner as in Example 1. The results are as follows (the following values ​​are average values).

[0194] base R 3 Analysis of the following; Hydrogen atom ratio: 21.5% Photochromic area ratio: 78.5% Ratio of polymerization reactive groups: 0% Other base ratio: 0%

[0195] <Example 3> Fabrication and evaluation of photochromic cured bodies (molded bodies); A curable composition was prepared using the photochromic hydroxyurethane compound (PHU1D1) obtained in Example 1, and a photochromic cured product was fabricated using this curable composition. Its photochromic properties were then evaluated.

[0196] Preparation of curable compositions; A polymerizable composition was prepared by thoroughly mixing each component according to the following formulation. Norbornene methane diisocyanate: 46.0 parts by mass Pentaerythritol-tetrakis(3-mercaptopropionate): 54.0 parts by mass The total amount of the polymerizable compounds described above was 100 parts by mass. The following additives were added to this total of 100 parts by mass of polymerizable compounds. Dimethyldichlorotin: 0.04 parts by mass Phosphorus-based release agent (JP-506H, manufactured by Johoku Chemical Industry Co., Ltd.): 0.1 part by mass.

[0197] Furthermore, when the total amount of polymerizable compounds was set to 100 g, a photochromic curable composition was prepared by kneading the PHU1D1 obtained in Example 1 so that the photochromic moiety amounted to 48 μmol.

[0198] Using the photochromic curable composition obtained by this mixing method, a photochromic cured product (polymer molded product) was obtained by curing it using the following polymerization method.

[0199] Polymerization method; A 2 mm thick mold was prepared using a glass mold and a gasket made of ethylene-vinyl acetate copolymer. The photochromic curable composition, which had been thoroughly degassed, was then poured into the mold. The polymerization reaction was then carried out by gradually increasing the temperature from 20°C to 120°C to cure the photochromic curable composition. After curing for 24 hours, the photochromic cured body was removed from the mold.

[0200] Evaluation of photochromic cured materials; The photochromic properties, L-scale Rockwell hardness, and transparency of the obtained photochromic cured material were evaluated using the following method, and the results are shown in Table 1.

[0201] (1) Photochromic properties Using a xenon lamp L-2480 (300W) SHL-100 manufactured by Hamamatsu Photonics Ltd., photochromic cured materials were irradiated with light through an air mass filter 2.0 (manufactured by Koyosha Co., Ltd.) to induce color development of the photochromic cured materials, and various photochromic properties were evaluated. The irradiation conditions were as follows. Irradiation temperature: 23±0.1℃ Luminous intensity: 50,000 lux in the range of 300-500 nm Irradiation time: 300 seconds The photochromic properties of the photochromic cured material were evaluated, including maximum absorption wavelength, color intensity, and fading rate. Measurements were performed using a spectrophotometer (instantaneous multi-channel photodetector MCPD1000) manufactured by Otsuka Electronics Industry Co., Ltd.

[0202] Maximum absorption wavelength (λmax); This is the maximum absorption wavelength in the visible light region of the photochromic cured material after color development. This maximum absorption wavelength is related to the color tone during color development. Color intensity {ε(300)-ε(0)}; The color intensity was evaluated by the difference between the absorbance {ε(300)} after 120 seconds of light irradiation at the maximum absorption wavelength and the absorbance ε(0) before light irradiation. A higher value indicates better photochromicity. Fading speed〔t1 / 2(sec.)〕; The photochromic cured material was irradiated with light for 300 seconds, and the fading rate was evaluated by the time it took for the absorbance at the maximum absorption wavelength to decrease to half of {ε(300)-ε(0)} after the light irradiation was stopped. A shorter time indicates better photochromicity.

[0203] (2) L-scale Rockwell hardness (HL) After storing a photochromic cured body (2 mm thick) in a desiccator at 23°C for one day, the L-scale Rockwell hardness of the cured body was measured using an Akashi Rockwell hardness tester (model: AR-10).

[0204] (3) Transparency of photochromic cured material The photochromic cured material was visually evaluated for turbidity under orthogonal nicols. The evaluation criteria were as follows: 1: The product is perfectly fine and there is no cloudiness. 2: The product is perfectly fine, but there is a very slight cloudiness. 3: The product is at an acceptable level, but there is a slight cloudiness. 4: The product is acceptable, but it is more cloudy than 3. 5: The product is cloudy and cannot be used.

[0205] <Example 4> A curable composition was prepared and a photochromic cured product was fabricated in exactly the same manner as in Example 3, except that the photochromic hydroxyurethane compound (PHU1D2) obtained in Example 2 was used instead of PHU1D1 obtained in Example 1, and the product was evaluated. The evaluation results are shown in Table 1.

[0206] <Comparative Examples 1-2> For comparison, photochromic cured products were obtained using compounds represented by the following formulas (A) and (B) in the same manner as in Example 1, and their properties were evaluated. The evaluation results are shown in Table 1.

[0207] [ka]

[0208] [Table 1]

[0209] As is clear from Table 1, the photochromic hydroxyurethane compound of the present invention exhibits superior photochromic properties in a high-hardness matrix compared to conventional photochromic compounds. Furthermore, by introducing the photochromic compound into the polyhydroxyurethane chain, it was demonstrated that the clouding of the cured product, which was difficult to solve with conventional photochromic compounds having oligomeric chains, can be suppressed.

[0210] <Example 5> Introduction of polymerizable substituents; Polymerizable substituents were introduced to the photochromic hydroxyurethane (PHU1D2) obtained in Example 2 by the following method. 0.75 g (0.08 mmol) of PHU1D2 was dissolved in 7.5 mL of THF, and 0.01 g (0.08 mmol) of 2-acryloyloxyethyl isocyanate was added dropwise to this solution. Two drops of dibutyltin dilaurate were then added as a catalyst, and the mixture was heated and stirred at room temperature for 24 hours. Water was added to stop the reaction. After extraction with toluene, the solution was concentrated using an evaporator and purified by silica gel chromatography to obtain photochromic polyhydroxyurethane (PHU1D2-2) in 80% yield.

[0211] This PHU1D2-2 has a photochromic group (a group having a photochromic moiety) represented by the aforementioned formula (15) and a polymerization-reactive group (containing an acrylic group as a polymerizable substituent) represented by the following formula (16).

[0212] [ka]

[0213] 1 ¹H-NMR confirmed that approximately 0.32 polymerization-reactive groups represented by formula (16) are introduced per repeat of PHU1 (approximately 0.9 groups per molecule).

[0214] Furthermore, the structural analysis of the obtained photochromic hydroxyurethane compound (PHU1D2-2), performed in the same manner as in Example 1, yielded the following results. base R 3 Analysis of the following; Hydrogen atom ratio: 5.5% Photochromic area ratio: 78.5% Ratio of polymerization-reactive groups: 16% Other base ratio: 0%

[0215] <Example 6> (Evaluation of physical properties of photochromic plastic lenses fabricated by coating method); A photochromic curable composition was prepared using the photochromic hydroxyurethane (PHU1D2-2) obtained in Example 5 above, according to the following formulation. This composition was applied to the surface of a lens substrate, and the coating film on the surface of the lens substrate was polymerized by irradiation with ultraviolet light.

[0216] In the photochromic curable composition prepared above, a mixture of the following compounds is used as the radical polymerizable monomer. Polyethylene glycol dimethacrylate (average molecular weight 736) 45 parts by mass Polyethylene glycol dimethacrylate (average molecular weight 536) 7 parts by mass Trimethylolpropane trimethacrylate 40 parts by mass γ-Methacryloyloxypropyltrimethoxysilane 2 parts by mass Glycidyl methacrylate 1 part by mass Furthermore, when the total amount of these radical polymerizable monomers is 100 parts by mass, the proportions of each component are as follows: Phenylbis(2,4,6-trimethylbenzoyl)phosphine Oxide (photopolymerization initiator, Irgacure 819, manufactured by BASF) 0.3 parts by mass Ethylenebis(oxyethylene)bis[3-(5-tert-butyl] (-4-hydroxy-m-tolyl)propionate) (stabilizer, Ciba) Irganox 245 (manufactured by Specialty Chemicals) 1 part by mass Bis(1,2,2,6,6-pentamethyl-4-piperidyl) Sebacate (molecular weight 508) 3 parts by mass Leveling agent (L7001, manufactured by Toray Dow Corning Co., Ltd.) 0.1 part by mass. Furthermore, the photochromic compound PHU1D2-2 was added in such a quantity that it amounted to 0.23 mmol when the total amount of the radical polymerizable monomers was 100 g.

[0217] Using the above-mentioned photochromic curable composition, polymerization curing was performed by lamination under the following conditions to obtain a photochromic laminate.

[0218] Polymerization hardening; A thiourethane-based plastic lens with a central thickness of 2 mm and a refractive index of 1.60 was prepared as the optical substrate. This thiourethane-based plastic lens was pre-etched using a 10% sodium hydroxide aqueous solution at 50°C for 5 minutes, and then thoroughly washed with distilled water.

[0219] Using a spin coater (1H-DX2, manufactured by MIKASA), a moisture-curing primer (product name: TR-SC-P, manufactured by Tokuyama Corporation) was applied to the surface of the above-mentioned plastic lens at a rotation speed of 70 rpm for 15 seconds, followed by 1000 rpm for 10 seconds. Subsequently, approximately 2 g of the photochromic composition obtained above was spin-coated at a rotation speed of 60 rpm for 40 seconds, followed by 600 rpm for 10-20 seconds, until the thickness of the photochromic coating layer reached 40 μm.

[0220] A lens with a coating agent applied to its surface in this manner is subjected to a 200 mW / cm² output in a nitrogen gas atmosphere. 2The coating was cured by irradiating it with light for 90 seconds using a metal halide lamp. Then, it was further heated at 110°C for 1 hour to create a photochromic laminate having a photochromic layer.

[0221] The photochromic properties and transparency of the obtained photochromic laminates were evaluated in the same manner as in Examples 3 and 4, and the Vickers hardness was further evaluated using the method described below. The evaluation results are shown in Table 2.

[0222] Vickers hardness The hardness was measured using an automatic measurement (reading) device equipped with a hardness tester (PMT-X7A, manufactured by Matsuzawa Co., Ltd.). Specifically, a Vickers indenter was pressed into the sample surface at 10 gf for 30 seconds, and the Vickers hardness was obtained from the indentation. Vickers hardness is an indicator of whether or not a lens will be scratched during the lens manufacturing process. As a general guideline, a Vickers hardness of 4.5 or higher indicates that the lens is less likely to be scratched, while a hardness of 4.5 or lower indicates that it is more susceptible to scratches.

[0223] [Table 2]

[0224] <Example 7> 1st step; In Example 1, the reaction was carried out in the same manner except that the compound of formula (17) below was used instead of the epoxy compound of formula (9) above, to obtain a cyclic carbonate compound represented by formula (18) below.

[0225] [ka]

[0226] [ka]

[0227] 2nd step; In Example 1, the reaction was carried out in the same manner as in Example 1, except that the compound of formula (19) below was used instead of dodecamethylenediamine, and the compound of formula (18) above was used instead of the compound of formula (10) above, to obtain PHU2 represented by the following formula (20).

[0228] [ka]

[0229] [ka]

[0230] Furthermore, the ratio of hydroxyl groups directly bonded to the main chain of the linear group to those bonded to the side chains extending from the linear chain is random. When the obtained PHU2 was analyzed by GPC, the weight-average molecular weight Mw(GPC) was found to be 8660 (approximately 4.4 repeats). Analysis of the obtained PHU2 using FT-IR confirmed the generation of C=O stretching vibrations originating from urethane bonds, as well as NH stretching vibrations.

[0231] 3rd step; The reaction was carried out in the same manner as in Example 1, except that the compounds of formulas (21) and (22) below were used instead of formulas (11) and (12) in the third step, to synthesize the compound represented by formula (23) below.

[0232] [ka]

[0233] [ka]

[0234] [ka]

[0235] 4th step; The reaction was carried out in the same manner as in Example 1, except that PHU2 was used instead of PHU1 in the fourth step, and formula (23) was used instead of formula (14), to obtain a photochromic hydroxyurethane (PHU2D1) having a photochromic group represented by the following formula (24). The yield was 65%.

[0236] [ka]

[0237] In formula (24), the dashed line indicates the bond with hydroxyurethane (PHU2). Regarding the compound obtained above, 1 ¹H-NMR confirmed that the number of photochromic sites (photochromic basic frameworks) per repeat of PHU2 (hydroxyurethane) is approximately 2.0 (approximately 8.8 per molecule). The number of photochromic sites corresponds to the number in equation (24) above. The structural formula of the obtained photochromic hydroxyurethane (PHU2D2) is as follows. The numerical values ​​in the formula are average values.

[0238] [ka]

[0239] base R 3 Analysis of the following; Hydrogen atom ratio: 0%. Ratio of groups containing photochromic moieties: 100%. Ratio of polymerization reactive groups: 0%. Other component ratio: 0%. Furthermore, the weight-average molecular weight (Mw) of the hydroxyurethane portion per photochromic group was 984.

[0240] <Example 8> 1st step; In Example 1, the reaction was carried out in the same manner except that the compound of formula (25) below was used instead of the epoxy compound of formula (9) above, to obtain a cyclic carbonate compound represented by formula (26) below.

[0241] [ka]

[0242] [ka]

[0243] 2nd step; The reaction was carried out in the same manner as in Example 1, except that the compound of formula (27) below was used instead of dodecamethylenediamine, and the compound of formula (26) above was used instead of the compound of formula (10), to obtain PHU3 represented by the following formula (28).

[0244] [ka]

[0245] [ka]

[0246] Furthermore, the ratio of hydroxyl groups directly bonded to the main chain of the linear group to those bonded to the side chains extending from the linear chain is random. When the obtained PHU3 was analyzed by GPC, the weight-average molecular weight Mw(GPC) was found to be 7784 (approximately 2.9 repeats). Analysis of the obtained PHU3 using FT-IR confirmed the generation of C=O stretching vibrations originating from urethane bonds, as well as NH stretching vibrations.

[0247] 3rd step; The reaction was carried out in the same manner as in Example 1, except that the compound of formula (29) below was used instead of formula (11) in the third step, to synthesize the compound represented by formula (30) below.

[0248] [ka]

[0249] [ka]

[0250] 4th step; The reaction was carried out in the same manner as in Example 1, except that PHU3 was used instead of PHU1 in the fourth step, and formula (30) was used instead of formula (14), to obtain a photochromic hydroxyurethane (PHU3D1) having a photochromic group represented by the following formula (31). The yield was 69%.

[0251] [ka]

[0252] In formula (31), the dashed line indicates the bond with hydroxyurethane (PHU3). Regarding the compound obtained above, 1 ¹H-NMR confirmed that the number of photochromic sites (photochromic basic frameworks) per repeat of PHU3 (hydroxyurethane) is approximately 2.0 (approximately 5.8 per molecule). The number of photochromic sites corresponds to the number in equation (31) above. The structural formula of the obtained photochromic polyhydroxyurethane compound (PHU3D1) is as follows. The numerical values ​​in the formula are average values.

[0253] [ka] In the formula, (31) represents formula (31), and the dashed line indicates the dashed portion in formula (31).

[0254] base R 3 Analysis of the following; Hydrogen atom ratio: 0%. Ratio of groups containing photochromic moieties: 100%. Ratio of polymerization reactive groups: 0%. Other component ratio: 0%. Furthermore, the weight-average molecular weight (Mw) of the hydroxyurethane portion per photochromic group was 1342.

[0255] <Example 9> 1st step; In Example 8, the reaction was carried out in the same manner, except that the compound of formula (32) below was used instead of the epoxy compound of formula (25), to obtain a cyclic carbonate compound represented by formula (33) below.

[0256] [ka]

[0257] [ka]

[0258] 2nd step; In the second step of Example 8, the reaction was carried out in the same manner except that the compound of formula (33) was used instead of the compound of formula (28), and HU4 represented by the following formula (34) was obtained.

[0259] [ka]

[0260] Furthermore, the ratio of hydroxyl groups directly bonded to the main chain of the linear group to those bonded to the side chains extending from the linear chain is random. When the obtained HU4 was analyzed by GPC, its weight-average molecular weight Mw(GPC) was found to be 5392. Analysis of the obtained HU4 using FT-IR confirmed the generation of C=O stretching vibrations originating from urethane bonds, as well as NH stretching vibrations.

[0261] 3rd step; The reaction was carried out in the same manner as in Example 8, except that HU4 was used instead of PHU3 in the fourth step, and formula (35) below was used instead of formula (30) above, to obtain a photochromic hydroxyurethane (HU4D1) having a photochromic group represented by formula (36) below. The yield was 78%.

[0262] [ka]

[0263] [ka]

[0264] In formula (36), the dashed line indicates the bond with hydroxyurethane (HU4). Regarding the compound obtained above, 1 ¹H-NMR confirmed that HU4 (hydroxyurethane) contains approximately 2.0 photochromic moieties (photochromic basic frameworks). The number of photochromic moieties corresponds to the number in equation (36) above. The structural formula of the obtained photochromic hydroxyurethane compound (HU4D1) is as follows. The numerical values ​​in the formula are average values.

[0265] [ka] In the formula, (36) represents the aforementioned formula (36), and the dashed line indicates the dashed portion in formula (36).

[0266] base R 3 Analysis of the following; Hydrogen atom ratio: 0%. Ratio of groups containing photochromic moieties: 100%. Ratio of polymerization reactive groups: 0%. Other component ratio: 0%. Furthermore, the weight-average molecular weight (Mw) of the hydroxyurethane portion per photochromic group was 2696.

[0267] <Example 10> 1st step; In the first step of Example 8, the reaction was carried out in the same manner except that the compound of formula (37) below was used instead of the epoxy compound of formula (25) above, to obtain a cyclic carbonate compound represented by formula (38) below.

[0268] [ka]

[0269] [ka]

[0270] 2nd step; In the second step of Example 8, the reaction was carried out in the same manner except that the compound of formula (38) was used instead of the compound of formula (27), and PHU5 represented by the following formula (39) was obtained.

[0271] [ka]

[0272] Furthermore, the ratio of hydroxyl groups directly bonded to the main chain of the linear group to those bonded to the side chains extending from the linear chain is random. When the obtained PHU5 was analyzed by GPC, the weight-average molecular weight Mw(GPC) was found to be 6608 (repeating count approximately 1.6). Analysis of the obtained PHU5 using FT-IR confirmed the generation of C=O stretching vibrations originating from urethane bonds, as well as NH stretching vibrations.

[0273] 3rd step; In the third step of Example 1, the reaction was carried out in the same manner except that the compound of formula (40) below was used instead of formula (11) above, and a compound represented by formula (41) below was synthesized.

[0274] [ka]

[0275] [ka]

[0276] 4th step; The reaction was carried out in the same manner as in Example 1, except that PHU5 was used instead of PHU1 in the fourth step, and formula (41) was used instead of formula (14), to obtain a photochromic hydroxyurethane (PHU5D1) having a photochromic group represented by the following formula (42). The yield was 62%.

[0277] [ka] In formula (42), the dashed line indicates the bond with hydroxyurethane (PHU5).

[0278] Regarding the compound obtained above, 1 ¹H-NMR confirmed that PHU5 (hydroxyurethane) contains approximately 2.0 photochromic sites (photochromic basic frameworks) (approximately 3.2 per molecule). The number of photochromic sites corresponds to the number in equation (42) above. The structural formula of the obtained photochromic polyhydroxyurethane compound (PHU5D1) is as follows. The numerical values ​​in the formula are average values. (The dashed line in the figure indicates bonding with PHU5.)

[0279] [ka]

[0280] base R 3 Analysis of the following; Hydrogen atom ratio: 0%. Ratio of groups containing photochromic moieties: 100%. Ratio of polymerization reactive groups: 0%. Other component ratio: 0%. Furthermore, the weight-average molecular weight (Mw) of the hydroxyurethane portion per photochromic group was 2065.

[0281] <Example 11> 1st step; In the fourth step of Example 10, the same procedure was followed except that the amount of the compound represented by formula (41) used was reduced to half (1 equivalent in addition to hydroxyurethane) and the reaction was carried out, yielding a photochromic polyhydroxyurethane compound (PHU5D2) in a yield of 54%. 1 ¹H-NMR confirmed that the number of photochromic sites (photochromic basic frameworks) per repeat of PHU5 is approximately 1.21 (approximately 1.94 per molecule). The number of photochromic sites corresponds to the number in equation (42) above. The properties of the obtained photochromic polyhydroxyurethane compound (PHU5D2) are shown below. The following values ​​are average values.

[0282] base R 3 Analysis of the following; Hydrogen atom ratio: 29.5%. Percentage of groups containing photochromic moieties: 60.5%. Ratio of polymerization reactive groups: 0%. Other component ratio: 0%. Furthermore, the weight-average molecular weight (Mw) of the hydroxyurethane portion per photochromic group was 3413.

[0283] <Example 12> 1st step; In the fourth step of Example 10, the same procedure was followed except that the amount of the compound represented by formula (41) used was reduced to 30% (0.6 equivalents of hydroxyurethane) to carry out the reaction, and a photochromic polyhydroxyurethane compound (PHU5D3) was obtained in a yield of 43%. 1 ¹H-NMR confirmed that the number of photochromic sites (photochromic basic frameworks) per repeat of PHU5 is approximately 0.68 (approximately 1.09 per molecule). The number of photochromic sites corresponds to the number in equation (42) above.

[0284] The properties of the obtained photochromic polyhydroxyurethane compound (PHU5D3) are shown below. The following values ​​are average values.

[0285] base R 3 Analysis of the following; Hydrogen atom ratio: 66.0%. Percentage of groups containing photochromic moieties: 34.0%. Ratio of polymerization reactive groups: 0%. Other component ratio: 0%. Furthermore, the weight-average molecular weight (Mw) of the hydroxyurethane portion per photochromic group was 6062.

[0286] <Examples 13-18> (Evaluation of physical properties of photochromic plastic lenses fabricated by lamination method); A photochromic curable composition was prepared using the photochromic hydroxyurethane obtained in Examples 7 to 12 above, according to the following formulation, and this composition was cast and polymerized on the surface of a lens substrate.

[0287] (Preparation of curable composition) A photochromic curable composition was prepared by thoroughly mixing each component according to the following formulation.

[0288] (Composition of polymerizable compounds) 1,3-Bis(isocyanatomethyl)cyclohexane: 43.0 parts by mass Pentaerythritol-tetrakis(3-mercaptopropionate): 49.4 parts by mass Tridecane 1-thiol: 3.3 parts by mass RX-1: (Polyrotaxane monomer synthesized by the method described in the third step of Example 1 of International Publication No. 2018 / 235771 (pr1 in International Publication No. 2018 / 235711; Reference Example 1)): 4.3 parts by mass. The total amount of the polymerizable compounds listed above was 100 parts by mass. For every 100 parts by mass of this polymerizable compound, 0.05 parts by mass of dimethyldichlorotin was added.

[0289] Furthermore, the photochromic curable composition was prepared by adding the photochromic polyhydroxyurethane compound to a total of 100g of polymerizable compounds, such that the photochromic portion was 0.1 mmol. Using the photochromic curable composition thus obtained, a photochromic laminate was obtained by a bonding method. The polymerization method is as follows.

[0290] After thoroughly degassing the above photochromic curable composition, it was injected into a mold consisting of a glass plate with a 1 mm gap and a thiourethane-based plastic lens with a refractive index of 1.60, and the photochromic curable composition was polymerized by casting polymerization. Polymerization was cured over 18 hours while gradually increasing the temperature from 27°C to 120°C. After polymerization, by removing only the glass plate, a bonded photochromic optical article was obtained in which a 1 mm thick photochromic layer was laminated on a thiourethane-based plastic lens with a refractive index of 1.60. The obtained photochromic laminate was used as a sample and evaluated.

[0291] <Comparative Examples 3 and 4> For comparison, see formula (A) above and formula (C) below. I used it. [ka]

[0292] The evaluation criteria were the same as in Example 3: photochromicity and turbidity. The evaluation results are shown in Table 3. [Table 3]

[0293] <Example 19> 1st step; In the second step of Example 10, the reaction was carried out in the same manner except that the compound of formula (38) was replaced with the compound of formula (43) below, to obtain PHU6 represented by the formula (44) below.

[0294] [ka]

[0295] [ka]

[0296] Furthermore, the ratio of hydroxyl groups directly bonded to the main chain of the linear group to those bonded to the side chains extending from the linear chain is random. When the obtained PHU6 was analyzed by GPC, the weight-average molecular weight Mw(GPC) was found to be 7070 (repeating count approximately 2.1). Analysis of the obtained PHU6 using FT-IR confirmed the generation of C=O stretching vibrations originating from urethane bonds, as well as NH stretching vibrations.

[0297] 2nd step; In the third step of Example 1, the reaction was carried out in the same manner except that the compound of formula (45) below was used instead of formula (11) and the compound of formula (46) below was used instead of formula (12), and a compound represented by formula (47) below was obtained.

[0298] [ka]

[0299] [ka]

[0300] [ka]

[0301] 3rd step; The reaction was carried out in the same manner as in Example 1, except that PHU6 was used instead of PHU1 in the fourth step, and formula (47) was used instead of formula (14), to obtain a photochromic hydroxyurethane (PHU6D1) having a photochromic group represented by the following formula (48). The yield was 60%.

[0302] [ka] In formula (48), the dashed line indicates the bond with hydroxyurethane (PHU6).

[0303] Regarding the compound obtained above, 1 ¹H-NMR confirmed that PHU6 (hydroxyurethane) contains approximately 2.0 photochromic sites (photochromic basic frameworks) (approximately 4.2 per molecule). The number of photochromic sites corresponds to the number in equation (48) above. The structural formula of the obtained photochromic polyhydroxyurethane compound (PHU6D1) is as follows. The numerical values ​​in the formula are average values. (The dashed line in the figure indicates bonding with PHU6.)

[0304] [ka]

[0305] base R 3 Analysis of the following; Hydrogen atom ratio: 0%. Ratio of groups containing photochromic moieties: 100%. Ratio of groups with polymerizable substituents: 0%. Ratio of groups with other groups: 0%. Furthermore, the weight-average molecular weight (Mw) of the hydroxyurethane portion per photochromic group was 1683.

[0306] <Example 20> 1st step; In the first step of Example 2, the procedure was carried out in the same manner except that the compound of formula (47) was used instead of the compound of formula (14) and PHU6 was used instead of PHU1, and a photochromic polyhydroxyurethane compound (PHU6D2) was obtained in a yield of 57%. 1 ¹H-NMR confirmed that approximately 1.48 photochromic sites, as shown in the above formula, are introduced per repeat of PHU6 (approximately 3.1 photochromic sites in total).

[0307] base R 3 Analysis of the following; Hydrogen atom ratio: 26.0%. Percentage of groups containing photochromic moieties: 74.0%. Ratio of polymerization reactive groups: 0%. Other component ratio: 0%.

[0308] 2nd step; Polyethylene glycol monomethacrylate with a number-average molecular weight of 500 10g (20 mmol) Succinic anhydride 2.2g (22 mmol) Triethylamine 3.3g (3.3 mmol) 100 mL of dichloromethane was added and the mixture was stirred at room temperature for 12 hours. After the reaction, the dichloromethane was removed by distillation under reduced pressure, and the resulting residue was purified by silica gel chromatography to obtain the compound represented by the following formula (49) in 88% yield.

[0309] [ka]

[0310] 0.6 g (0.10 mmol) of the compound of formula (49) obtained above. and PHU6D2 0.83g (0.10 mmol) Dissolve in 15 mL of THF. WSC(water-soluble carbodiimide) 192mg DMAP (Dimethylaminopyridine) 63mg The mixture was added and stirred for 12 hours under light shielding. After the reaction, water was added to stop the reaction, and the mixture was extracted with toluene and concentrated using an evaporator. The obtained residue was dissolved in chloroform and purified using a recycled preparative HPLC (Labo-Ace7080) manufactured by Nippon Analytical Engineering Co., Ltd. The purification was performed using chloroform as the mobile phase and a preparative column consisting of JAIGELHR-2.5HR and JAIGELHR-3HR connected in series, yielding photochromic polyhydroxyurethane (PHU6D2-2) in 75% yield. This PHU6D2-2 has a photochromic group (a group having a photochromic moiety) represented by the aforementioned formula (48) and a polymerization-reactive group (containing a methacrylic group as a polymerizable substituent) represented by the following formula (50).

[0311] [ka]

[0312] 1 ¹H-NMR confirmed that approximately 0.51 polymerization-reactive groups represented by the above formula are introduced per repeat of PHU6 (approximately 1.07 groups per molecule). The properties of the obtained photochromic polyhydroxyurethane compound (PHU6D2-2) are shown below. The following values ​​are average values.

[0313] base R 3 Analysis of the following; Hydrogen atom ratio: 0.5%. Percentage of groups containing photochromic moieties: 74.0%. Ratio of polymerization-reactive groups: 25.5%. Other component ratio: 0%. Furthermore, the weight-average molecular weight (Mw) of the hydroxyurethane portion per photochromic group was 2275.

[0314] <Examples 21-26> (Evaluation of physical properties of photochromic plastic lenses fabricated by coating method); A photochromic laminate was fabricated using the same method as in Example 6, and evaluated using the same method. Compound C was evaluated similarly as Comparative Example 5. The results are shown in Table 4.

[0315] [Table 4]

[0316] As is clear from the comparison between Example 21 and the comparative example in Table 4, the compound of the present invention exhibits excellent photochromic properties.

[0317] <Example 27> 1st step; In the first step of Example 8, the reaction was carried out in the same manner except that the compound of formula (25) was replaced with the compound of formula (51) below, to obtain a cyclic carbonate compound represented by the formula (52) below.

[0318] [ka]

[0319] [ka]

[0320] 2nd step; In the second step of Example 8, the reaction was carried out in the same manner, except that the compound shown in formula (52) was used instead of the compound of formula (26), to obtain PHU7 represented by the following formula (53).

[0321] [ka]

[0322] Furthermore, the ratio of hydroxyl groups directly bonded to the main chain of the linear group to those bonded to the side chains extending from the linear chain is random. When the obtained PHU7 was analyzed by GPC, the weight-average molecular weight Mw(GPC) was found to be 11640 (approximately 3.6 repeats). Analysis of the obtained PHU7 using FT-IR confirmed the generation of C=O stretching vibrations originating from urethane bonds, as well as NH stretching vibrations.

[0323] 3rd step; The reaction was carried out in the same manner as in the third step of Example 1, except that formula (54) below was used instead of formula (13), to obtain the compound represented by formula (55) below.

[0324] [ka]

[0325] [ka]

[0326] 4th step; In the fourth step of Example 1, PHU7 was used instead of PHU1, and the compound of formula (55) was used instead of formula (14), but the reaction was carried out in the same manner to obtain a photochromic hydroxyurethane (PHU7D1) having a photochromic group represented by the following formula (56). The yield was 58%.

[0327] [ka] In formula (56), the dashed line indicates the bond with hydroxyurethane (PHU7).

[0328] Regarding the compound obtained above, 1 ¹H-NMR confirmed that the number of photochromic sites (photochromic basic frameworks) per repeat of PHU7 (hydroxyurethane) is approximately 2.0 (approximately 7.2 per molecule). The number of photochromic sites corresponds to the number in equation (56) above. The structural formula of the obtained photochromic polyhydroxyurethane compound (PHU7D1) is as follows. The numerical values ​​in the formula are average values.

[0329] [ka]

[0330] base R 3 Analysis of the following; Hydrogen atom ratio: 0%. Ratio of groups containing photochromic moieties: 100%. Ratio of polymerization reactive groups: 0%. Other component ratio: 0%. Furthermore, the weight-average molecular weight (Mw) of the hydroxyurethane portion per photochromic group was 1617.

[0331] <Example 28> (Evaluation of physical properties of photochromic laminates fabricated by the binder method); (Fabrication of photochromic layer (photochromic adhesive layer)) The photochromic layer was fabricated using the following method.

[0332] 1. Production of terminally non-reactive urethane urea resin A 2L four-necked flask fitted with a stirring blade, condenser, thermometer, and nitrogen gas inlet tube, 158 parts by mass of polycarbonate diol with a number-average molecular weight of 500 Isophorone diisocyanate 100 parts by mass Toluene 72 parts by mass The mixture was prepared and reacted at 100°C for 7 hours under a nitrogen atmosphere to synthesize a urethane prepolymer having isocyanate groups at its ends. After synthesizing the urethane prepolymer, the reaction solution was cooled to around 0°C, dissolved in 205 parts by mass of isopropyl alcohol and 382 parts by mass of diethyl ketone, and then the solution temperature was maintained at 0°C. Next, a mixed solution of 23 parts by mass of bis-(4-aminocyclohexyl)methane and 20 parts by mass of diethyl ketone, which are chain extenders, was added dropwise within 30 minutes, and the mixture was reacted at 0°C for 1 hour. Subsequently, 5.7 parts by mass of 1,2,2,6,6-pentamethyl-4-aminopiperidine were added dropwise, and the mixture was reacted at 0°C for 1 hour to obtain a diethyl ketone solution of terminally unreactive urethane urea resin.

[0333] 2. Preparation of a composition for forming a photochromic layer Per 100 parts by mass of the solid content of the obtained end-unreactive urethane urea resin solution, 4 parts by mass of an isomer mixture of 4,4'-methylenebis(cyclohexyl isocyanate) (polyisocyanate compound) Ethylene bis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] is used as an antioxidant. 0.4 parts by mass As a surfactant, the product name is DOW CORNING TORAY L-7001 0.06 parts by mass It contains [ingredient]. Furthermore, when the solid content of the solution of the terminally nonreactive urethane urea resin was assumed to be 100 g, PHU7D1 was added so that the photochromic portion was 0.23 mmol, and the mixture was stirred and mixed at room temperature to obtain a composition for forming a photochromic layer.

[0334] 3. Synthesis of adhesive for bonding layers (end-response non-reactive urethane urea resin) Prepare a 5L separable flask (with four necks) fitted with a stirring blade, condenser, thermometer, and nitrogen gas inlet tube, and in this container, 400 parts by mass of polycarbonate diol with a number-average molecular weight of 1000 Isophorone diisocyanate 175 parts by mass 120 parts by mass of toluene The mixture was prepared and reacted at 110°C for 7 hours under a nitrogen atmosphere to synthesize a urethane prepolymer having isocyanate groups at its ends. After the urethane prepolymer was synthesized, the reaction solution was cooled to approximately 20°C, dissolved in 2500 parts by mass of propylene glycol-monomethyl ether, and then the solution temperature was maintained at 20°C. Next, 60 parts by mass of isophorone diamine, a chain extender, was added dropwise, and the mixture was reacted at 20°C for 1 hour. Subsequently, 3 parts by mass of n-butylamine was added dropwise, and the mixture was reacted at 20°C for 1 hour to obtain a propylene glycol-monomethyl ether solution of terminally unreactive urethane urea resin. To 500 parts by mass of the obtained terminally nonreactive urethane urea resin solution, 0.2 parts by mass of the surfactant (product name DOW CORNING TORAY L-7001) was added, and the mixture was stirred and mixed at room temperature to obtain an adhesive for the bonding layer.

[0335] 4. Manufacturing of photochromic laminates Using a coater (manufactured by Tester Industries), the adhesive for the bonding layer was applied to a 400 μm thick polycarbonate sheet (first and second optical sheets; one being an optical substrate and the other a layer not containing a photochromic compound) at a coating speed of 0.5 m / min, and dried at a drying temperature of 110°C for 3 minutes to obtain a polycarbonate sheet having an adhesive resin layer with a thickness of 5 μm.

[0336] Next, using a coater (manufactured by Tester Industries), the photochromic layer-forming composition was applied to a 50 μm thick OPP film (stretched polypropylene film) at a coating speed of 0.3 m / min and dried at a drying temperature of 100°C for 5 minutes. This formed a photochromic layer. Subsequently, the photochromic layer (40 μm thick) was placed on the adhesive resin layer of the first optical sheet having the adhesive resin layer and bonded together.

[0337] Furthermore, a structure obtained by peeling off the OPP film from a first optical sheet / adhesive resin layer / photochromic layer / OPP film laminated in the order prepared by the above method was bonded to a polycarbonate sheet (second optical sheet) having an adhesive resin layer, such that the photochromic layer and the adhesive resin layer on the polycarbonate sheet (second optical sheet) were joined together. Next, the resulting laminate was left to stand at 40°C under vacuum for 24 hours, then heat-treated at 110°C for 60 minutes, followed by humidification at 60°C and 100% RH for 24 hours, and finally left to stand at 40°C under vacuum for 24 hours to obtain a photochromic laminate. The obtained photochromic laminate was evaluated in the same manner as in Example 13. For comparison, a compound of formula (D) below was used (Comparative Example 6). The evaluation results are shown in Table 5.

[0338] [ka]

[0339] [Table 5]

[0340] From the results above, it can be seen that the photochromic compound of the present invention exhibits excellent photochromic properties even in the binder method.

Claims

1. A photochromic urethane compound having a urethane structural unit represented by the following formula (1), provided that it has at least one photochromic moiety within the molecule, which is the smallest photochromic unit consisting of a naphthopyran skeleton; -X-O-CO-NH- (1) During the ceremony, X is an oxygen-containing chain organic group having a hydroxyl group as a substituent, or an oxygen-containing chain organic group in which the hydrogen atom of the hydroxyl group is substituted with any of the following groups (A) to (D); (A) Photochromic group having the photochromic moiety, (B) Polymerization-reactive group having a polymerizable substituent, (C) C1-C10 alkyl group, (D) Cycloalkyl groups having 3 to 10 carbon atoms, However, each of the above groups (C) to (D) may be bonded to an oxygen atom derived from a hydroxyl group via an oxygen-containing chain organic group. The urethane structural unit comprises a plurality of such units, and the photochromic portion is present in at least one of the urethane structural units. The aforementioned photochromic urethane compound is represented by the following formula (2): 【Chemistry 1】 During the ceremony, n is an integer between 2 and 100. R １００ This includes a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or an aryl group having 6 to 14 carbon atoms. R ２００ This includes a hydroxyl group, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or an aryl group having 6 to 14 carbon atoms. -X １ -R １ -X ２ - is a group corresponding to group X in formula (1) above, X １ and X ２ These are divalent groups represented by either formula (2a) or (2b) below, 【Chemistry 2】 In formulas (2a) to (2b), R ３ is a hydrogen atom or any of the groups (A) to (D), and among the plurality of Rs present in formula (2), at least one is a photochromic group, ３ ​ R ４ It is a hydrogen atom, R １ and R ２ These are, respectively, an alkylene group having 1 to 15 carbon atoms, a poly(oxyethylene) group having 2 to 200 carbon atoms, a poly(oxypropylene) group having 3 to 300 carbon atoms, or a poly(oxydimethylsilylene) group. The aforementioned photochromic site is an indeno[2,1-f]naphtho[1,2-b]pyran skeleton, A photochromic urethane compound characterized in that the photochromic group is represented by the following formula (4); 【Transformation 3】 During the ceremony, d and e are both 0, PC is a group that has a photochromic site, R ８ This is an alkylene group having 1 to 30 carbon atoms. R ９ This is an alkylene group having 1 to 30 carbon atoms, or an alkylene group having 1 to 30 carbon atoms with an ether bond. Z １ is an oxygen atom, a sulfur atom, or NH, L can be expressed by one of the following formulas. 【Chemistry 4】

2. The photochromic urethane compound according to claim 1, wherein the polymerizable substituent is at least one group selected from the group consisting of an acrylic group, a methacrylic group, an allyl group, a vinyl group, a 4-vinylphenyl group, an epoxy group, an episulfide group, a thietanyl group, a carboxyl group, a hydroxyl group, a thiol group, an amino group, an isocyanate group, and a thiocyanate group.

3. The photochromic urethane compound according to claim 1, wherein the polymerization reactive group is represented by the following formula (6); 【Transformation 5】 During the ceremony, PG is a polymerizable substituent, d １ and e １ These are all 0, R ８１ This is an alkylene group having 1 to 30 carbon atoms. R ９１ This is an alkylene group having 1 to 30 carbon atoms, or an alkylene group having 1 to 30 carbon atoms with an ether bond. Z １１ is an oxygen atom, a sulfur atom, or an NH group, L' can be expressed by one of the following formulas. 【Transformation 6】

4. The photochromic urethane compound according to Claim 1, wherein the photochromic urethane compound is represented by any of the following formulas. 【Transformation 7】 In the equation, equation (15) is expressed as follows: 【Transformation 8】 ， 【Chemistry 9】 In the equation, equation (24) is expressed as follows: 【Chemistry 10】 ， 【Chemistry 11】 In the formula, equation (31) is expressed as follows: 【Chemistry 12】 ， 【Chemistry 13】 In the formula, equation (36) is expressed as follows: 【Chemistry 14】 ， 【Chemistry 15】 In the equation, equation (42) is expressed as follows: 【Chemistry 16】 ， 【Chemistry 17】 In the equation, equation (48) is expressed as follows: [Chemistry 18] ， 【Chemistry 19】 In the formula, equation (56) is expressed as follows: 【Chemistry 20】

5. A curable composition comprising the photochromic urethane compound described in claim 1 and other polymerizable compounds.

6. The curable composition according to claim 5, wherein the other polymerizable compound has at least one selected from the group consisting of a carboxyl group, a hydroxyl group, a thiol group, an amino group, an isocyanate group, and a thiocyanate group as a polymerizable substituent.

7. The curable composition according to claim 5, wherein the other polymerizable compound has at least one radical polymerizable group selected from the group consisting of an acrylic group, a methacrylic group, an allyl group, a vinyl group, and a 4-vinylphenyl group as a polymerizable substituent.

8. The curable composition according to claim 5, wherein the other polymerizable compound is a compound having at least one polymerizable substituent selected from the group consisting of epoxy groups, episulfide groups, and thietanyl groups.

9. A photochromic cured body obtained by curing the curable composition described in claim 5.

10. A polymer molded article having the photochromic urethane compound described in claim 1 dispersed inside.

11. An optical article coated with a polymer film in which the photochromic urethane compound described in claim 1 is dispersed.

Images