Photochromic compound and curable composition containing said photochromic compound

Abstract

A photochromic compound according to the present invention is characterized by comprising at least two monovalent photochromic basic structural groups PC that include a T-type photochromic site, wherein the photochromic base structural groups are bonded to an organic group having a non-SO aromatic ring that does not include a sulfur atom or an oxygen atom.

Description

[Technical Field]

[0001] The present invention relates to a novel photochromic compound having temperature dependence. [Background technology]

[0002] Photochromic compounds are compounds that can reversibly transform into two isomers with different absorption spectra when irradiated with ultraviolet light, such as sunlight or mercury lamp light. Generally, when a colorless, bleached compound is irradiated with ultraviolet light, it quickly changes color and isomerizes (coloring reaction) to a colored state. Among these photochromic compounds, those that return to their original colorless state not only when exposed to light of a specific wavelength but also when exposed to heat during isomerization (fading reaction) from the colored state to the bleached state are called T-type photochromic compounds, and are particularly well researched and developed as materials for photochromic lenses.

[0003] Photochromic compounds used in such photochromic lenses are generally required to have the following properties: (I) The degree of coloring (initial coloring) in the visible light region before irradiation with ultraviolet light is small. (II) The color density reaches saturation quickly after the start of ultraviolet irradiation. (III) The speed at which the color returns to its original state after the UV irradiation is stopped (fading speed) is fast. (IV) This reversible action has good durability against repeated use. (V) To be dissolved at a high concentration in a monomer composition that will become a host material after curing so as to have high dispersibility in the host material used.

[0004] Many chromene compounds have been studied as photochromic compounds that satisfy these properties.

[0005] Furthermore, with the recent widespread use of photochromic compounds, it is desired that photochromic compounds also satisfy properties that have not been previously required.

[0006] It is generally known that T-type photochromic compounds have a trade-off between fading speed and color density. Therefore, when used in high temperatures, such as in the summer when sunlight is strong, fading reactions are more likely to occur, resulting in a decrease in color density. They are known to be susceptible to the effects of ambient temperature (high temperature dependency). To address this issue, increasing the amount of photochromic compound can improve color density and produce photochromic lenses with high color density even at high temperatures. However, as the amount of compound increases, the relationship between color density and compound amount generally becomes less proportional. Therefore, this solution has limitations due to the solubility of the photochromic compound itself and cost.

[0007] As described above, the method of simply increasing the amount of T-type photochromic compound does not currently provide sufficient improvement when used under high temperatures such as in summer. Therefore, there is a particular need for the development of photochromic compounds that have high color density even under high temperatures such as in summer.

[0008] Furthermore, in T-type photochromic compounds, there is a trade-off between the fading rate and the color density, so in order to obtain high color density at high temperatures, it is necessary to improve the thermal stability of the color state, which results in a slower fading rate. In general, it is difficult to achieve both a fast fading rate and a low temperature dependency.

[0009] To solve this problem, the present inventors have proposed a chromene compound having a substituent at a specific position (see Patent Document 1), which can make the temperature dependency relatively small. However, the chromene compound described in Patent Document 1 has a problem in that it has a substituent at a specific position, resulting in limited color tone. Generally, chromene compounds are molecularly designed by introducing various substituents to satisfy the desired photochromic properties for each application. Therefore, although it is possible to obtain a chromene compound with reduced temperature dependency by limiting the substituents, other properties are impaired, making it difficult to achieve a satisfactory color tone, for example.

[0010] Furthermore, Patent Document 2 proposes a photochromic compound in which two naphthopyran skeletons are linked by an aromatic ring group (SO-based aromatic ring group) containing a sulfur atom (S) and an oxygen atom (O). However, this photochromic compound has a problem in that it has low photochromic durability. Furthermore, Patent Document 2 does not consider temperature dependency at all. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] Patent Publication No. 2018-062496 [Patent Document 2] Special Publication 2005-508897 Summary of the Invention [Problem to be solved by the invention]

[0012] Therefore, an object of the present invention is to provide a photochromic compound which not only has low temperature dependency and exhibits high color density even under high temperatures such as in summer, but also can maintain a constant color tone during color development and fading, and also has excellent photochromic durability. Another object of the present invention is to provide a curable composition, an optical article, and a polymer molded article, each containing the above photochromic compound. [Means for solving the problem]

[0013] The present inventors have investigated various structures, substituents, positions of the substituents, and combinations of substituents for compounds having a T-type photochromic moiety (basic skeleton), and have discovered that when a group having such a T-type photochromic moiety is linked via a specific aromatic ring group, the temperature dependency is improved, which led to the completion of the present invention.

[0014] According to the present invention, there is provided a photochromic compound having at least two monovalent photochromic basic structural groups PC each containing a T-shaped photochromic moiety, wherein the photochromic basic structural groups are bonded to an organic group having a non-SO-based aromatic ring that does not contain a sulfur atom or an oxygen atom.

[0015] In the photochromic compound of the present invention, the following embodiments are preferably adopted. (A) It is represented by the following formula (1). [ka] During the ceremony, m is an integer of 2 or greater, PC represents the monovalent photochromic basic structural group, L and R 3 provided that at least one of them contains the non-SO aromatic ring. L represents a divalent organic group or a direct bond to which the PC is bonded at the terminal thereof, R 3 represents an m-valent organic group or a direct bond, and when represents a direct bond, m=2 and L is a divalent organic group containing the non-SO-based aromatic ring.

[0016] (B) The above R 3is at least one selected from the group consisting of a non-SO-based aromatic ring group, a saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms, a saturated or unsaturated aliphatic ring group having 3 to 20 carbon atoms, which may have a heteroatom in the aliphatic ring, a polyvalent silylene group having 1 to 3 silicon atoms and having at least one substituent selected from an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, and a non-SO-based aromatic ring group having 6 to 30 carbon atoms, an oxygen atom or a sulfur atom (m=2), and a polyvalent amino group.

[0017] (C) It is represented by the following formula (1a). [ka] During the ceremony, m, PC and R 3 has the same meaning as explained in the formula (1), n is a number from 1 to 5, -(R 1 )nR 2 - is a divalent organic group corresponding to L in formula (1), R 1 is a direct bond or a divalent non-SO aromatic ring group having 6 to 30 carbon atoms, R 2 is the above R 1 and R in Eq. (1) 3 and is a direct bond or a divalent organic group selected from the following: A divalent acyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms; A divalent saturated or unsaturated aliphatic cyclic group having 3 to 20 carbon atoms, The aliphatic ring may contain a heteroatom; oxygen or sulfur atoms; Divalent amino groups; A silylene group having 1 to 3 silicon atoms, and having as a substituent a carbon number alkyl groups having 1 to 15 carbon atoms, alkoxy groups having 1 to 15 carbon atoms, and At least one non-SO aromatic ring group having a prime number of 6 to 30 is contained. silylene groups;

[0018] (D) The T-type photochromic moiety contained in the photochromic basic structural group PC has at least one basic skeleton selected from the group consisting of a naphthopyran moiety, a spirooxazine moiety, and a spiropyran moiety.

[0019] (E) The T-type photochromic moiety is a naphthopyran moiety, and the naphthopyran moiety has an indenonaphthopyran basic skeleton.

[0020] (F) Said R 3 The molecular weight of the organic group bonded to the PC containing the group is less than 1,000 per PC.

[0021] (G) The monovalent photochromic basic structural group PC is represented by the following formula (2): [ka] During the ceremony, a is an integer from 0 to 4, b is an integer from 0 to 4, R 4 and R 5 respectively represent the following groups: hydroxyl groups; alkyl groups; cycloalkyl groups; alkoxy groups; amino group; cyano group; halogen atoms; nitro group; Formyl group; hydroxycarbonyl group; Alkylcarbonyl group; alkoxycarbonyl groups; aryl groups; heterocyclic groups; Alkylthio groups; cycloalkylthio groups; arylthio groups; aralkyl groups; aralkoxy group; aryloxy groups; thiol groups; Alkoxyalkylthio groups; A group represented by the following formula (X):

[0022] [ka] During the ceremony, E is an oxygen atom or NR 101 and R 101 is a hydrogen atom or an alkyl group, F is an oxygen atom or a sulfur atom, R 201 represents a hydrogen atom, an alkyl group, a cycloalkyl group, G is an oxygen atom, a sulfur atom, or NR 202 and R 202 is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group, and when G is an oxygen atom or a sulfur atom, R 201 is a group other than a hydrogen atom, g is an integer of 0 or 1; A group represented by the following formula (Y):

[0023] [ka] During the ceremony, R 300 is an alkylene group or a silylene group having an alkyl group or an aryl group as a substituent, R 301 is an alkyl group or an aryl group, R 302 , R 303 and R 304 is an alkylene group, h, j, k, and l are integers of 0 or 1; i is an integer from 2 to 200, and multiple i units may be the same or different; Multiple R exists depending on the value of a or b 4 Or R 5may be the same or different, and R 4 Or R 5 If there is a 4 Or R 5 Together, R 4 Or R 5 may form a ring together with the carbon atom to which it is attached which may contain an oxygen atom, a carbon atom, a sulfur atom or a nitrogen atom, R 6 and R 7 are each an aryl group or a heteroaryl group, provided that one of them represents a direct bond to an organic group; R 8 and R 9 respectively represent the following groups: hydrogen atoms; hydroxyl groups; alkyl groups; cycloalkyl groups; alkoxy groups; alkoxyalkyl groups; Formyl group; hydroxycarbonyl group; Alkylcarbonyl group; alkoxycarbonyl groups; halogen atoms; aralkyl groups; aralkoxy group; aryl groups; aryloxy groups; heterocyclic groups; a group represented by the formula (Y); Also, R 8 and R 9 may combine together with the carbon atom at position 13 to which they are bonded to form an aliphatic ring having 3 to 20 carbon atoms, a condensed polycycle in which an aromatic ring or an aromatic heterocycle is condensed to the aliphatic ring, a heterocycle having 3 to 20 ring atoms, or a condensed polycycle in which an aromatic ring or an aromatic heterocycle is condensed to the heterocycle.

[0024] (H) In the formula (2), R 8 and R 9together with the carbon atom at position 13 to which they are bonded, form an aliphatic ring having 3 to 20 carbon atoms, a condensed polycyclic ring in which an aromatic ring or an aromatic heterocycle is condensed to the aliphatic ring, a heterocycle having 3 to 20 ring atoms, or a condensed polycyclic ring in which an aromatic ring or an aromatic heterocycle is condensed to the heterocycle.

[0025] (I) In the formula (2), R 8 and R 9 The aliphatic ring formed by these together is a cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, or spirodicyclohexane ring, and the ring may have 1 to 10 alkyl groups having 1 to 3 carbon atoms or cycloalkyl groups having 5 to 7 carbon atoms as substituents, or the ring may be condensed with a cycloalkyl group having 5 to 7 carbon atoms.

[0026] The present invention also provides a photochromic curable composition comprising the above photochromic compound and a polymerizable compound.

[0027] The present invention further provides a photochromic optical article obtained by polymerizing the photochromic curable composition, a polymer molded product having the photochromic compound dispersed therein, and an optical article coated with a polymer film having the photochromic compound dispersed therein. [Effects of the Invention]

[0028] T-type photochromic compounds have temperature dependency, changing from a colored state to a colorless state depending on the temperature. However, the photochromic compound of the present invention has a molecular structure in which multiple T-type photochromic molecules are linked via specific aromatic rings, which reduces the temperature dependency of T-type photochromic compounds and allows the compound to maintain a stable color tone even at high temperatures such as in summer. The reduction in temperature dependency due to such a molecular structure was discovered as a result of many experiments, and although the reason for this has not yet been clarified, the present inventors speculate as follows.

[0029] In other words, by linking multiple T-type photochromic molecules with rigid bonds such as aromatic rings that are prone to intermolecular interactions such as π-π stacking, molecular motion is restricted, allowing the T-type photochromic molecules to approach each other more easily. This makes the color fading reaction less likely to occur, and as a result, it is presumed that the colored state is maintained even at high temperatures compared to when the photochromic molecules exist individually.

[0030] Furthermore, in the present invention, the reduction in temperature dependency is not caused by introducing a specific substituent into the photochromic compound, and therefore, no limitation is imposed on the color tone.

[0031] Furthermore, the aromatic rings interposed between the multiple T-shaped photochromic molecules must be non-SO-based aromatic rings that do not contain sulfur or oxygen atoms, because, as shown in the examples below, if a heteroaromatic ring containing a sulfur atom (S) or an oxygen atom (O) is used as a linking group, the photochromic durability will be reduced.

[0032] When a photochromic lens is produced using such a photochromic compound of the present invention, it is possible to obtain a photochromic lens that has high color density and little temperature dependency even under high temperatures such as those in summer. [Brief explanation of the drawings]

[0033] [Figure 1] FIG. 1 is a graph showing the relationship between temperature dependency and fading half-life for compounds of examples and compounds of comparative examples. DETAILED DESCRIPTION OF THE INVENTION

[0034] The photochromic compound of the present invention has at least two monovalent photochromic basic structural groups PC each containing a T-type photochromic moiety, and has a structure in which these photochromic basic structural groups PC are bonded via an organic group having a non-SO-based aromatic ring.

[0035] <Monovalent photochromic basic structural group PC> In the present invention, the monovalent photochromic basic structural group PC has a photochromic moiety, which is the basic skeleton of a T-type photochromic compound. Due to the presence of such a photochromic moiety, the compound exhibits temperature dependency specific to T-type photochromic compounds, and isomerizes from a colored state to a colorless state upon application of heat.

[0036] In the present invention, such a T-type photochromic moiety is preferably one that undergoes a change in molecular conformation upon isomerization, and is more preferably, for example, a naphthopyran moiety, a spirooxazine moiety, or a spiropyran moiety, and even more preferably, a naphthopyran moiety. Among these, an indenonaphthopyran moiety, particularly an indeno[2,1-f]naphtho[1,2-b]pyran moiety, is most preferably, having a basic skeleton. It is believed that by bonding a moiety having such a basic skeleton via a specific aromatic ring group, isomerization due to a structural change is effectively suppressed, and temperature dependency is effectively reduced.

[0037] The monovalent photochromic basic structural group PC having the above-mentioned indeno[2,1-f]naphtho[1,2-b]pyran basic skeleton is represented by the following formula (2). [ka]

[0038] In the above photochromic basic structural group PC, the group R 4 ~R 9 The structure obtained by removing the isotope shows the basic skeleton of the indeno[2,1-f]naphtho[1,2-b]pyran, which is the T-type photochromic moiety.

[0039] In the above formula (2), the group R 4 a, which indicates the number of groups, is an integer of 0 to 4; 5 b, which indicates the number of the groups, is an integer of 0 to 4.

[0040] R 4 and R 5 respectively represent the following groups: hydroxyl groups; alkyl groups, especially those containing 1 to 6 carbon atoms; cycloalkyl groups, especially those containing 3 to 8 carbon atoms; alkoxy groups, especially those having 1 to 6 carbon atoms; amino group; cyano group; halogen atoms; nitro group; Formyl group; hydroxycarbonyl group; Alkylcarbonyl groups, especially those containing 2 to 7 carbon atoms; alkoxycarbonyl groups, especially those having 1 to 7 carbon atoms; aryl groups, especially those containing 6 to 12 carbon atoms; heterocyclic groups, especially those having nitrogen atoms as ring members; Alkylthio groups, especially those having 1 to 6 carbon atoms; cycloalkylthio groups, especially those having 3 to 8 carbon atoms; arylthio groups, especially those containing 6 to 12 carbon atoms; aralkyl groups, especially those containing 7 to 11 carbon atoms; aralkoxy groups, especially those containing 7 to 11 carbon atoms; aryloxy groups, especially those having 6 to 12 carbon atoms; thiol groups; Alkoxyalkylthio groups; especially those having 1 to 6 carbon atoms; A group represented by the following formula (X) or formula (Y):

[0041] [ka]

[0042] [ka]

[0043] In the formula (X), E is an oxygen atom or NR 101 and (R 101 represents a hydrogen atom or an alkyl group), F is an oxygen atom or a sulfur atom, G is an oxygen atom, a sulfur atom, or NR 202 and (R 202 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group), g is an integer of 0 or 1, R 201 is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group, When G is an oxygen atom or a sulfur atom, R 201 is a group other than a hydrogen atom. In addition, in the formula (Y), R 300 is an alkylene group or a silylene group having an alkyl group or an aryl group as a substituent, R 301 is an alkyl group or an aryl group, R 302 , R 303 and R 304 is an alkylene group, h, j, k, and l are integers of 0 or 1, and i is an integer of 2 to 200, and multiple i units may be the same or different.

[0044] Multiple R exists depending on the value of a or b 4 Or R 5 may be the same or different, and R 4 Or R 5 If there is a 4 Or R 5 Together, R 4 Or R 5may form a ring together with the carbon atom to which it is attached. Such a ring may contain an oxygen atom, a carbon atom, a sulfur atom, or a nitrogen atom as a ring member.

[0045] In the above formula (X), E is NR 101 and R 101 is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. F is preferably an oxygen atom. G is NH, i.e., R 202 is preferably a hydrogen atom. G is also preferably an oxygen atom. Also, R 201 is preferably an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms. Particularly preferred groups of formula (X) are as follows:

[0046] [ka]

[0047] In addition, in the above formula (Y), R 300 is preferably an alkylene group having 1 to 6 carbon atoms or a silylene group having an alkyl group having 1 to 6 carbon atoms as a substituent. Also, R 301 is preferably an alkyl group having 1 to 6 carbon atoms. R 302 is preferably an alkylene group having 1 to 6 carbon atoms. R 303 is preferably an alkylene group having 1 to 6 carbon atoms. R 304 is preferably an alkylene group having 1 to 6 carbon atoms. Furthermore, i is an integer of 2 to 200, preferably 5 to 100, more preferably 8 to 75, and most preferably 10 to 70.

[0048] Particularly preferred groups of formula (Y) are shown below: [ka]

[0049] Each of the above groups may have a substituent such as a halogen atom, as long as the substituent can be bonded to the group and does not inhibit photochromic properties. Furthermore, the chain group such as an alkyl group may be linear or branched. Furthermore, unless otherwise specified, any group or ring that can have a substituent that does not inhibit photochromic properties, including but not limited to the above groups, may have such a substituent, and further, a chain group may be linear or branched.

[0050] In the present invention, the above R 4 As the R, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an amino group, a heterocyclic group, an alkylthio group, an arylthio group, or an aryl group having 6 to 12 carbon atoms is preferred. Among these, it is more preferred that these groups are present at the 6th and / or 7th positions. In addition, when R is present at the 6th and 7th positions of indeno[2,1-f]naphtho[1,2-b]pyran, 4 are preferably present and together form an aliphatic ring which may contain an oxygen atom, a nitrogen atom, or a sulfur atom. In this case, the number of atoms in the aliphatic ring containing the oxygen atom, the nitrogen atom, or the sulfur atom (the number of atoms including the heteroatom and the carbon atoms bonded to the 6th and 7th positions) is preferably 5 to 8. Furthermore, the aliphatic ring may have a substituent, and the substituent is preferably an alkyl group having 1 to 6 carbon atoms. R 5 is preferably a hydrogen atom (when b=0), an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an arylthio group.More preferably, it is located at the 11th position of indeno[2,1-f]naphtho[1,2-b]pyran and is a hydrogen atom (when b=0), an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms which may have a substituent, or an arylthio group.

[0051] In addition, in the above formula (2), R 6and R 7 One of the two is a direct bond to an organic group having a non-SO aromatic ring, which will be described later. This direct bond allows for adequate control of the molecular motion of ring-opening and ring-closing, which is thought to be one of the reasons for the reduced temperature dependence. R 6 and R 7 and represent an aryl group or a heteroaryl group, respectively, provided that one of them represents such a direct bond.

[0052] Also, R 8 and R 9 respectively represent the following atoms or groups: hydrogen atoms; hydroxyl groups; alkyl groups, especially those containing 1 to 6 carbon atoms; cycloalkyl groups, especially those containing 3 to 8 carbon atoms; alkoxy groups, especially those having 1 to 6 carbon atoms; alkoxyalkyl groups; Formyl group; hydroxycarbonyl group; Alkylcarbonyl groups, especially those containing 2 to 7 carbon atoms; alkoxycarbonyl groups, especially those having 1 to 7 carbon atoms; halogen atoms; aralkyl groups, especially those containing 7 to 11 carbon atoms; aralkoxy groups, especially those containing 7 to 11 carbon atoms; aryl groups, especially those containing 6 to 12 carbon atoms; aryloxy groups, especially those having 6 to 12 carbon atoms; heterocyclic groups; The group represented by the formula (Y) is preferably R 4 and R 5 Specifically, It is an exemplified group;

[0053] Also, the above R 8 and R 9may combine together with the carbon atom at position 13 to which they are bonded to form an aliphatic ring having 3 to 20 carbon atoms, a condensed polycycle in which an aromatic ring or an aromatic heterocycle is condensed to the aliphatic ring, a heterocycle having 3 to 20 ring atoms, or a condensed polycycle in which an aromatic ring or an aromatic heterocycle is condensed to the heterocycle.

[0054] Furthermore, R 8 and R 9 The ring formed by these together is preferably an aliphatic ring having 3 to 20 carbon atoms, such as a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cycloundecane ring, a cyclododecane ring, or a spirodicyclohexane ring. These aliphatic rings also preferably have 1 to 10 substituents, and examples of such substituents include an alkyl group having 1 to 3 carbon atoms and a cycloalkyl group having 5 to 7 carbon atoms. Such aliphatic rings may also be condensed with a cycloalkyl group having 5 to 7 carbon atoms.

[0055] Particularly preferred examples of the above aliphatic ring are those represented by the following formula: [ka]

[0056] The monovalent photochromic basic structural group PC of formula (2) having the above-mentioned T-shaped photochromic basic skeleton is present in a plurality of molecules, and in the photochromic compound of the present invention, the plurality of photochromic basic structural groups PC are bonded via an organic group containing a non-SO-based aromatic ring as described below.

[0057] <Organic group containing a non-SO-based aromatic ring> In the present invention, the organic group linking the monovalent photochromic basic structural group PC may be a non-SO-based aromatic ring itself as the linking group, a non-SO-based aromatic ring may be present in the main chain of an aliphatic group, or a structure in which multiple non-SO-based aromatic rings are linked. The non-SO-based aromatic ring is an aromatic hydrocarbon ring or an aromatic heterocycle that does not contain a sulfur atom (S) or an oxygen atom (O) within the ring. Such an aromatic ring is rigid and serves as a bond that is prone to intermolecular interactions such as π-π stacking. As a result, the molecular motion of the T-shaped photochromic moiety bonded to this bond is restricted, reducing temperature dependency. Furthermore, in the case of an aromatic heterocycle containing a sulfur atom (S) or an oxygen atom (O), although temperature dependency is reduced, photochromic durability is reduced.

[0058] In the present invention, such a non-SO-based aromatic ring preferably has 6 to 30 carbon atoms or ring atoms. Among these, examples of aromatic hydrocarbon rings include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and polycyclic aromatic rings in which a benzene ring or the like is further condensed to these rings, specifically a tetracene ring, a pentacene ring, a benzopyrene ring, a chrysene ring, a pyrene ring, and a triphenylene ring. The aromatic heterocycle is not particularly limited as long as it does not contain a sulfur atom or an oxygen atom in the ring, and examples thereof include a pyrrole ring, an indole ring, an isoindole ring, a pyridine ring, a pyrimidine ring, a quinazoline ring, a pyridazine ring, a cinnoline ring, a phthalazine ring, and a 1,2,3-, 1,2,4-, or 1,3,5-triazine ring.

[0059] In the present invention, particularly preferred non-SO-based aromatic rings are benzene rings and polycyclic aromatic hydrocarbon rings in which one or more benzene rings are condensed to a benzene ring.

[0060] In the present invention, the organic group containing the non-SO aromatic ring has a plurality of bonds, but the positions of the bonds are not particularly limited. Preferred examples of the molecular structure of a photochromic compound in which a plurality of PCs are bonded to such an organic group containing a non-SO aromatic ring are shown below.

[0061] <Suitable molecular structure of photochromic compound> The photochromic compound in which a plurality of T-type photochromic moieties are linked by an organic group containing a non-SO-based aromatic ring is represented by the following formula (1). [ka]

[0062] In the above formula (1), m is an integer of 2 or more, and PC represents the above-mentioned monovalent photochromic basic structural group. As can be seen from this equation, m is R 3 It also corresponds to the number of PCs contained in the molecule, that is, the number of T-type photochromic moieties (basic skeletons). If the value of m is too large, it tends to be difficult to achieve the reduced temperature dependence that is the objective of the present invention, and furthermore, the greater the number of PCs contained in the molecule, the more difficult production becomes. Therefore, the value of m is preferably 20 or less, more preferably 10 or less, even more preferably 6 or less, and most preferably 2 to 4.

[0063] L and R in formula (1) 3 represents a linking group for multiple PCs, and therefore, L and R 3 At least one of the groups must contain a non-SO aromatic ring. 3 and L represents the following groups:

[0064] First, R 3is an m-valent organic group or a direct bond, but when it represents a direct bond, m=2, and in this case, L becomes a group containing a divalent non-SO-based aromatic ring. That is, in this case, L does not become a direct bond. Also, R 3 Examples of the m-valent organic group represented by the formula (I) that does not contain a non-SO-based aromatic ring include the following groups. Saturated or unsaturated hydrocarbon groups containing 1 to 15 carbon atoms; A saturated or unsaturated aliphatic ring group having 3 to 20 carbon atoms, may contain a heteroatom; A polyvalent silylene group having 1 to 3 silicon atoms, Alkyl groups with 1 to 15 prime numbers, alkoxy groups with 1 to 15 carbon atoms, and carbon At least one non-SO aromatic ring group having a prime number of 6 to 30 is contained. silylene groups; oxygen or sulfur atoms (m=2); amino group;

[0065] In the present invention, R 3 is preferably a direct bond, an m-valent non-SO-based aromatic ring group, an oxygen atom, a nitrogen atom, a methylene group, or a combination thereof. For example, an oxygen atom can be combined with a methylene group to form -O-CH-, and can also be combined with a methylene group to form a trivalent group such as -O-CH<.

[0066] In the present invention, R 3 The molecular weight of R is preferably less than 200. 3 If the value is large, the effect of restricting the movement of the photochromic moiety becomes smaller, and the effect of reducing the temperature dependency tends to decrease.

[0067] Furthermore, L represents a divalent organic group or a direct bond to which the PC is bonded at the end. This divalent organic group naturally includes a divalent non-SO-based aromatic ring group, but other groups may also be various organic groups other than SO-based aromatic ring groups. When L is a direct bond, R3 is a group containing a non-SO-based aromatic ring group.

[0068] Also, such a divalent group L may be represented by the formula: -(R 1 )nR 2 - That is, when L is a divalent organic group, the photochromic compound of general formula (1) is represented by the following general formula (1a).

[0069] [ka]

[0070] That is, in formula (1a), -(R 1 )nR 2 - is a divalent organic group corresponding to L in formula (1), and m, PC, and R 3 has the same meaning as explained in the above formula (1).

[0071] In addition, n is a number from 1 to 5, and R 1 represents a direct bond or a divalent non-SO aromatic ring group, provided that when it is a direct bond, n=1. This non-SO aromatic ring group is one of the above-mentioned non-SO aromatic rings having two bonds.

[0072] In the formula (1a), R 1 is a direct bond or a non-SO-based aromatic ring group, and when n is 2 or more, multiple R 1 may be different. 1 If is a direct bond, PC is R 2 It will be directly bonded to

[0073] Furthermore, although it depends on the size of the photochromic moiety, if the number of photochromic moieties is too large, molecular motion is overly controlled, and the effect of reducing temperature dependency tends to decrease. Also, the production of the photochromic compound itself tends to become complicated. Therefore, 1The number (n) is preferably 5 or less, particularly 3 or less, more preferably 2 or less, and most preferably n=1.

[0074] Furthermore, in the formula (1a), R 2 is the above R 1 and R in Eq. (1) 3 and is a direct bond or a divalent organic group selected from the following: A divalent acyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms; A divalent aliphatic cyclic group having 3 to 20 carbon atoms, wherein the aliphatic ring does not contain a heteroatom. May have children; oxygen or sulfur atoms; Divalent amino groups; A silylene group having 1 to 3 silicon atoms, and having as a substituent a carbon number alkyl groups having 1 to 15 carbon atoms, alkoxy groups having 1 to 15 carbon atoms, and At least one non-SO aromatic ring group having a prime number of 6 to 30 is contained. silylene groups;

[0075] Among the above, R 2 Preferred examples of the alkyl group include a direct bond, a methylene group, an ethylene group, a vinylene group, an ethynylene group, a cyclohexylene group, an oxygen atom, a sulfur atom, a polyvalent amino group, an azo group, a silylene group, a tetramethylsiloxane group, a tetramethyldisilylene group, and combinations thereof (excluding direct bonds). Particularly preferred examples of the alkyl group include a direct bond, a methylene group, a vinylene group, an ethynylene group, a cyclohexylene group, an oxygen atom, a sulfur atom, a polyvalent amino group, an azo group, and combinations thereof. The combined group is, for example, a group consisting of an oxygen atom and a methylene group, such as (R 2 ;-O-CH2-).

[0076] Also, R 3 Similarly, R 2If R is large, the effect of restricting the movement of the photochromic moiety becomes smaller, and the effect of reducing temperature dependency tends to decrease. 2 The molecular weight of the copolymer should be less than 500, preferably less than 300, more preferably less than 150, and most preferably 100 or less.

[0077] In this way, in order to most effectively restrict the movement of the photochromic moiety within a range that does not impair the photochromic properties and greatly reduce the temperature dependency, the R 3 It is preferable that the organic group bonded to the PC containing the group is not larger than a certain size. For example, the organic group (L+R 3 ) is preferably less than 1000, particularly preferably less than 750, more preferably less than 500, and most preferably less than 300. Therefore, taking such molecular weight into consideration, the type of each group (R 3 , R 1 , R 2 Molecular design should be performed by selecting the molecular structure (m, n) and their numbers (m, n). The molecular weight of the organic group is such that L is a direct bond and R 3 is a benzene ring and all its hydrogen atoms are replaced by PC (m=6), the minimum value is 72.

[0078] In any case, in the photochromic compound of the present invention, a non-SO-based aromatic ring is always present between a plurality of PCs. Particularly suitable photochromic compounds are those represented by the following formula:

[0079] [ka]

[0080] [ka]

[0081] [ka]

[0082] <Identification of photochromic compounds> The photochromic compound of the present invention generally exists as a solid at room temperature and normal pressure, and can be confirmed by the following means (a) to (c).

[0083] (a) Proton nuclear magnetic resonance spectrum ( 1 The following peaks are observed by H-NMR: δ: 5.0 to 9.0 ppm (peaks due to aromatic protons and alkene protons) δ: 1.0 to 4.0 ppm (peaks due to protons of alkyl and alkylene groups) By comparing the respective spectral intensities, the number of protons in each bonding group can be determined. This allows identification of the bonds.

[0084] (b) The composition of the corresponding product can be determined by elemental analysis.

[0085] (c) 13 C-nuclear magnetic resonance spectrum ( 13 The following peaks are observed by C-NMR: δ: 110 to 160 ppm (peaks due to carbon atoms in aromatic hydrocarbon groups) δ: 80 to 140 ppm (peaks based on alkene and alkyne carbons) δ: 20 to 80 ppm (Peaks based on carbon atoms of alkyl and alkylene groups) appears.

[0086] <Production of photochromic compounds> The photochromic compound of the present invention can be synthesized, for example, by utilizing a cross-coupling reaction. For example, a compound having a halogen atom, a triflate group, or the like is prepared as a starting compound, and this compound is subjected to a cross-coupling reaction with an organozinc compound, an organoboron compound, or an organotin compound in the presence of a transition metal catalyst such as palladium or nickel, thereby producing the compound. The indenonaphthopyran compound represented by the formula (2) can be suitably produced by the following method. In the following description, unless otherwise specified, the symbols in each formula have the same meaning as explained for the formula above.

[0087] The indenonaphthopyran compound represented by formula (2) can be synthesized by reacting a naphthol compound represented by formula (3) below with a propargyl alcohol compound represented by formula (4) below in the presence of an acid catalyst.

[0088] [ka]

[0089] [ka]

[0090] In the above reaction, the acid catalyst used may be sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, acidic alumina, etc. The acid catalyst is used in an amount of preferably 0.1 to 10 parts by mass per 100 parts by mass of the total of the naphthol compound and the propargyl alcohol compound. The reaction temperature is preferably 0 to 200° C. As the solvent, an aprotic organic solvent such as N-methylpyrrolidone, dimethylformamide, tetrahydrofuran, benzene, toluene, methyl ethyl ketone, or methyl isobutyl ketone is preferably used. The product obtained by such a reaction is purified, for example, by silica gel column purification and further by recrystallization.

[0091] Among the naphthol compounds represented by the formula (3), preferred compounds have a structure that allows the production of the suitable indenonaphthopyran (chromene) compound represented by the formula (2). For example, the compound represented by the following formula can be mentioned as a particularly preferred one.

[0092] [ka]

[0093] The naphthol compound represented by the formula (3) can be synthesized, for example, as follows.

[0094] First, a benzophenone compound represented by the following formula (5) is prepared. [ka]

[0095] This benzophenone compound is subjected to a Stobbe reaction, a cyclization reaction, a hydrolysis reaction using an alkali or an acid, benzyl protection, debenzylation by hydrolysis reaction using an alkali or an acid, or the like to obtain a benzyl-protected carboxylic acid represented by the following formula (6) (in formula (6), Bn is a benzyl group).

[0096] [ka]

[0097] Next, the benzyl-protected carboxylic acid is converted to an amine by a method such as Curtius rearrangement, Hofmann rearrangement, or Lossen rearrangement, and a diazonium salt is prepared from the amine by a method known per se. This diazonium salt is converted to a bromide by a Sandmeyer reaction or the like, and the resulting bromide is reacted with magnesium, lithium, or the like to prepare an organometallic compound. This organometallic compound is reacted with a ketone represented by the following formula (7) in an organic solvent at −80 to 70° C. for 10 minutes to 4 hours to obtain an alcohol compound.

[0098] [ka]

[0099] The resulting alcohol compound is subjected to the Friedel-Crafts reaction, that is, the reaction is carried out under neutral to acidic conditions at 10 to 120°C for 10 minutes to 2 hours, and the alcohol moiety is converted into a spiro compound by a nucleophilic substitution reaction, thereby synthesizing the naphthol compound represented by the formula (3).

[0100] [ka]

[0101] In this reaction, the reaction ratio between the organometallic compound and the ketone represented by the formula (7) is preferably selected from the range of 1:10 to 10:1 (molar ratio). The reaction temperature is preferably -80 to 70°C. As the solvent, an aprotic organic solvent such as diethyl ether, tetrahydrofuran, benzene, or toluene is preferably used. The Friedel-Crafts reaction is preferably carried out using an acid catalyst such as acetic acid, hydrochloric acid, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, acidic alumina, etc. In this reaction, an aprotic organic solvent such as tetrahydrofuran, benzene, toluene, etc. is used.

[0102] On the other hand, the propargyl alcohol compound represented by the formula (4) can be easily synthesized, for example, by reacting a ketone compound corresponding to the formula (4) with a metal acetylene compound such as lithium acetylide.

[0103] The photochromic (chromene) compounds synthesized as described above are highly soluble in common organic solvents such as toluene, chloroform, tetrahydrofuran, etc. When the photochromic compound of the present invention is dissolved in such a solvent, the solution is generally nearly colorless and transparent, and exhibits good photochromic properties, rapidly developing color when irradiated with sunlight or ultraviolet light and rapidly returning to its original colorless state when the light is blocked.

[0104] The photochromic compound of the present invention can be used in combination with other photochromic compounds depending on the intended use. For example, to obtain various color tones required for photochromic lenses, it can be used in combination with other known photochromic compounds, such as fulgides, fulgimides, spirooxazines, chromenes, etc. Among these, the use of a chromene compound in combination is particularly preferred, since it can maintain a uniform color tone during color development and fading, suppress color shift during color development due to deterioration of photochromic properties, and further reduce initial coloring. In this case, it is preferable to use multiple photochromic compounds of the present invention to adjust the color tone, from the viewpoint of reducing temperature dependency.

[0105] When a photochromic composition containing the photochromic compound of the present invention and other photochromic compounds is prepared, the blending ratio of each chromene compound is appropriately determined depending on the desired color tone.

[0106] <Photochromic curable composition> The photochromic compound of the present invention and the photochromic composition are preferably used as a photochromic curable composition in combination with a polymerizable compound. In the present invention, the amount of the photochromic curable composition depends on the color intensity of the photochromic compound, the selected lens material, and the lens thickness, and therefore cannot be generalized, but it is preferable to use the photochromic compound (or photochromic composition) of the present invention in an amount of 0.001 to 10 parts by mass per 100 parts by mass of the polymerizable compound.

[0107] The optimum blending amount varies depending on the intended use, for example, when the photochromic curable composition is used as a thin-film optical article and when it is used as a thick-film optical article, as follows.

[0108] Use as thin film optical articles; For example, when the photochromic curable composition is formed into a thin film of about 100 μm (a polymer film obtained by polymerizing the photochromic curable composition), it is preferable to adjust the color tone by adding 0.001 to 10 parts by mass of the photochromic compound (or photochromic composition) of the present invention to 100 parts by mass of other polymerizable monomers.

[0109] Use of thick films as optical articles; In the case of a thick cured product (a polymer molded product obtained by polymerizing the photochromic curable composition), for example, a cured product having a thickness of 1 mm or more, it is preferable to adjust the color tone by adding 0.001 to 1 part by mass of the photochromic compound (or photochromic composition) of the present invention to 100 parts by mass of the thick cured product or another polymerizable monomer that gives a thick cured product.

[0110] <Polymerizable compound> As described above, the photochromic compound of the present invention is preferably used in combination with a polymerizable compound to form a photochromic curable composition. Examples of the polymerizable compound include urethane or urea-based polymerizable compounds capable of forming urethane bonds, urea bonds, etc., radical polymerizable compounds, and epoxy-based polymerizable compounds. These polymerizable compounds are not particularly limited, but for example, the polymerizable compounds described in International Publication WO2018-235771 can be suitably used. Among these, the following polymerizable compounds are particularly preferably used.

[0111] Iso(thio)cyanate compounds: The isocyanate compound is a compound having an isocyanate group or an isothiocyanate group, and may contain both an isocyanate group and an isothiocyanate group. This compound is preferably used in combination with a compound containing active hydrogen, which will be described later.

[0112] Such iso(thio)cyanate compounds include, but are not limited to, the following compounds: Polyiso(thio)cyanate having at least two iso(thio)cyanate groups in one molecule: Aromatic polyiso(thio)cyanates containing aromatic rings, such as m-xylene diisocyanate and 4,4'-diphenylmethane diisocyanate; Aliphatic polyiso(thio)cyanates such as norbornane diisocyanate and dicyclohexylmethane-4,4'-diisocyanate;

[0113] Compounds with active hydrogen; The compound having active hydrogen is preferably a compound having a hydroxyl group and / or a thiol group, and particularly preferably a polyfunctional compound having two or more active hydrogens in one molecule, although not limited thereto. Specific examples of the compound having active hydrogen include polyfunctional thiol compounds such as pentaerythritol tetrakis(3-mercaptopropionate) and 4-mercaptomethyl-3,6-dithia-octanedithiol; and polyfunctional alcohols such as trimethylolpropane and pentaerythritol.

[0114] radically polymerizable compounds; The radical polymerizable compound can be classified into a polyfunctional radical polymerizable compound and a monofunctional radical polymerizable compound, and each can be used alone or in combination. The radical polymerizable substituent includes a group having an unsaturated double bond, that is, a vinyl group (including a styryl group, a (meth)acrylic group, an allyl group, etc.).

[0115] A 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.

[0116] The first radical polymerizable compound is not particularly limited, but more preferably has a number of radical polymerizable substituents of 2 to 6. Specific examples thereof are as follows. Polyfunctional (meth)acrylic acid ester compounds; 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 allylic compounds; Diallyl Phthalate Diallyl Terephthalate Diallyl Isophthalate Diallyl tartrate Diallyl epoxysuccinate Diallyl fumarate Diallyl Chlorendate Diallyl hexaphthalate Diallyl Carbonate Allyl Diglycol Carbonate Trimethylolpropane triallyl carbonate Polyfunctional thio(meth)acrylate compounds; 1,2-Bis(methacryloylthio)ethane Bis(2-acryloylthioethyl) ether 1,4-Bis(methacryloylthiomethyl)benzene vinyl compounds; Divinylbenzene

[0117] Examples of the second polyfunctional radically polymerizable compound having more than 10 radically polymerizable substituents include compounds with relatively large molecular weights, such as silsesquioxane compounds having radically polymerizable substituents and polyrotaxane compounds having radically polymerizable substituents.

[0118] Furthermore, the monofunctional radically polymerizable compound is a compound having one radically polymerizable substituent in the molecule, and specific examples thereof include, but are not limited to, the following compounds.

[0119] Unsaturated carboxylic acids; acrylic acid methacrylic acid Maleic Anhydride (Meth)acrylic acid esters; 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 Fumaric acid esters; Diethyl fumarate Diphenyl fumarate Thio(meth)acrylic acid; Methylthioacrylate Benzylthioacrylate Benzylthiomethacrylate vinyl compounds; styrene Chlorostyrene Methylstyrene Vinylnaphthalene α-methylstyrene dimer Bromostyrene

[0120] The radical polymerizable compounds can be used alone or in combination. In this case, the amount of the polyfunctional radical polymerizable compound is preferably 80 to 100 parts by mass and the amount of the monofunctional radical polymerizable compound is preferably 0 to 20 parts by mass per 100 parts by mass of the total radical polymerizable compounds. More preferably, the amount of the polyfunctional radical polymerizable compound is 90 to 100 parts by mass and the amount of the monofunctional radical polymerizable compound is 0 to 10 parts by mass. Furthermore, the amount of the first polyfunctional radical polymerizable compound is preferably 80 to 100 parts by mass, the amount of the second radical polymerizable compound is 0 to 20 parts by mass, and the amount of the monofunctional radical polymerizable compound is 0 to 20 parts by mass per 100 parts by mass of the total radical polymerizable compounds. More preferably, the amount of the first polyfunctional radical polymerizable compound is 85 to 100 parts by mass, the amount of the second polyfunctional radical polymerizable compound is 0 to 15 parts by mass, and the amount of the monofunctional radical polymerizable compound is 0 to 15 parts by mass.

[0121] Various compounding agents; The curable composition of the present invention may contain various known additives, such as release agents, ultraviolet absorbers, infrared absorbers, ultraviolet stabilizers, antioxidants, coloring inhibitors, antistatic agents, fluorescent dyes, dyes, pigments, fragrances, etc., within the scope of not impairing the effects of the present invention. In addition, solvents and leveling agents may also be added, and further, thiols such as t-dodecyl mercaptan may be added as polymerization regulators, if necessary.

[0122] Among the above-mentioned compounding ingredients, ultraviolet stabilizers are preferred because they can improve the durability of the photochromic moiety. Known examples of such ultraviolet stabilizers include hindered amine light stabilizers, hindered phenol antioxidants, and sulfur-based antioxidants. Particularly preferred ultraviolet stabilizers are as follows: Bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate; ADK STAB (registered trademark) 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-methyl-phenol; Ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate]; Ciba Specialty Chemicals IRGANOX® 1010, 1035, 1075, 1098, 1135, 1141, 1222, 1330, 1425, 1520, 259, 3114, 3790, 5057, 565

[0123] The amount of such 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 weight, particularly 0.01 to 1 part by weight, per 100 parts by weight of the photochromic hydroxyurethane compound of the present invention. In particular, when a hindered amine light stabilizer is used, the durability improvement effect varies depending on the type of photochromic moiety, resulting in color shifts in the adjusted color tone. To suppress such color shifts, the blending amount is preferably 0.5 to 30 moles, more preferably 1 to 20 moles, and even more preferably 2 to 15 moles, per mole of the photochromic moiety.

[0124] In addition to the ultraviolet stabilizer, an ultraviolet absorber can also be used. Known ultraviolet absorbers such as benzophenone-based compounds, benzotriazole-based compounds, cyanoacrylate-based compounds, triazine-based compounds, and benzoate-based compounds can be used as the ultraviolet absorber, with cyanoacrylate-based compounds and benzophenone-based compounds being particularly preferred. The ultraviolet stabilizer is preferably used in an amount of 0.001 to 5 parts by mass relative to 100 parts by mass of the photochromic curable composition containing the photochromic compound and the polymerizable compound.

[0125] <Method of using photochromic curable composition; optical article> In the present invention, the polymerizable compounds used in the photochromic curable composition are as exemplified above, and the blending ratio of these other polymerizable compounds may be appropriately determined depending on the application. However, the blending ratio of the preferred chromene compound or photochromic composition is as described above.

[0126] In the present invention, the photochromic curable composition can be prepared by mixing the photochromic compound (photochromic composition) to be used, the polymerizable compound, additives to be blended as necessary, and the like. Polymerization and curing for producing a photochromic cured body is carried out by radical polymerization, ring-opening polymerization, anionic polymerization, or condensation polymerization using irradiation with active energy rays such as ultraviolet rays, α-rays, β-rays, and γ-rays, heat, or a combination of both. That is, an appropriate polymerization means may be adopted depending on the types of polymerizable compound and polymerization and curing accelerator and the form of the photochromic cured body to be formed.

[0127] When the curable composition of the present invention containing a polymerizable compound is thermally polymerized, the temperature affects the properties of the resulting photochromic cured product. The temperature conditions cannot be generally defined because they are affected by the type and amount of the thermal polymerization initiator and the type of polymerizable compound. However, it is generally preferable to start the polymerization at a relatively low temperature and slowly increase the temperature. Since the polymerization time, like the temperature, also varies depending on various factors, it is preferable to determine the optimal time in advance based on these conditions. Generally, it is preferable to select conditions so that the polymerization is completed within 2 to 48 hours. When obtaining a photochromic laminate sheet, it is preferable to carry out the polymerization at a temperature at which the reaction between polymerizable functional groups proceeds, and to determine the optimal temperature and time to achieve the desired molecular weight.

[0128] Furthermore, when photopolymerizing the curable composition of the present invention, among the polymerization conditions, UV intensity in particular affects the properties of the resulting photochromic cured product. The illuminance conditions cannot be generally limited because they are affected by the type and amount of the photopolymerization initiator and the type of polymerizable monomer, but are generally 50 to 500 mW / cm at a wavelength of 365 nm. 2 It is preferable to select the conditions so that the UV light is irradiated for 0.5 to 5 minutes.

[0129] The photochromic compound of the present invention can be used in a wide range of applications as a photochromic material, including, for example, various storage materials replacing silver halide photosensitive materials, copying materials, printing photoreceptors, storage materials for cathode ray tubes, photosensitive materials for lasers, photosensitive materials for holography, etc. In addition, photochromic materials using the chromene compound of the present invention can also be used as materials for photochromic lenses, optical filters, display materials, actinometers, decorations, etc.

[0130] For example, any known method can be used to manufacture a photochromic lens using the photochromic compound of the present invention by utilizing the above-mentioned polymerization curing, as long as it is a method that can provide uniform photochromic performance.

[0131] When photochromic properties are expressed by the kneading method, the above-mentioned curable composition is injected between glass molds held by elastomer gaskets or spacers, and depending on the types of polymerizable compound and polymerization curing accelerator, a photochromic cured product molded into the shape of an optical material such as a lens can be obtained by casting polymerization using heating in an air oven or irradiation with active energy rays such as ultraviolet rays.

[0132] When photochromic properties are expressed by a lamination method, a coating liquid is prepared by dissolving the curable composition in an appropriate organic solvent, and the coating liquid is applied to the surface of an optical substrate such as a lens substrate by spin coating, dipping, or the like, and then dried to remove the organic solvent. Subsequently, polymerization and curing are carried out by UV irradiation or heating in an inert gas such as nitrogen, thereby forming a photochromic layer made of a photochromic cured product on the surface of the optical substrate (coating method).

[0133] Alternatively, a photochromic layer made of a photochromic cured product can be formed on the surface of an optical substrate by cast polymerization using an inner mold in which an optical substrate such as a lens substrate is placed facing a glass mold so that a predetermined gap is formed, a curable composition is injected into this gap, and then polymerization and curing are carried out in this state by UV irradiation, heating, etc. (cast polymerization method).

[0134] When forming a photochromic layer on the surface of an optical substrate by the above-mentioned lamination methods (coating method and cast polymerization method), the adhesion between the photochromic layer and the optical substrate can be improved by previously subjecting the surface of the optical substrate to a chemical treatment using an alkaline solution, an acid solution, etc., or a physical treatment using corona discharge, plasma discharge, polishing, etc. Of course, it is also possible to provide a transparent adhesive resin layer on the surface of the optical substrate.

[0135] Furthermore, when photochromic properties are expressed by a binder method, a photochromic sheet is produced by sheet molding using a curable composition, and this is sandwiched between two transparent sheets (optical sheets) and subjected to the aforementioned polymerization and curing, thereby obtaining a photochromic laminate in which the photochromic layer serves as an adhesive layer.

[0136] In this case, the photochromic sheet can also be produced by coating with a coating liquid prepared by dissolving the curable composition in an organic solvent.

[0137] The photochromic laminate thus produced is, for example, placed in a mold, and then a thermoplastic resin for optical substrates such as lenses (e.g., polycarbonate) is injection molded to obtain an optical substrate such as a lens of a predetermined shape to which photochromic properties have been imparted. This photochromic laminate can also be adhered to the surface of an optical substrate with an adhesive or the like, thereby obtaining a photochromic lens.

[0138] When preparing 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, and adjust it so that polyurethane is formed, in order to obtain particularly high adhesion to the optical substrate.

[0139] The curable composition of the present invention described above can exhibit photochromic properties with excellent color density at high temperatures.

[0140] Furthermore, the photochromic layer or photochromic cured product formed from the curable composition of the present invention can be subjected to post-processing such as dyeing with a dye such as a disperse dye, preparation of a hard coat film using a hard coat agent mainly composed of a silane coupling agent or a sol of silicon, zirconium, antimony, aluminum, tin, tungsten, or the like, formation of a thin film by vapor deposition of a metal oxide such as SiO2, TiO2, or ZrO2, anti-reflection treatment using a thin film by coating with an organic polymer, or anti-static treatment, depending on the application. [Example]

[0141] Example 1 1st step: 4,4'-Stilbenedicarboxylic acid 2.68g (10.0mmol) Thionyl chloride 50mL 3 drops of DMF The mixture was refluxed under nitrogen for 2 hours. After confirming that the raw material had been consumed, the mixture was concentrated under reduced pressure and dried to obtain 4,4'-stilbene dicarbonyl chloride as a yellow solid in a yield of 100%.

[0142] Second step: The 4,4'-stilbene dicarbonyl chloride obtained in the first step is Aluminum chloride 2.93g (22.0mmol) 30mL of dichloromethane was added and stirred under nitrogen for 1 hour.

[0143] Anisole 2.70g (25.0mmol) Dichloromethane 50mL The mixture was stirred under ice cooling, and the dichloromethane solution of 4,4'-stilbene dicarbonyl chloride and ammonium chloride obtained above was added thereto, followed by stirring for 12 hours while warming to room temperature. 500 mL of methanol was added under ice cooling, and the precipitated solid was filtered off and washed with methanol. 100 mL of chloroform was added to the obtained solid, and after refluxing for 1 hour, the solid was cooled to room temperature and filtered off to obtain bisbenzophenone represented by the following formula (8) in a yield of 75%.

[0144] [ka]

[0145] Third step: Trimethylsilylacetylene 2.95g (30.0mmol) THF 30mL The mixture was stirred and cooled to -20°C, and then 18.8 mL of n-BuLi (1.6 mM hexane solution) was slowly added thereto, followed by stirring for 1 hour. To this was added 2.24 g (5.0 mmol) of the bisbenzophenone obtained in the second step, and the mixture was stirred for 12 hours while being warmed to room temperature. After confirming the consumption of the raw materials, the mixture was cooled with ice, and a solution of 1.74 g (31.0 mmol) of potassium hydroxide in 20 mL of methanol was added and stirred for another 3 hours. The mixture was separated using a 10% aqueous ammonium chloride solution, and bispropargyl alcohol represented by the following formula (9) was obtained in a yield of 90%.

[0146] [ka]

[0147] 4th step: A naphthol compound represented by the following formula (10) was prepared. [ka]

[0148] 1.33g (3.0mmol) of the above naphthol compound The bispropargyl alcohol compound obtained in the third step 2.00g (4.0mmol) Dissolve in 50 ml of toluene, and Pyridinium p-toluenesulfonate 0.75g (0.3mmol) was added and stirred for 1 hour at 85° C. After the reaction, the solvent was removed and the residue was purified by silica gel chromatography to obtain a compound represented by the following formula (11) in a yield of 70%.

[0149] [ka]

[0150] The elemental analysis of this product was as follows: C81.5%, H6.7%, S4.7% This analytical value is C 92 H 88 This was in excellent agreement with the calculated values for O6S2: C 81.6%, H 6.6%, and S 4.7%.

[0151] Furthermore, when the proton nuclear magnetic resonance spectrum was measured, the following peaks were observed. 48H peaks due to cyclohexane ring, ethyl group, and methyl group in the vicinity of 1.0 to 3.0 ppm 6H peak due to methoxy group around δ2.3-4.0 ppm Aromatic protons and 34H peaks due to alkene protons around δ5.0-9.0 ppm

[0152] moreover 13 The C-nuclear magnetic resonance spectrum was measured, and the following peaks were observed. Peaks due to aromatic ring carbon around δ110-160 ppm Peaks based on alkene carbon around δ80-140 ppm Peaks due to alkyl carbon at δ20-60 ppm

[0153] <Examples 2 to 4> In the same manner as in Example 1, the propargyl alcohol compounds shown in Table 1 (Examples 2 to 4) were prepared and reacted with the naphthol compound of Example 1 to synthesize chromene compounds (photochromic compounds).

[0154] [Table 1]

[0155] The resulting chromene compound was subjected to structural analysis using the same structural confirmation means as in Example 1, and was confirmed to be a compound represented by the structural formula shown in Table 1. Table 2 also shows the elemental analysis values of these compounds, the calculated values obtained from the structural formulas of each compound, and 1 The H-NMR spectrum showed a characteristic spectrum.

[0156] [Table 2]

[0157] <Examples 5 to 8> (Evaluation in toluene solution) A 0.05 mmol / L (0.1 mmol / L in terms of the photochromic moiety) toluene solution of each of the photochromic compounds of Examples 1 to 4 was prepared, and the following evaluation was carried out using a quartz cell with an optical path length of 1 cm. The results are shown in Table 3.

[0158] (1) Photochromic properties [1] Maximum absorption wavelength (λmax): This is the maximum absorption wavelength after color development, determined using a spectrophotometer (instant multichannel photodetector MCPD3000) manufactured by Otsuka Electronics Co., Ltd., and was used as an index of the color tone during color development.

[0159] [2] 23℃ color density (A 23 ): The difference between the absorbance {ε(180)} after 180 seconds of light irradiation at 23°C and the absorbance ε(0) before light irradiation at the maximum absorption wavelength was used as an index of color density. The higher this value, the better the photochromic properties.

[0160] [3] 36℃ color density (A 36 ): The difference between the absorbance {ε(180)} after 180 seconds of light irradiation at 36°C and the absorbance ε(0) before light irradiation at the maximum absorption wavelength was used as an index of color density. The higher this value, the better the photochromic properties.

[0161] [4] Temperature dependence (A 36 / A 23 x100): 23℃ color density (A 23 ) at 36℃ color density (A 36 The higher this value, the smaller the temperature dependency, and the better it can be said to be.

[0162] [5] 23℃ Fading Half-Life [τ1 / 2 (sec.)]: After 180 seconds of light irradiation at 23°C, the time required for the absorbance of the sample at the maximum absorption wavelength to decrease to half of {ε(180) - ε(0)} when the light irradiation was stopped was measured. This time was used as an index of the fading rate. The shorter this time, the faster the fading rate.

[0163] [Table 3]

[0164] In Table 1, the compound synthesized in Example 1 was designated as Compound 1. Similarly, the compounds synthesized in Examples 2 to 4 were designated as Compounds 2 to 4.

[0165] <Comparative Examples 1 to 3> For comparison, a 0.1 mmol / L toluene solution was prepared using the compounds represented by the following formulas (A) to (C) in the same manner as in the examples, and its properties were evaluated. The results are shown in Table 4.

[0166] [ka]

[0167] [Table 4]

[0168] The temperature dependence results of Examples 5 to 8 and Comparative Examples 1 to 3 (A in Tables 3 and 4) 36 / A 23 × 100(%)) and the fading half-life at 23°C are plotted in Figure 1.

[0169] As can be seen from FIG. 1, the temperature dependency and 23°C fading half-life of the compounds of the comparative examples are in a linear relationship. In other words, compounds with a fast fading rate have a low temperature dependency. The difference between the compounds of the examples and the comparative examples is that they have the same structure, except for the presence or absence of bonds. Therefore, Examples 5 to 8 and Comparative Examples 1 to 3, which have the same concentration in terms of photochromic moiety, can be directly compared. 1, Examples 5 to 8 (compounds No. 1 to 4) using the photochromic compounds of the present invention are positioned above the linear relationship of the comparative examples. As a result, it is clear that the photochromic compounds of the present invention have excellent temperature dependency (low temperature dependency) when compared at the same fading rate.

[0170] Example 9 (Evaluation of physical properties of photochromic plastic lenses produced by coating method) Chromene Compound No. 1 obtained in Example 1 above was mixed with a photopolymerization initiator and a polymerizable monomer, and then coated on the surface of a lens substrate. The coating on the surface of the lens substrate was then polymerized by irradiating with ultraviolet light.

[0171] The photochromic curable composition used was a composition containing the following radical polymerizable monomers in combination. 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

[0172] The total amount of the radical polymerizable monomers was 100 parts by mass. When the total amount of the radical polymerizable monomers was 100 g, the photochromic compound was added to the radical polymerizable monomers so that the amount was 0.27 mmol. The following additives were added thereto and mixed thoroughly to obtain a photochromic curable composition. Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide Cid (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 Speci (Irganox 245, manufactured by Chalty Chemicals) 1 part by mass Bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate Molecular weight 508 3 parts by mass Leveling agent manufactured by Toray Dow Corning Co., Ltd.: L7001 0.1 part by mass The additives are blended in proportions based on 100 parts by mass of the total amount of radically polymerizable monomers.

[0173] Using this curable composition, a photochromic laminate (photochromic optical article) was obtained by a lamination method in which polymerization was carried out as follows.

[0174] First, a thiourethane-based plastic lens with a center thickness of 2 mm and a refractive index of 1.60 was prepared as an optical substrate. This thiourethane-based plastic lens was previously subjected to alkaline etching using a 10% aqueous sodium hydroxide solution at 50°C for 5 minutes, and then thoroughly washed with distilled water.

[0175] Using a spin coater (1H-DX2, manufactured by MIKASA), the surface of the plastic lens was coated with a moisture-curable primer (product name: TR-SC-P, manufactured by Tokuyama Corporation) at a rotation speed of 70 rpm for 15 seconds, followed by 1000 rpm for 10 seconds. Approximately 2 g of the photochromic curable composition obtained above was then spin coated at a rotation speed of 60 rpm for 40 seconds, followed by 600 rpm for 10 to 20 seconds, to form a photochromic coating layer with a thickness of 40 μm.

[0176] The lens having the photochromic curable composition (photochromic coating layer) applied to its surface was heated in a nitrogen gas atmosphere at an output of 200 mW / cm 2 The coating was cured by irradiating it with light for 90 seconds using a metal halide lamp, and then heated at 110°C for an additional hour to prepare a photochromic laminate having a photochromic layer.

[0177] The obtained photochromic laminate was used as a sample and evaluated in the same manner as in Examples 5 to 8. The results are shown in Table 5.

[0178] <Examples 10 to 12> Photochromic laminates were produced in the same manner as in Example 9, except that the compound of Example 2 (Compound 2) was used (Example 10), the compound of Example 3 (Compound 3) was used (Example 11), and the compound of Example 4 (Compound 4) was used (Example 12). The results are shown in Table 5.

[0179] [Table 5]

[0180] <Examples 13 to 31> In the same manner as in Example 1, the propargyl alcohol compounds and naphthol compounds shown in Tables 6 to 9 were reacted to synthesize the chromene compounds shown in Tables 10 to 15.

[0181] [Table 6]

[0182]

Table 7

[0183]

Table 8

[0184]

Table 9

[0185]

Table 10

[0186]

Table 11

[0187]

Table 12

[0188]

Table 13

[0189]

Table 14

[0190]

Table 15

[0191] The obtained chromene compounds were subjected to structural analysis using the same structural confirmation means as in Example 1, and as a result, they were confirmed to be compounds represented by the structural formulas shown in Tables 10 to 15. Table 16 also shows the elemental analysis values of these compounds, the calculated values obtained from the structural formulas of each compound, and the 1 The H-NMR spectrum showed a characteristic spectrum.

[0192] [Table 16]

[0193] Example 32 1st step; A reaction was carried out by referring to the method described in Example 1 of WO2013 / 052338, except that a compound of the following formula (12) was used instead of anisoyl chloride, to obtain a bisbenzophenone represented by the following formula (13) in a yield of 65%.

[0194] [ka]

[0195] [ka]

[0196] 2nd step; In the third step of Example 1 of the present invention, a reaction was carried out in the same manner as in Example 1, except that the bisbenzophenone of the above formula (13) was used instead of the bisbenzophenone of the formula (8), to obtain a compound represented by the following formula (14) in a yield of 64%.

[0197] [ka]

[0198] 3rd step; Polyethylene glycol monomethyl ether with a number average molecular weight of 750 75g (0.10mol) Succinic anhydride 20g (0.20mol) Triethylamine 30.3g (0.30mol) Dichloromethane 1000mL The mixture was mixed and stirred at room temperature for 12 hours. After the reaction was completed, the mixture was separated with 10% brine. The resulting organic layer was dried over anhydrous magnesium sulfate. The magnesium sulfate was filtered off and the solvent was distilled off to obtain the compound represented by the following formula (15) as an oil.

[0199] [ka]

[0200] 4th step; Compound of formula (14) (photochromic compound) obtained in the second step 2.8g (2.0mmol) Compound of formula (15) obtained in the third step: 4.3 g (5.0 mmol) 50ml dichloromethane After mixing and stirring, WSC(water-soluble carbodiimide) 768mg DMAP (dimethylaminopyridine) 252mg The mixture was added and stirred for 12 hours in the dark. After confirming the disappearance of the raw materials by TLC (Thin Layer Chromatography), water was added to stop the reaction. After extraction with toluene, the mixture was concentrated using an evaporator and purified by silica gel chromatography to obtain the photochromic compound represented by the following formula (16). The yield was 75%.

[0201] [ka]

[0202] When the proton nuclear magnetic resonance spectrum of the above compound was measured, the following peaks were observed. At around δ1.0 to 5.0 ppm, there are peaks of approximately 206H due to the cyclohexane ring, ethyl group, methyl group, succinic acid moiety, methoxy group, ethylene glycol moiety, and polyethylene glycol chain; 32H peaks due to aromatic protons and alkene protons at around δ5.0-9.0 ppm;

[0203] Example 33 1st step; The reaction was carried out in the same manner as in Example 1, except that paraphenylenedicarbonyl chloride was used instead of 4,4'-stilbene dicarbonyl chloride and dimethylaniline was used instead of anisole, to synthesize a bispropargyl alcohol compound represented by the following formula (17).

[0204] [ka]

[0205] The above bispropargyl alcohol compound was reacted with a naphthol compound represented by the following formula (18) in the same manner as in Example 1 to obtain a photochromic compound represented by the following formula (19) in a yield of 50%.

[0206] [ka]

[0207] [ka]

[0208] 2nd step; The same operation as in the third step of Example 32 was carried out, except that in the third step, a compound represented by the following formula (20) having a number average molecular weight of 1,100 was used instead of polyethylene glycol monomethyl ether having a number average molecular weight of 750, to obtain a compound represented by the following formula (21).

[0209] [ka]

[0210] [ka]

[0211] 3rd step; A photochromic compound represented by the following formula (22) was obtained in a yield of 79% in the same manner as in the fourth step of Example 32, except that the compounds of the formulae (19) and (21) were used instead of the compounds of the formulae (14) and (15).

[0212] [ka]

[0213] When the proton nuclear magnetic resonance spectrum of the above photochromic compound was measured, the following peaks were observed. At around δ1.0 to 5.0 ppm, there are peaks of approximately 208H due to methyl groups, ethylene glycol moieties, succinic acid moieties, propyl groups, diethylamino groups, and polydimethylsiloxane chains; Aromatic protons and 32H peaks due to alkene protons are present around δ5.0-9.0 ppm;

[0214] <Examples 34 to 54> Photochromic laminates were produced in the same manner as in Example 9, and evaluations were carried out in the same manner, except that the compounds shown in Tables 10 to 15 were used. The results are shown in Tables 17 and 18. In Example 53, the compound synthesized in Example 32 (Compound 32) was used, and in Example 54, the compound synthesized in Example 33 (Compound 33) was used.

[0215] [Table 17]

[0216] [Table 18]

[0217] Example 55 (Evaluation of physical properties of photochromic plastic lenses produced by the binder method) The photochromic layer was prepared by the following method.

[0218] Preparation of terminally non-reactive urethane urea resin; In a 2L four-neck flask equipped with a stirring blade, a condenser, a thermometer, and a nitrogen gas inlet tube, 220 parts by mass of polycarbonate diol with a number average molecular weight of 700 Isophorone diisocyanate 100 parts by mass Toluene 72 parts by mass The mixture was reacted at 100°C for 7 hours under a nitrogen atmosphere to synthesize a urethane prepolymer having an isocyanate group at its terminal. After the synthesis of the urethane prepolymer, the reaction liquid was cooled to around 0°C and dissolved in 205 parts by mass of isopropyl alcohol and 382 parts by mass of diethyl ketone, and the liquid 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 is a chain extender, was added dropwise within 30 minutes, and the mixture was allowed to react at 0° C. for 1 hour. Thereafter, 5.7 parts by mass of 1,2,2,6,6-pentamethyl-4-aminopiperidine was further added dropwise, and the mixture was allowed to react at 0° C. for 1 hour to obtain a diethyl ketone solution of a terminally unreactive urethane urea resin.

[0219] Preparation of a composition for forming a photochromic layer; Per 100 parts by mass of the solid content of the terminally non-reactive urethane urea resin solution obtained above, 4 parts by mass of 4,4'-methylenebis(cyclohexyl isocyanate) isomer mixture (polyisocyanate compound) Ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] (antioxidant) 0.4 parts by mass Surfactant (DOW CORNING TORAY L-7001) 0.06 parts by mass was added to the solution. Furthermore, the photochromic compound synthesized in Example 1 (Compound 1; 0.26 mmol) was added per 100 g of the solid content, and these were stirred and mixed at room temperature to obtain a composition for forming a photochromic layer.

[0220] Synthesis of adhesive for adhesive layer (non-reactive terminal urethane urea resin); Prepare a 5L separable flask (4 necks) equipped with a stirring blade, a condenser, a thermometer, and a nitrogen gas inlet tube. 400 parts by mass of polycarbonate diol with a number average molecular weight of 1000 Isophorone diisocyanate 175 parts by mass Toluene 120 parts by mass The mixture was reacted at 110°C for 7 hours under a nitrogen atmosphere to synthesize a urethane prepolymer having an isocyanate group at its terminal. After the reaction was completed, the reaction mixture was cooled to about 20°C and dissolved in 2500 parts by mass of propylene glycol monomethyl ether, and the liquid temperature was maintained at 20°C. Next, 60 parts by mass of isophoronediamine, a chain extender, was added dropwise, and the mixture was allowed to react for 1 hour at 20° C. Thereafter, 3 parts by mass of n-butylamine was added dropwise, and the mixture was allowed to react for 1 hour at 20° C., thereby obtaining a propylene glycol-monomethyl ether solution of a terminally unreactive urethane urea resin.

[0221] 500 parts by mass of the obtained terminally non-reactive urethane urea resin solution, Surfactant (DOW CORNING TORAY L-7001) 0.2 parts by mass The mixture was stirred and mixed at room temperature to obtain an adhesive for adhesive layers.

[0222] Production of photochromic laminates; Using a coater (manufactured by Tester Sangyo), the adhesive for the adhesive layer was applied to a 400 μm thick polycarbonate sheet (first and second optical sheets; one being the optical substrate and the other being a layer not containing a photochromic compound) at a coating speed of 0.5 m / min, and the sheet was 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. Next, using a coater (manufactured by Tester Sangyo Co., Ltd.), 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. Thereafter, the photochromic layer (40 μm thick) side was placed on the adhesive resin layer of the first optical sheet having the adhesive resin layer, and they were laminated together.

[0223] Furthermore, a structure obtained by peeling off the OPP film from the laminate of the first optical sheet / adhesive resin layer / photochromic layer / OPP film prepared by the above method was bonded to a polycarbonate sheet (second optical sheet) having an adhesive resin layer so that the photochromic layer and the adhesive resin layer on the polycarbonate sheet (second optical sheet) were bonded. The resulting laminate was then left to stand at 40°C under vacuum for 24 hours, then heat-treated at 110°C for 60 minutes, then humidified 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.

[0224] The obtained photochromic laminate was used as a sample and evaluated in the same manner as in Example 5. The results are shown in Table 19.

[0225] <Examples 56 to 59> Photochromic laminates were produced in the same manner as in Example 55, and evaluations were carried out in the same manner, except that the photochromic compounds shown in Table 19 were used. The results are shown in Table 19. From this result, it is clear that the binder method also exhibits excellent temperature dependency.

[0226] [Table 19]

[0227] Example 60 (Evaluation of the physical properties of photochromic plastic lenses manufactured by lamination method) A photochromic curable composition was prepared according to the following formulation, and this composition was cast and polymerized on the surface of the lens substrate.

[0228] Preparation of the curable composition; Each component was thoroughly mixed according to the following formulation to prepare a polymerizable composition. 1,3-bis(isocyanatomethyl)cyclohexane 38.3 parts by mass Pentaerythritol tetrakis(3-mercaptopropionate) 42.5 parts by mass Tridecane 1-thiol 2.9 parts by mass Polyoxyethylene polyoxypropylene monododecyl ether (number average molecular weight 1200) 12.3 parts by mass RX-1 4.0 parts by mass of a polyrotaxane monomer synthesized by the method described in the third step of Example 1 of WO 2018 / 235771 (pr1 in WO 2018 / 235771; Reference Example 1). The total amount of the above polymerizable compositions was 100 parts by mass. 0.05 parts by mass of dimethyldichlorotin was blended with a total of 100 parts by mass of this polymerizable composition. Furthermore, the photochromic compound (Compound 2) synthesized in Example 2 was added in an amount of 0.1 mmol per 100 g of the total polymerizable composition to prepare a photochromic curable composition.

[0229] Production of photochromic laminates; The photochromic laminate was obtained by laminating the photochromic curable composition described above. The polymerization method was as follows.

[0230] After the photochromic curable composition was thoroughly degassed, it was poured into a mold consisting of a glass plate with a gap of 1 mm and a thiourethane-based plastic lens with a refractive index of 1.60, and the photochromic curable composition was polymerized by cast polymerization. The polymerization was carried out over 18 hours while gradually increasing the temperature from 27°C to 120°C. After polymerization, only the glass plate was removed to obtain a laminated photochromic optical article in which a 1 mm thick photochromic layer was laminated on a thiourethane plastic lens with a refractive index of 1.60.

[0231] The obtained photochromic laminate was used as a sample and evaluated in the same manner as in Example 5. The results are shown in Table 20.

[0232] <Examples 61 to 63> Photochromic laminates were produced in the same manner as in Example 60, and evaluations were carried out in the same manner, except that the photochromic compounds shown in Table 20 were used. The results are shown in Table 20.

[0233] [Table 20]

[0234] <Example 64, Comparative Examples 4 and 5> (Weather resistance evaluation) 3 mL of a toluene solution (1 mmol / L concentration of the photochromic basic structural group) of the photochromic compound (Compound 3) synthesized in Example 3 and a stirring bar were placed in a 6 mL vial, sealed, and then the vial was placed sideways and stirred while being irradiated with simulated sunlight for 10 minutes at a temperature range of 23 to 24°C using a XENON LAMP POWER SUPPLY MODEL YSS-50 manufactured by Yamashita Denso Co., Ltd. The toluene solution was analyzed before and after irradiation using high-performance liquid chromatography (HPLC), and the residual rate was calculated using the following formula.

[0235] Residual rate (%) = (area of photochromic compound after 10 minutes of irradiation) / (area of photochromic compound before irradiation) x 100 The higher the survival rate, the better the weather resistance. For comparison, compounds bonded via an organic group having an S-containing aromatic ring represented by the above formula (B) and the following formula (D), which were synthesized with reference to the examples in JP-A No. 2005-508897, were evaluated in the same manner as in Example 64 (Comparative Examples 4 and 5). The results are shown in Table 21.

[0236] [ka]

[0237] [Table 21] As is clear from Table 21, the photochromic compounds of the present invention have superior weather resistance compared to photochromic compounds bonded via an organic group having an S-containing aromatic ring.

Claims

1. A photochromic compound having at least two monovalent photochromic basic structural groups PC each containing a T-shaped photochromic moiety, wherein the photochromic basic structural groups are bonded to an organic group having a non-SO-based aromatic ring containing no sulfur atom or oxygen atom, and represented by the following formula (1): 【Chemical 1】 During the ceremony, m is an integer of 2 or greater; PC represents the monovalent photochromic basic structural group, L and R ３ provided that at least one of them contains the non-SO aromatic ring. L represents a phenylene group or a direct bond to which the PC is bonded at the terminal thereof, R ３ represents an m-valent organic group or a direct bond, and when represents a direct bond, m=2 and L is the phenylene group; The R ３ is at least one selected from the group consisting of a non-SO-based aromatic ring group, a saturated or unsaturated hydrocarbon group having 1 to 3 carbon atoms, a polyvalent silylene group having 1 to 3 silicon atoms and having an alkyl group having 1 to 15 carbon atoms as a substituent, an oxygen atom, or a sulfur atom (m=2), The R ３ the molecular weight of the organic group bonded to the PC containing the group per PC is less than 1000; The monovalent photochromic basic structural group PC is represented by the following formula (2): 【Chemistry 2】 During the ceremony, a is an integer from 0 to 4, b is an integer from 0 to 4; R ４ and R ５ respectively represent the following groups: hydroxyl groups; an alkyl group having 1 to 6 carbon atoms; a cycloalkyl group having 3 to 8 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; Amino group; cyano group; halogen atoms; nitro group; formyl group; hydroxycarbonyl group; an alkylcarbonyl group having 2 to 7 carbon atoms; an alkoxycarbonyl group having 1 to 7 carbon atoms; an aryl group having 6 to 12 carbon atoms; heterocyclic groups; an alkylthio group having 1 to 6 carbon atoms; a cycloalkylthio group having 3 to 8 carbon atoms; an arylthio group having 6 to 12 carbon atoms; an aralkyl group having 7 to 11 carbon atoms; an aralkoxy group having 7 to 11 carbon atoms; an aryloxy group having 6 to 12 carbon atoms; thiol groups; an alkoxyalkylthio group having 1 to 6 carbon atoms; A group represented by the following formula (X): 【Chemistry 3】 During the ceremony, E is an oxygen atom or NR １０１ and R １０１ is a hydrogen atom or an alkyl group, F is an oxygen atom or a sulfur atom, R ２０１ represents a hydrogen atom, an alkyl group, a cycloalkyl group, G is an oxygen atom, a sulfur atom, or NR ２０２ and R ２０２ is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group, and when G is an oxygen atom or a sulfur atom, R ２０１ is a group other than a hydrogen atom, g is an integer of 0 or 1; A group represented by the following formula (Y): 【Chemistry 4】 During the ceremony, R ３００ is an alkylene group or a silylene group having an alkyl group or an aryl group as a substituent, R ３０１ is an alkyl group or an aryl group, R ３０２ , R ３０３ and R ３０４ is an alkylene group, h, j, k, and l are integers of 0 or 1; i is an integer of 2 to 200, and multiple i units may be the same or different; Multiple R exists depending on the value of a or b ４ Or R ５ may be the same or different, and R ４ Or R ５ If there is a ４ Or R ５ Together, R ４ Or R ５ may form a ring together with the carbon atom to which it is attached which may contain an oxygen atom, a carbon atom, a sulfur atom or a nitrogen atom, R ６ and R ７ are each an aryl group or a heteroaryl group, provided that either one of them represents a direct bond to the organic group bonded to PC containing the R 3 group; R ８ and R ９ respectively represent the following groups: hydrogen atom; hydroxyl groups; an alkyl group having 1 to 6 carbon atoms; a cycloalkyl group having 3 to 8 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; alkoxyalkyl groups; formyl group; hydroxycarbonyl group; an alkylcarbonyl group having 2 to 7 carbon atoms; an alkoxycarbonyl group having 1 to 7 carbon atoms; halogen atoms; an aralkyl group having 7 to 11 carbon atoms; an aralkoxy group having 7 to 11 carbon atoms; an aryl group having 6 to 12 carbon atoms; an aryloxy group having 6 to 12 carbon atoms; heterocyclic groups; A group represented by the formula (Y); In the formula (2), R ８ and R ９ may combine together with the carbon atom at position 13 to which they are bonded to form an aliphatic ring having 3 to 20 carbon atoms, a condensed polycycle in which an aromatic ring or an aromatic heterocycle is condensed to the aliphatic ring, a heterocycle having 3 to 20 ring atoms, or a condensed polycycle in which an aromatic ring or an aromatic heterocycle is condensed to the heterocycle.

2. In the formula (2), R ８ and R ９ are taken together to form an aliphatic ring, the aliphatic ring being a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cycloundecane ring, a cyclododecane ring, or a spirodicyclohexane ring, and the ring may have, as a substituent, 1 to 10 alkyl groups having 1 to 3 carbon atoms or cycloalkyl groups having 5 to 7 carbon atoms, or the ring may be fused with a cycloalkyl group having 5 to 7 carbon atoms.

3. A photochromic curable composition comprising the photochromic compound according to claim 1 and a polymerizable compound.

4. A photochromic optical article obtained by polymerizing the photochromic curable composition according to claim 3.

5. A polymer molded product having the photochromic compound according to claim 1 dispersed therein.

6. An optical article coated with a polymer film in which the photochromic compound according to claim 1 is dispersed.

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