JP7195209B2 - A photochromic compound, a curable composition containing the photochromic compound, and a photochromic cured body comprising the curable composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel photochromic compound, a novel photochromic curable composition containing the photochromic compound, and a novel cured body comprising the curable composition.

Photochromic compounds typified by chromene compounds, fulgide compounds, spirooxazine compounds, etc., change color quickly when exposed to light containing ultraviolet rays such as sunlight or mercury lamp light, and when the light irradiation is stopped and placed in a dark place. It has a property of returning to the original color (photochromic property), and is used in various applications, especially as an optical material, taking advantage of this property.

For example, photochromic spectacle lenses that have been given photochromic properties through the use of photochromic compounds are rapidly colored and function as sunglasses outdoors where they are irradiated with light including ultraviolet rays such as sunlight. In indoor environments where there is no glasses, the color fades and the glasses function as normal transparent glasses, and the demand for them has been increasing in recent years.

In order to impart photochromic properties to optical materials, photochromic compounds are generally used in combination with plastic materials. Specifically, the following means are known.
(a) A method of directly forming an optical material such as a lens by dissolving a photochromic compound in a compound and polymerizing it. This method is called a kneading method.
(b) A method of providing a resin layer in which a photochromic compound is dispersed on the surface of a plastic molded article such as a lens by coating or casting polymerization. This method is called a lamination method.
(c) bonding two optical sheets with an adhesive layer formed of an adhesive resin in which a photochromic compound is dispersed; This method is called the binder method.

Optical materials such as optical articles to which photochromic properties are imparted are further required to have the following properties.
(I) The degree of coloration (initial coloration) in the visible light region before irradiation with ultraviolet rays is low.
(II) The degree of coloring (coloring density) when irradiated with ultraviolet rays is high.
(III) The speed (discoloration speed) from the time when the irradiation of ultraviolet rays is stopped until the film returns to its original state is fast.
(IV) Good durability against repeated reversible action from coloring to fading.
(V) high storage stability;
(VI) It should be easy to mold into various shapes.

Various photochromic compounds have been reported so far, but even photochromic compounds with good photoresponsivity in liquid matrices have poor photoresponsivity in solid matrices and tend to have long fading half-lives. has been reported. This is probably because the free space in the solid matrix is overwhelmingly smaller than in the liquid matrix, which limits the structural change of the photochromic compound. As a method for solving this problem, a photochromic compound capable of nanoencapsulation has been proposed. Specifically, in recent years, photochromic compounds having oligomer chain groups such as polyalkyleneoxy oligomer chain groups and polysiloxane oligomer chain groups (hereinafter referred to as polymer photochromic compounds) have been disclosed. These polymer photochromic compounds are reported to have low matrix dependency and exhibit excellent photoresponsivity even in a solid matrix (see Patent Documents 1 and 2).

Although the above polymer photochromic compound is a technique that has been attracting attention in recent years, it is also known that a cured body containing the polymer photochromic compound becomes cloudy. As a solution to this problem, in the case of (thio)urethane lenses, by controlling the functional group equivalent ratio between the isocyanate compound and the bifunctional alcohol, photochromic properties can be expressed and, in addition, cloudiness of the lens can be suppressed. known (see Patent Document 3).

WO2004/041961 WO2000/015630 WO2017/047745

As described above, the polymeric photochromic compound exhibits high photochromic properties in each matrix. On the other hand, however, it is known that the resulting photochromic cured product becomes cloudy, probably because the polymer photochromic compound aggregates during curing.

On the other hand, a low-molecular-weight photochromic compound having no oligomer chain group does not aggregate in a solid matrix, and a transparent photochromic cured product can be obtained. However, it is highly matrix-dependent, and the fading rate in a solid matrix may be a problem.

Moreover, from the viewpoint of production of the photochromic cured product, both the polymer and the low-molecular-weight photochromic compound preferably dissolve rapidly in the monomer composition serving as the base material of the optical article.

As described above, in recent years, photochromic properties can be expressed without depending on the matrix, it has excellent solubility in the monomer composition that is the base material of the optical article, and does not aggregate during the molding process (during curing) of the optical base material. Development of a photochromic compound that is stably dispersed has been desired.

Accordingly, an object of the present invention is to provide a photochromic compound having the above effects.

The inventors of the present invention have made intensive studies to solve the above problems. Then, the introduction of various substituents into polymer photochromic compounds that exhibit excellent photochromic properties in solid matrices was investigated so that they could be highly dispersed in the matrix. As a result, they have found that a polymeric photochromic compound having an alkenyl group with 10 to 30 carbon atoms is useful for solving the above problems. That is, by introducing an alkenyl group having 10 to 30 carbon atoms into a polymer photochromic compound, it is possible to maintain the photochromic properties in the solid matrix and at the same time exhibit excellent solubility in the monomer composition and during curing. The inventors have also found that the aggregation of is suppressed, and have completed the present invention.

That is, the first invention is
having an indenonaphthopyran moiety,
The indenonaphthopyran moiety includes
an alkenyl group having 10 to 30 carbon atoms;
A photochromic compound having an oligomer chain group A having 3 or more repeating units selected from a polyalkylene oxide oligomer chain group, a polyester oligomer chain group, a polysiloxane chain group, and a polyester polyether oligomer chain group.

The second invention is a photochromic curable composition comprising the photochromic compound of the first invention and a polymerizable compound.

The third aspect of the present invention is a photochromic optical article obtained by polymerizing the photochromic curable composition of the second aspect of the present invention.

The fourth aspect of the present invention is a polymer molded body in which the photochromic compound of the first aspect of the present invention is dispersed.

The fifth invention is an optical article coated with a polymer film in which the photochromic compound of the first invention is dispersed.

The photochromic compounds of the present invention exhibit excellent photochromic properties in polymeric matrices. In addition, when existing photochromic compounds are used, problems such as clouding of the cured product may occur. A photochromic cured product can be produced.

The photochromic compound of the present invention has an indenonaphthopyran site, and the indenonaphthopyran site comprises an alkenyl group having 10 to 30 carbon atoms, a polyalkylene oxide oligomer chain group, a polyester oligomer chain group, and a polysiloxane chain group. , and a polyester polyether oligomer chain group, and an oligomer chain group A having 3 or more repeating units.

In the photochromic compound of the present invention, the number of indenonaphthopyran moieties is not particularly limited as long as it is at least one. Among them, the number of the indenonaphthopyran moieties is preferably 1 to 10, more preferably 1 to 6, in consideration of the productivity, photochromic properties, solubility, etc. of the photochromic compound of the present invention. , more preferably 1 to 4, and most preferably 1 to 2.

In the case of having a plurality of indenonaphthopyran moieties, the indenonaphthopyran skeletons may have the same structure or different structures. In the present invention, having three or more repeating units means that "three or more binding sites with the same composition are present". Specifically, in the polyalkylene oxide oligomer chain group having three or more repeating units, the following formula -(RO)s-
wherein R is an alkylene group, s is a repeating unit, and s is a group of 3 or more.

If the oligomer chain group A has less than 3 repeating units, excellent photochromic properties cannot be obtained in a solid matrix, which is not preferred. The upper limit of the repeating unit is not particularly limited, and may be appropriately determined according to the photochromic properties of the desired photochromic compound. Among them, the number of repeats of the oligomer chain is preferably less than 200, more preferably 3 to 170, more preferably 10 to 150, considering the productivity, photochromic properties, etc. of the photochromic compound itself of the present invention. More preferably, it is most preferably 15-80.

When the oligomer chain group A has a small average molecular weight (short oligomer chain length), the effect of reducing matrix dependence tends to decrease. It is speculated that this is because the formation of nanocapsules enveloping the photochromic compound is difficult and the size of the nanocapsules is small, resulting in insufficient free space. Moreover, when the average molecular weight increases, the proportion of the photochromic compound per unit weight tends to decrease, resulting in insufficient color density. Therefore, it becomes necessary to increase the amount of the photochromic compound added. The average molecular weight of the oligomer chain group is not particularly limited, but considering the above circumstances, the average molecular weight is preferably 300 to 30,000, more preferably 350 to 25,000. It is preferably from 400 to 20,000, and particularly preferably from 440 to 15,000.

In the photochromic compound of the present invention, the number of oligomer chain groups A is not particularly limited, and at least one should be present in one molecule of the photochromic compound. Among them, considering the productivity, photochromic properties, etc. of the photochromic compound itself of the present invention, the number of the oligomer chain groups A in one molecule of the photochromic compound is preferably 1 to 10, more preferably 1 to 5. more preferred. The number of oligomer chain groups A per indenonaphthopyran moiety is preferably 0.25 to 6, more preferably 0.25 to 3, more preferably 0.5 to 2. is more preferable. Above all, considering the productivity and photochromic properties of the photochromic compound of the present invention, it is preferably from 0.5 to 1. When the number of oligomer chain groups A is 0.5 for one indenonaphthopyran moiety, it means that the oligomer chain group A has indenonaphthopyran moieties at both ends thereof. In addition, when the oligomer chain group A is present in plurality, the oligomer chain group A may be the same group or different groups. However, considering the productivity of the photochromic compound of the present invention, the groups are preferably the same. In consideration of photochromic properties, polyalkylene oxide oligomer chain groups and polysiloxane oligomer chain groups are most preferred.

In addition, considering the productivity and photochromic properties of the photochromic compound of the present invention, the oligomer chain group A should be substituted at the 3-, 6-, 7-, 11-, or 13-position of the indenonaphthopyran moiety. is preferred.

In the present invention, the number of alkenyl groups having 10 to 30 carbon atoms or groups having terminal alkenyl groups having 10 to 30 carbon atoms is not particularly limited. It can be appropriately changed depending on the type and molecular weight of the oligomer chain group and the number of substitutions. Among them, considering the productivity and photochromic properties of the photochromic compound itself of the present invention, and suppression of white turbidity of the photochromic cured product produced using the same, an alkenyl group having 10 to 30 carbon atoms, or an alkenyl group having 10 carbon atoms, or The number of groups having terminal alkenyl groups of up to 30 is preferably 1 to 12, more preferably 1 to 6, even more preferably 1 to 4, per one oligomer chain group. , 1-2.

In the present invention, among alkenyl groups having 10 to 30 carbon atoms or groups having an alkenyl group having 10 to 30 carbon atoms at their ends, those which exhibit particularly excellent effects are those having 15 carbon atoms in the alkenyl group portion. ~25 is preferred, and 15-20 is more preferred. Among them, considering the productivity of the photochromic compound, an oleyl group having 18 carbon atoms or a group having an oleyl group having 18 carbon atoms at its end is preferable.

Further, the alkenyl group having 10 to 30 carbon atoms or the group having an alkenyl group having 10 to 30 carbon atoms at the end may be present on the oligomer chain group A at the end. Moreover, it may exist at a different position from the oligomer chain group A in the indenonaphthopyran site. Or it may be both. When present on the oligomer chain group A, an alkenyl group having 10 to 30 carbon atoms is preferably introduced at the end of the oligomer chain group A. Above all, considering the photochromic properties and the productivity of the photochromic compound itself of the present invention, it is preferred that it exists at a position different from that of the oligomer chain group. The position at which the alkenyl group having 10 to 30 carbon atoms is present is not particularly limited, but considering the productivity of the photochromic compound of the present invention itself, the 3-position, 6-position, and 6-position of the indenonaphthopyran moiety. Substitution at the 7-, 11- or 13-position is preferred.

<Suitable photochromic compound>
In the photochromic compound of the present invention, the indenonaphthopyran moiety is represented by the following formula (1)

It is preferable to have a structure represented by Hereinafter, the photochromic compound having the above site may be simply referred to as "chromene compound".

<About a and b>
In the above formula (1), a represents the number of ^R1 . b indicates the number of ^R2 . and,
a is an integer from 0 to 4, b is an integer from 0 to 4,
When a is 2 to 4, multiple R ¹ may be the same or different,
When b is 2 to 4, multiple R ² may be the same or different.

<When a and b are 2 or more>
Further, when a is 2 to 4 and there are adjacent R ^1s , the two adjacent R ^1s are combined together with the carbon atoms bonded to those R ^1s , an oxygen atom, a sulfur atom, a carbon A ring may be formed which may contain an atom or a nitrogen atom, and the ring may further have a substituent. The ring can also have two or more atoms selected from oxygen, sulfur, carbon, and nitrogen atoms at the same time. Combinations of adjacent R ¹ are 5-position and 6-position, 6-position and 7-position, or 7-position and 8-position of the chromene compound.

Further, when b is 2 to 4 and adjacent R ² are present, the two adjacent R ² are combined together with the carbon atom bonded to these R ² , an oxygen atom, a sulfur atom, a carbon A ring may be formed which may contain an atom or a nitrogen atom, and the ring may further have a substituent. The ring can also have two or more atoms selected from oxygen, sulfur, carbon, and nitrogen atoms at the same time. Combinations of adjacent R ² are 9-position and 10-position, 10-position and 11-position, or 11-position and 12-position of the chromene compound.

At least one oligomer chain group A must be bound to the indenonaphthopyran moiety represented by formula (1). That is, at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ should be the oligomer chain group A (or the group A having the oligomer chain group).

Specific substituents will be described in order below. The preferred number, type, etc. of the indenonaphthopyran moieties represented by formula (1) and the preferred number, type, etc. of the oligomer chain group A are the same as those described above.

<R ¹ and R ² >
<R ¹ and R ² > are each independently an oligomer chain group A having 3 or more of the repeating units, the alkenyl group having 10 to 30 carbon atoms, and a group having an alkenyl group having 10 to 30 carbon atoms at the end. , a hydroxyl group, an alkyl group, a haloalkyl group, an optionally substituted cycloalkyl group, an alkoxy group, an amino group, a substituted amino group, an optionally substituted heterocyclic group, a cyano group, a halogen atom, Alkylthio group, optionally substituted arylthio group, nitro group, formyl group, hydroxycarbonyl group, alkylcarbonyl group, alkoxycarbonyl group, optionally substituted aralkyl group, optionally substituted aralkoxy group, optionally substituted aryloxy group, optionally substituted aryl group, optionally substituted heteroaryl group, thiol group, alkoxyalkylthio group, haloalkylthio group, or an optionally substituted cycloalkylthio group.

The alkyl group that can be R ¹ and R ² is not particularly limited, but is preferably an alkyl group having 1 to 6 carbon atoms. Examples of suitable alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, pentyl group, hexyl group and the like. can be mentioned.

Although the haloalkyl group is not particularly limited, it is preferably a haloalkyl group having 1 to 6 carbon atoms. As the haloalkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a fluorine atom, a chlorine atom or a bromine atom is preferred. Examples of suitable haloalkyl groups include trifluoromethyl, tetrafluoroethyl, chloromethyl, 2-chloroethyl, bromomethyl and the like.

Although the cycloalkyl group is not particularly limited, it is preferably a cycloalkyl group having 3 to 8 carbon atoms (a cycloalkyl group having 3 to 8 carbon atoms forming a ring). Examples of the cycloalkyl group having 3 to 8 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like. The cycloalkyl group may have a substituent, but the number of carbon atoms (3 to 8 carbon atoms) does not include the number of carbon atoms in the substituent.

Although the alkoxy group is not particularly limited, it is preferably an alkoxy group having 1 to 6 carbon atoms. Examples of suitable alkoxy groups having 1 to 6 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, s-butoxy and t-butoxy groups. can.

The amino group is a primary amino group (—NH ₂ ), and the substituted amino group is a secondary or tertiary amino group substituted with one or two hydrogen atoms. The substituents of the substituted amino group are not particularly limited, but are the oligomer chain group, the alkenyl group having 10 to 30 carbon atoms, the alkyl group having 1 to 6 carbon atoms, and the haloalkyl group having 1 to 6 carbon atoms. alkoxy groups having 1 to 6 carbon atoms, cycloalkyl groups having 3 to 7 carbon atoms, aryl groups having 6 to 14 carbon atoms, heteroaryl groups having 4 to 14 carbon atoms, and the like. Examples of suitable amino groups include amino group, methylamino group, dimethylamino group, ethylamino group, diethylamino group, phenylamino group, diphenylamino group and the like.

As the heterocyclic group which may have a substituent, a heterocyclic group having 3 to 10 atoms is preferable. Specific examples include aliphatic heterocyclic groups such as morpholino group, piperidino group, pyrrolidinyl group, piperazino group and N-methylpiperazino group, and aromatic heterocyclic groups such as indolinyl group. Furthermore, the heterocyclic group may naturally have a substituent, and preferred substituents are the oligomer chain group A, the alkenyl group having 10 to 30 carbon atoms, or the alkyl group having 1 to 6 carbon atoms. is mentioned. Suitable heterocyclic groups having substituents include, for example, 2,6-dimethylmorpholino group, 2,6-dimethylpiperidino group and 2,2,6,6-tetramethylpiperidino group. Halogen atoms include, for example, fluorine, chlorine, bromine and iodine atoms.

Although the alkylthio group is not particularly limited, an alkylthio group having 1 to 6 carbon atoms is preferable. Examples of alkylthio groups having 1 to 6 carbon atoms include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, s-butylthio and t-butylthio groups.

The arylthio group which may have a substituent is not particularly limited, but an arylthio group having 6 to 10 carbon atoms is preferable. Examples of the arylthio group having 6 to 10 carbon atoms include a phenylthio group, a 1-naphthylthio group and a 2-naphthylthio group. Furthermore, the arylthiox group may naturally have a substituent, and preferred substituents include the oligomer chain group A, the alkenyl group having 10 to 30 carbon atoms, or the alkyl group having 1 to 6 carbon atoms, Alternatively, a group having an alkenyl group having 10 to 30 carbon atoms at its terminal can be mentioned.

The group having a terminal alkenyl group having 10 to 30 carbon atoms is preferably an oxyalkenyl group, a monoalkylene glycol oxyalkenyl group, or a dialkylene glycol oxyalkenyl group (in these three groups, the terminal alkenyl group has 10 to 30 carbon atoms.Hereinafter, these three groups may be simply referred to as "terminal alkenyl groups"). Also, the alkylene glycol moiety is preferably ethylene glycol or propylene glycol. As the group having an alkenyl group having 10 to 30 carbon atoms at its terminal, the terminal of the oligomer chain group A may be the "terminal alkenyl group". Among the groups having a terminal alkenyl group having 10 to 30 carbon atoms, a preferred group can be represented by a general formula, for example, "--O--(R ¹⁶ O) _n --R ¹⁷ ". . R ¹⁶ is an alkylene group having 1 to 10 carbon atoms, preferably an alkylene group having 2 to 3 carbon atoms. R ¹⁷ is an alkenyl group having 10 to 30 carbon atoms. n is an integer of 0-2.

Although the alkylcarbonyl group is not particularly limited, an alkylcarbonyl group having 2 to 7 carbon atoms is preferable. The alkylcarbonyl group having 2 to 7 carbon atoms includes an acetyl group and an ethylcarbonyl group.

The alkoxycarbonyl group is not particularly limited, but an alkoxycarbonyl group having 2 to 7 carbon atoms is preferable. The alkoxycarbonyl group having 2 to 7 carbon atoms includes methoxycarbonyl group and ethoxycarbonyl group.

Although the aralkyl group which may have a substituent is not particularly limited, it is preferably an aralkyl group having 7 to 11 carbon atoms. Examples of aralkyl groups having 7 to 11 carbon atoms include benzyl, phenylethyl, phenylpropyl, phenylbutyl and naphthylmethyl groups. Furthermore, the aralkyl group may naturally have a substituent, and preferable substituents include the oligomer chain group A, the alkenyl group having 10 to 30 carbon atoms, and the alkenyl group having 10 to 30 carbon atoms. A terminal group or an alkyl group having 1 to 6 carbon atoms may be mentioned.

The aralkoxy group which may have a substituent is not particularly limited, but an aralkoxy group having 7 to 11 carbon atoms is preferable. Examples of the aralkoxy group having 7 to 11 carbon atoms include a benzyloxy group and a naphthylmethoxy group. Furthermore, the aralkoxy group may naturally have a substituent, and preferred substituents include the oligomer chain group A, the alkenyl group having 10 to 30 carbon atoms, and the alkenyl group having 10 to 30 carbon atoms. A terminal group or an alkyl group having 1 to 6 carbon atoms may be mentioned.

The aryloxy group which may have a substituent is not particularly limited, but an aryloxy group having 6 to 12 carbon atoms is preferable. Examples of the aryloxy group having 6 to 12 carbon atoms include a phenyloxy group and a naphthyloxy group. Furthermore, the aryloxy group may of course have a substituent, and preferred substituents include the oligomer chain group A, the alkenyl group having 10 to 30 carbon atoms, the alkenyl group having 10 to 30 carbon atoms. or an alkyl group having 1 to 6 carbon atoms.

The aryl group which may have a substituent is not particularly limited, but an aryl group having 6 to 12 carbon atoms is preferable. Examples of the aryl group having 6 to 12 carbon atoms include phenyl group, 1-naphthyl group and 2-naphthyl group. Furthermore, the aryl group may naturally have a substituent, and preferred substituents include the oligomer chain group A, the alkenyl group having 10 to 30 carbon atoms, and the alkenyl group having 10 to 30 carbon atoms. A terminal group or an alkyl group having 1 to 6 carbon atoms may be mentioned.

Although the heteroaryl group which may have a substituent is not particularly limited, a heteroaryl group having 3 to 12 carbon atoms is preferable. Examples of heteroaryl groups having 3 to 12 carbon atoms include thienyl, furyl, pyrrolinyl, pyridyl, benzothienyl, benzofuranyl, and benzopyrrolinyl groups. Furthermore, the heteroaryl group may naturally have a substituent, and preferred substituents include the oligomer chain group A, the alkenyl group having 10 to 30 carbon atoms, and the alkenyl group having 10 to 30 carbon atoms. or an alkyl group having 1 to 6 carbon atoms.

The alkoxyalkylthio group is not particularly limited, but an alkoxyalkylthio group having 2 to 9 carbon atoms is preferable. Examples of the alkoxyalkylthio group having 2 to 9 carbon atoms include methoxymethylthio group, methoxyethylthio group, methoxy n-propylthio group, methoxy n-butylthio group, ethoxyethylthio group, n-propoxypropylthio group and the like. .

Although the haloalkylthio group is not particularly limited, a haloalkylthio group having 1 to 6 carbon atoms is preferable. Examples of haloalkylthio groups having 1 to 6 carbon atoms include trifluoromethylthio, tetrafluoroethylthio, chloromethylthio, 2-chloroethylthio and bromomethylthio groups.

Although the cycloalkylthio group is not particularly limited, a cycloalkylthio group having 3 to 8 carbon atoms is preferable. Examples of the cycloalkylthio group having 3 to 8 carbon atoms include cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio and the like. The cycloalkylthio group may have a substituent, but the number of carbon atoms (3 to 8 carbon atoms) does not include the number of carbon atoms in the substituent.

The cycloalkyl group, the arylthio group, the aralkyl group, the aralkoxy group, the aryloxy group, the aryl group, the heteroaryl group, and the cycloalkylthio group may be unsubstituted. However, when it has a substituent, 1 to 8 hydrogen atoms, particularly preferably 1 to 4 hydrogen atoms in the ring-forming group are the oligomer chain group A, the alkenyl group having 10 to 30 carbon atoms, A group having an alkenyl group having 10 to 30 carbon atoms at its end, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and a cycloalkyl group having 1 to 8 carbon atoms. It is preferably substituted with a substituent selected from an alkoxy group of 6, an amino group, a substituted amino group, a heterocyclic group having 3 to 8 atoms, a cyano group, a nitro group and a halogen atom. Specific examples of these substituents include the same groups as described above.

The number of carbon atoms described for the aralkyl group, the aralkoxy group, the aryloxy group, the aryl group, and the heteroaryl group does not include the carbon number of the substituent.

When a and b are 2 or more, R ¹ and R ² are each independently adjacent to each other and together form a cyclic group which may contain an oxygen atom, a sulfur atom, a carbon atom, or a nitrogen atom. can be formed. Although this ring group is not particularly limited, it is preferably a ring having 5 to 7 atoms including the carbon atoms to which R ¹ and R ² are bonded. The ring may have a substituent, and the substituent includes the oligomer chain group A, the alkenyl group having 10 to 30 carbon atoms, and the alkenyl group having 10 to 30 carbon atoms at the end. group, hydroxyl group, alkyl group having 1 to 6 carbon atoms, haloalkyl group having 1 to 6 carbon atoms, cycloalkyl group having 3 to 8 carbon atoms, alkoxy group having 1 to 6 carbon atoms, amino group, substituted amino group, atom Substituents selected from 3 to 8 heterocyclic groups, cyano groups, nitro groups and halogen atoms are included. Specific examples of these substituents include the same groups as described above. Among them, a ring represented by formula (3) described later is preferable.

<Particularly Suitable R ¹ and R ² >
Among the above groups, considering the color tone and density of the resulting photochromic compound, the presence or absence of white turbidity in the resulting cured product, etc., R ¹ and R ² are the oligomer chain group A, the carbon number 10 to 30 alkenyl groups, groups having terminal alkenyl groups having 10 to 30 carbon atoms, the above alkyl groups, the above alkoxy groups, the above heterocyclic groups which may have substituents, and the above substituents and arylthio groups which may have the above-mentioned substituents are preferred. Adjacent R ^1s or adjacent R ^2s are also preferably bonded to form a group to form a ring. Further, the substituent of the group which may have a substituent may be the oligomer chain group A or the alkenyl group having 10 to 30 carbon atoms.

<R ³ and R ⁴ >
R ³ and R ⁴ are each independently an optionally substituted aryl group or an optionally substituted heteroaryl group.

The substituents each independently include the oligomer chain group A, the alkenyl group having 10 to 30 carbon atoms, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, and a haloalkyl group having 1 to 6 carbon atoms. cycloalkyl group of 8, alkoxy group of 1 to 6 carbon atoms, amino group, heterocyclic group, cyano group, halogen atom, alkylthio group of 1 to 6 carbon atoms, optionally substituted carbon number of 6 to 10 arylthio group, a nitro group, and a group having an alkenyl group having 10 to 30 carbon atoms at its terminal. These specific substituents include the specific groups exemplified for <R ¹ and R ² > above. Among them, the oligomer chain group and the group having an alkenyl group having 10 to 30 carbon atoms at the end are preferable.

As substituents for the aryl group and the heteroaryl group, among others, from the viewpoint of exhibiting excellent photochromic properties, the oligomer chain group, the alkenyl group having 10 to 30 carbon atoms, the alkyl group, the alkoxy group, It is preferably a group selected from the amino group, the substituted amino group, the heterocyclic group, the halogen atom, the arylthio group and the group having an alkenyl group having 10 to 30 carbon atoms at its end. These specific substituents include the specific groups exemplified for <R ¹ and R ² > above.

<R ⁵ and R ⁶ >
R ⁵ and R ⁶ each independently represent an alkenyl group having 10 to 30 carbon atoms, a group having a terminal alkenyl group having 10 to 30 carbon atoms, the oligomer chain group A, a hydrogen atom, a hydroxyl group, an alkyl group, haloalkyl group, cycloalkyl group, alkoxy group, alkoxyalkyl group, formyl group, hydroxycarbonyl group, alkylcarbonyl group, alkoxycarbonyl group, halogen atom, optionally substituted aralkyl group, optionally substituted aralkoxy group, optionally substituted aryloxy group, optionally substituted aryl group, optionally substituted heterocyclic group. Examples of these substituents include the same groups as those already explained in <R ¹ and R ² >.

R ⁵ and R ⁶ together are an aliphatic ring having 3 to 20 ring carbon atoms together with the carbon atom at position 13 of the indenonaphthopyran moiety to which they are bonded; a condensed polycyclic ring in which an aromatic ring or aromatic heterocyclic ring is condensed, a heterocyclic ring having 3 to 20 ring member atoms, or a condensed polycyclic ring in which an aromatic ring or aromatic heterocyclic ring is condensed to the above heterocyclic ring provided that these rings may have substituents. or an aliphatic hydrocarbon ring having 3 to 20 ring member carbon atoms together with the carbon atom at the 13th position of the indenonaphthopyran moiety to which they are bonded, and an aromatic ring or aromatic heterocyclic ring in the aliphatic hydrocarbon ring A condensed condensed polycyclic ring, a heterocyclic ring having 3 to 20 ring member atoms, or a condensed polycyclic group obtained by condensing an aromatic hydrocarbon ring or an aromatic heterocyclic ring to the above heterocyclic ring can be formed. As a matter of course, the number of carbon atoms or number of atoms shown in the ring group indicates the number of carbon atoms or atoms constituting the ring, and includes the number of carbon atoms or number of atoms of the substituent. not a thing

Examples of the aliphatic ring include cyclopentane ring, cyclohexane ring, cyclooctane ring, cycloheptane ring, norbornane ring, bicyclononane ring, adamantane ring, and spirodicyclohexane ring.

Examples of the condensed polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is condensed to the aliphatic ring include a phenanthrene ring. Examples of the heterocyclic ring include thiophene ring, furan ring, and pyridine ring. Moreover, examples of the condensed polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is fused to the heterocyclic ring include a phenylfuran ring and a biphenylthiophene ring.

the above-mentioned aliphatic ring, a condensed polycyclic ring obtained by condensing an aromatic ring or an aromatic heterocyclic ring to the above-mentioned aliphatic ring, the above-mentioned heterocyclic ring, or a condensed polycyclic ring obtained by condensing an aromatic ring or an aromatic heterocyclic ring to the above-mentioned heterocyclic ring; may have a substituent. Examples of substituents to be substituted on the ring (condensed polycyclic ring) include the oligomer chain group A, the alkenyl group having 10 to 30 carbon atoms, the alkyl group having 1 to 6 carbon atoms, the haloalkyl group having 1 to 6 carbon atoms, and carbon Substituents selected from 3 to 8 cycloalkyl groups, alkoxy groups having 1 to 6 carbon atoms, amino groups, substituted amino groups, and halogen atoms can be mentioned. These substituents include the same groups as those already explained in <R ¹ and R ² >.

Among the substituents of the rings, the chromene compound of the present invention exhibits particularly excellent effects, for example, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, a haloalkyl group having 1 to 6 carbon atoms, and a Alkoxy groups of 1 to 6 are particularly preferred. These specific substituents include the specific groups exemplified for <R ¹ and R ² > above.

<Particularly Suitable R ⁵ and R ⁶ >
R ⁵ and R ⁶ each independently represent the oligomer chain group A, the alkenyl group having 10 to 30 carbon atoms, a group having an alkenyl group having 10 to 30 carbon atoms at its end, a hydrogen atom, a hydroxyl group, an alkyl group, haloalkyl group, cycloalkyl group, alkoxy group, alkoxyalkyl group, formyl group, hydroxycarbonyl group, alkylcarbonyl group, alkoxycarbonyl group, halogen atom, optionally substituted aralkyl group, optionally substituted aralkoxy group, optionally substituted aryloxy group, optionally substituted aryl group, optionally substituted heterocyclic group. These specific substituents include the specific groups exemplified for <R ¹ and R ² > above.

R ⁵ and R ⁶ together are an aliphatic ring having 3 to 20 carbon atoms together with the carbon atom at position 13 of the indenonaphthopyran moiety to which they are bonded; A condensed polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is condensed to the ring, a heterocyclic ring having 3 to 20 ring member atoms, or a condensed polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is condensed to the above heterocycle A ring may be formed, provided that these rings may have a substituent. or an aliphatic hydrocarbon ring having 3 to 20 ring member carbon atoms together with the carbon atom at the 13th position of the indenonaphthopyran moiety to which they are bonded, and an aromatic ring or aromatic heterocyclic ring in the aliphatic hydrocarbon ring A condensed polycyclic ring, a heterocyclic ring having 3 to 20 ring member atoms, or a condensed polycyclic group in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is condensed to the above heterocyclic ring may be formed.

In the present invention, suitable substituents for R ⁵ and R ⁶ include the oligomer chain group A, the alkenyl group having 10 to 30 carbon atoms, a group having an alkenyl group having 10 to 30 carbon atoms at its end, a hydroxyl group, ^Examples include the case where an alkyl group, an alkoxy group, and a ring is formed together with the carbon atom at the 13th position of the ^{indenonaphthopyran} site to which R5 and R6 are bonded. These specific substituents include the specific groups exemplified for <R ¹ and R ² > above.

Among these, it is preferable to form a ring together with the 13-position carbon atom of the indenonaphthopyran moiety to which they are bonded, from the viewpoint that excellent photochromic properties can be exhibited and the durability of the photochromic compound is high. Among them, from the viewpoint of increasing the fading rate, it is more preferable to form a condensed polycyclic ring in which the aliphatic ring or the aromatic ring or the aromatic heterocyclic ring is condensed to the aliphatic ring. From the viewpoint of reducing initial coloration due to chromism, it is particularly preferable to form the above-mentioned alicyclic ring.

Suitable aliphatic ring groups formed by R ⁵ and R ⁶ are unsubstituted aliphatic hydrocarbon ring groups having 6 to 16 carbon atoms in the ring, alkyl groups, haloalkyl groups, cycloalkyl groups, It is an aliphatic hydrocarbon ring group having at least one substituent selected from the group consisting of an alkoxy group, an amino group, an aralkyl group, an aryl group and a halogen atom. These specific substituents include the specific groups exemplified for <R ¹ and R ² > above.

Among the aliphatic hydrocarbon ring groups, a particularly suitable one is a ring group in which an aliphatic hydrocarbon ring is substituted with an alkyl group having 1 to 6 carbon atoms (preferably an alkyl group having 1 to 3 carbon atoms), or It is preferably a cyclic group in which a cycloalkyl group having 3 to 8 carbon atoms is bonded or condensed to the aliphatic hydrocarbon ring.

Among these, the aliphatic hydrocarbon ring groups from the viewpoint of obtaining excellent color fading speed and high color density include cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cyclo A ring (particularly preferably a cyclohexane ring) selected from an undecane ring, a cyclododecane ring, and a spirodicyclohexane ring,
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 is preferably a ring to which a cycloalkyl group having 5 to 7 carbon atoms may be condensed.

Specific examples of particularly suitable aliphatic hydrocarbon ring groups include the following formula

It is preferable to be a ring represented by. In the above formula, the carbon atom having the dotted bond is the 13-position carbon atom of the indenonaphthopyran moiety.

The substituents at each position to be substituted on the chromene compound have been described above. Therefore, the oligomer chain group A may be used. Further, the substituents of the groups optionally having substituents are such that the alkenyl groups having 10 to 30 carbon atoms are 1 to 12 per oligomer chain group A contained in one molecule, It may be an alkenyl group having 10 to 30 carbon atoms. The number of alkenyl groups having 10 to 30 carbon atoms includes the number of alkenyl groups having 10 to 30 carbon atoms at the end of the substituent.
A suitable oligomer chain group A will now be described.

<Oligomer chain group A>
In the chromene compound of the present invention, the indenonaphthopyran moiety represented by the formula (1) has at least the oligomer chain group A, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , At least one of ^R6 can be the oligomer chain group A (or a group having an oligomer chain group).

The oligomer chain group A is not particularly limited as long as it has 3 or more repeating units. Among them, a group having a polyalkylene oxide oligomer chain or a polysiloxane oligomer chain having 3 or more repeating units is preferable. As described above, the number of repeating units of the oligomer chain group A is preferably 3-200, more preferably 3-170, and most preferably 15-80. Furthermore, the average molecular weight of the oligomer chain group A is preferably from 300 to 30,000, more preferably from 350 to 25,000, even more preferably from 400 to 20,000, 000 is particularly preferred.

In the present invention, among others, the average molecular weight of the oligomer chain group with respect to 1 mol of the indenonaphthopyran moiety is very important. That is, in order to exhibit an excellent effect especially in a hard matrix (in a resin), the average molecular weight of the oligomer chain group is preferably 350 to 10,000 with respect to 1 mol of the indenonaphthopyran moiety. It is more preferable to be ∼5000. The average molecular weight of the oligomer chain group (A) can be adjusted depending on the type of raw material used when synthesizing the photochromic compound. In addition, the average molecular weight here means a number average molecular weight. The number-average molecular weight can be confirmed from the raw material compounds used when synthesizing the photochromic compound of the present invention. Also, after the synthesis of the photochromic compound, the number average molecular weight can be obtained by measurement by ¹ H-NMR.

Among the oligomer chain groups A as described above, groups represented by formulas (5a) to (5d) described in detail below are preferable in order to achieve excellent photochromic properties and reduce the dependency on the matrix. . A chromene compound that always has one of these groups in the molecule and has an alkenyl group of 10 to 30 carbon atoms exhibits particularly excellent effects.

<Suitable oligomer chain group A>
In the present invention, the oligomer chain group A used has three or more repeating units and is an oligomer chain selected from polyalkylene oxide oligomer chain groups, polyester oligomer chain groups, polysiloxane chain groups, and polyester polyether oligomer chain groups. Although it is not particularly limited as long as it is a group, a particularly preferable oligomer chain group A is represented by the following formulas (5a) to (5d)

is mentioned.

In the above formulas (5a) to (5c), R ¹⁰ is a linear or branched alkylene group having 1 to 20 carbon atoms, and when multiple R ¹⁰ are contained in the same molecule, R ¹⁰ is They may be the same or different. From the viewpoint of production, R ¹⁰ is preferably an ethylene group, a propylene group, or a butylene group, and particularly preferably a propylene group. n indicates a repeating unit of the oligomer chain group and is an integer of 3-200. Considering the productivity and photochromic properties of the polymer photochromic compound, n is preferably 3-170, more preferably 15-80.

In the above formulas (5a) to (5d), the dashed line represents the bond with the indenonaphthopyran moiety, and t indicates the number of the oligomer chain groups A and is an integer of 1 to 10. .

when t is 1, R ¹¹ is a group having at its end an alkenyl group having 10 to 30 carbon atoms, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 10 to 30 carbon atoms;
when t is 2, R ¹¹ is a bond or a divalent organic residue,
When t is 3-10, R ¹¹ is an organic residue with the same valence as the number of t.

As a matter of course, the group having an alkenyl group having 10 to 30 carbon atoms at its terminal, which is explained here, is preferably the same as the aforementioned "terminal alkenyl group".

In the above formula (5d), R ¹² is a linear or branched alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 14 carbon atoms, and multiple R ¹² are contained in the same molecule. , R ¹² may be the same or different from each other. From the viewpoint of production, preferable R ¹² includes methyl group, ethyl group, propyl group, butyl group, or phenyl group.

In the above formulas (5a) to (5d), L is a divalent bonding group, and the following formula (6)

is a group represented by

In the above formula (6), R ¹³ is a divalent group, a linear or branched alkylene group having 1 to 20 carbon atoms, and a substituent having 3 to 12 carbon atoms forming a ring. an optionally substituted arylene group having 6 to 12 carbon atoms forming a ring, or a substituent having 3 to 12 atoms forming a ring is a good heterocyclic group.

R ¹⁴ is a divalent group, a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms forming a ring and optionally having a substituent. , or an optionally substituted arylene group having 6 to 12 carbon atoms forming a ring.

R ¹⁵ is a divalent group, a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms forming a ring and optionally having a substituent , or an optionally substituted arylene group having 6 to 12 carbon atoms forming a ring. X ¹ and X ² are divalent groups each independently a direct bond, an oxygen atom, a sulfur atom, an amino group, a substituted amino group, a (thio)amide group, or a (thio)ester group.

The substituent of the group which may have a substituent may be the alkenyl group having 10 to 30 carbon atoms, or the group having the alkenyl group having 10 to 30 carbon atoms at its end.

d is an integer of 0-50, e is an integer of 0-50, and f is an integer of 0-50.

When d is 2 or more, multiple R ¹³ may be the same or different,
When e is 2 or more, the divalent groups of the multiple e units may be the same or different,
When f is 2 or more, the divalent groups of multiple units of f may be the same or different.

Moreover, multiple L's may be the same or different.

Particularly preferred examples of L include the following formula

A divalent group represented by is exemplified.

In the oligomer chain groups represented by formulas (5a) to (5d) above, t corresponds to the number of oligomer chain groups. When t is 1, that is, when there is one oligomer chain group, the alkyl group having 1 to 20 carbon atoms for R ¹¹ is a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, or A hexyl group is preferred. Further, when t is 1, it is preferable that the end of the oligomer chain is an alkenyl group having 10 to 30 carbon atoms or a group having the alkenyl group having 10 to 30 carbon atoms at the end.

When t is 2, R ¹¹ may be a bond. That is, when R11 serves as a bond, the length of the oligomer chain is substantially doubled, and both ends have ^{indenonaphthopyran} moieties.

When t is 3-10, R ¹¹ is an organic residue whose valence depends on the number of t. In this case, t is preferably 3-6. Preferred organic residues (R ¹¹ ) are exemplified by the following formula:

Any polyvalent organic residue represented by can be mentioned. In the polyvalent organic residue, the dashed line indicates the bond with L.
The above are suitable oligomer chain groups A.

<Preferred Substitution Position of Oligomer Chain Group A>
The polymeric photochromic compound of the present invention must have at least one oligomer chain group A in the molecule. Therefore, in the groups described for R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ , the substituent possessed by the optionally substituted group may be the oligomer chain group A. good. Among others, the oligomeric chain group A is at the 3-position (R ³ and R ⁴ ), 6-position (R ¹ ), 7-position (R ¹ ), 11-position (R ² ), or 13-position of the indenonaphthopyran moiety. Substitution with (R ⁵ and R ⁶ ) is preferable because the effects of the present invention and the productivity of the chromene compound itself can be improved.

The oligomer chain group may be directly bonded to the position, or an oligomer chain group A may be introduced as a substituent of the group bonded to the position.

<Suitable substitution position of alkenyl group having 10 to 30 carbon atoms>
The photochromic compound of the present invention must have at least one alkenyl group having 10 to 30 carbon atoms in the molecule. The alkenyl group having 10 to 30 carbon atoms may be directly substituted on the oligomer chain group A (the end of the oligomer chain group is an alkenyl group having 10 to 30 carbon atoms), or an indyl group different from the oligomer chain group A may be substituted. It may be substituted at the substitution position of the nonaphthopyran moiety, or both. Among them, considering the effect of the present invention and the productivity of the chromene compound itself, the 3-position (R ³ and R ⁴ ), 6-position (R ¹ ), 7-position (R 1 ), 11-position (R ¹ ), 11-position ( R ² ), or 13-position (R ⁵ and R ⁶ ).

The alkenyl group having 10 to 30 carbon atoms may be directly bonded to the position, or an alkenyl group having 10 to 30 carbon atoms is introduced as a substituent of the group bonded to the position. good too. Further, the substituents of the groups optionally having substituents are such that the alkenyl groups having 10 to 30 carbon atoms are 1 to 12 per oligomer chain group A contained in one molecule, It may be an alkenyl group having 10 to 30 carbon atoms or a group having an alkenyl group having 10 to 30 carbon atoms at its end.

<Particularly Suitable Chromene Compound>
Suitable chromene compounds in the present invention include chromene compounds represented by the following formula (2). However, this chromene compound must also have at least one oligomer chain group A and an alkenyl group having 10 to 30 carbon atoms in its molecule.

During the ceremony,
R ¹ , R ² , R ⁵ and R ⁶ have the same definitions as in formula (1) above.

a'' is an integer of 0 to 2; when a'' is 2, a plurality of R ¹ may be the same or different; b'' is an integer of 0 to 3; is 2 or 3, the plurality of R ² may be the same or different.

<R ¹⁰⁰ and R ¹⁰¹ >
Among the groups described in <R ¹ and R ² > above, R ¹⁰⁰ and R ¹⁰¹ are preferably the following groups. Specifically, the oligomer chain group A, the alkenyl group having 10 to 30 carbon atoms, the group having the alkenyl group having 10 to 30 carbon atoms at the end, a hydrogen atom, a hydroxyl group, and an alkyl group having 1 to 6 carbon atoms , a haloalkyl 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, an amino group, a substituted amino group, a heterocyclic group which may have a substituent, a cyano group , a halogen atom, an alkylthio group having 1 to 6 carbon atoms, an arylthio group having 6 to 10 carbon atoms which may have a substituent, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group having 2 to 7 carbon atoms, An alkoxycarbonyl group having 2 to 7 carbon atoms, an aralkyl group having 7 to 11 carbon atoms which may have a substituent, an aralkoxy group having 7 to 11 carbon atoms which may have a substituent, and having a substituent an aryloxy group having 6 to 12 carbon atoms which may be substituted, an aryl group having 6 to 12 carbon atoms which may have a substituent, a heteroaryl group which may have a substituent and having 3 to 12 carbon atoms, a thiol group, It is an alkoxyalkylthio group having 2 to 9 carbon atoms, a haloalkylthio group having 1 to 6 carbon atoms, or a cycloalkylthio group having 3 to 8 carbon atoms. These specific groups include the same groups as those described in <R ¹ and R ² > above.

Further, R ¹⁰⁰ and R ¹⁰¹ are together represented by the following formula (3)

in which c is an integer of 1-3. In the formula, * indicates the carbon atom at the 6- or 7-position of the indenonaphthopyran moiety.

<X, and Y>
In the formula, one or both of X and Y are a sulfur atom, a methylene group, an oxygen atom, or the following formula (4)

is a group represented by In the above formula, R ⁹ is the oligomer chain group, the alkenyl group having 10 to 30 carbon atoms, the alkenyl group having 10 to 30 carbon atoms at the end, a hydrogen atom, a hydroxyl group, or an alkyl group, a haloalkyl 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, an aryl group having 6 to 12 carbon atoms which may have a substituent, a substituent It is a heteroaryl group which may have 3 to 12 carbon atoms. These specific groups include the specific groups exemplified for <R ¹ and R ² > above, and the preferred groups are also the same.

<R ⁷ and R ⁸ >
R ⁷ and R ⁸ each independently represent the oligomer chain group A, the alkenyl group having 10 to 30 carbon atoms, the alkenyl group having 10 to 30 carbon atoms at the end, a hydroxy group, or 1 to 6 carbon atoms. Alkyl groups of 1 to 6 haloalkyl groups, cycloalkyl groups of 3 to 8 carbon atoms, alkoxy groups of 1 to 6 carbon atoms, amino groups, substituted amino groups, optionally substituted heterocyclic groups , a cyano group, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a halogen atom, optionally having a substituent, 7 to 11 carbon atoms aralkyl group, an aralkoxy group having 7 to 11 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, a thiol group, an alkylthio group having 1 to 6 carbon atoms, An alkoxyalkylthio group having 2 to 9 carbon atoms, a haloalkylthio group having 1 to 6 carbon atoms, a cycloalkylthio group having 3 to 8 carbon atoms, or an optionally substituted arylthio group having 6 to 10 carbon atoms. is preferred. These specific groups include the specific groups exemplified for <R ¹ and R ² > above, and the preferred groups are also the same.

^In addition, ^R7 and R8 may form an optionally substituted aliphatic ring together with the carbon atom to which they are attached. Specific examples of the aliphatic ring include cyclopentane ring and cyclohexane ring. Further, the substituents possessed by the aliphatic ring are not particularly limited, but 1 to 8 hydrogen atoms, particularly preferably 1 to 4 hydrogen atoms, in the group forming the ring are Group A, the alkenyl group having 10 to 30 carbon atoms, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and a cycloalkyl group having 1 to 6 carbon atoms. It is preferably substituted with a substituent selected from an alkoxy group, an amino group, a substituted amino group, a heterocyclic group having 3 to 8 atoms, a cyano group, a nitro group and a halogen atom. Specific examples of these substituents include the same groups as described in <R ¹ and R ² > above.

<Particularly Suitable R ¹⁰⁰ and R ¹⁰¹ >
Considering the color tone, color density, etc. of the obtained photochromic compound among the above groups, R ¹⁰⁰ and R ¹⁰¹ are the oligomer chain group A, the alkenyl group having 10 to 30 carbon atoms, the carbon Groups having 10 to 30 alkenyl groups at their ends, hydrogen atoms, the above alkyl groups, the above alkoxy groups, the above heterocyclic groups, the above aryl groups, and the above arylthio groups are preferred. These specific substituents include the specific groups exemplified for <R ¹ and R ² > above. Moreover, it may be a ring represented by the above formula (3). The substituent of the group which may have a substituent may be the oligomer chain group A or an alkenyl group having 10 to 30 carbon atoms.

< ^R200 >
Among the groups described in <R ¹ and R ² > above, R ²⁰⁰ is preferably the following groups. Specifically, the oligomer chain group A, the alkenyl group having 10 to 30 carbon atoms, the group having an alkenyl group having 10 to 30 carbon atoms at its end, a hydrogen atom, a hydroxy group, and an alkyl group having 1 to 6 carbon atoms , a haloalkyl 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, an amino group, a substituted amino group, a heterocyclic group which may have a substituent, a cyano group , a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a halogen atom, an optionally substituted aralkyl group having 7 to 11 carbon atoms. , optionally substituted C7-11 aralkoxy group, optionally substituted C6-12 aryl group, thiol group, C1-6 alkylthio group, C2 9 to 9 alkoxyalkylthio groups, haloalkylthio groups having 1 to 6 carbon atoms, cycloalkylthio groups having 3 to 8 carbon atoms, or optionally substituted arylthio groups having 6 to 10 carbon atoms. Specific examples of these groups include the same groups as described in <R ¹ and R ² > above. Preferred groups are also the same.

<Particularly Suitable R ²⁰⁰ >
Considering the color tone, color density, etc. of the resulting photochromic compound among the above groups, R ²⁰⁰ is the oligomer chain group A, the alkenyl group having 10 to 30 carbon atoms, the alkenyl group having 10 to 30 carbon atoms, is preferably an alkenyl group-terminated group, a hydrogen atom, the alkoxy group, the heterocyclic group, or the aryl group. These specific groups include the specific groups exemplified for <R ¹ and R ² > above, and the preferred groups are also the same. The substituent of the group optionally having a substituent is a group having the alkenyl group having 10 to 30 carbon atoms or the alkenyl group having 10 to 30 carbon atoms at the end even in the oligomer chain group A. There may be.

<R ³⁰⁰ and R ⁴⁰⁰ >
R ³⁰⁰ and R ⁴⁰⁰ each independently represent the oligomer chain group, the alkenyl group having 10 to 30 carbon atoms, the alkenyl group having 10 to 30 carbon atoms at the end, a hydroxyl group, or a group having 1 to 6 carbon atoms. Alkyl groups of 1 to 6 haloalkyl groups, cycloalkyl groups of 3 to 8 carbon atoms, alkoxy groups of 1 to 6 carbon atoms, amino groups, substituted amino groups, optionally substituted heterocyclic groups , a cyano group, a halogen atom, an alkylthio group having 1 to 6 carbon atoms, or an arylthio group having 6 to 10 carbon atoms which may have a substituent. These specific groups include the specific groups exemplified for <R ¹ and R ² > above, and the preferred groups are also the same.

a' represents the number of R ³⁰⁰ and is an integer of 0 to 5. When a' is 2 or more, R ³⁰⁰ may be the same or different groups.

b' represents the number of R ⁴⁰⁰ and is an integer of 0 to 5. When b' is 2 or more, R ⁴⁰⁰ may be the same or different groups.

<Particularly Suitable R ³⁰⁰ and R ⁴⁰⁰ >
Among the above groups, considering the color tone and density of the resulting photochromic compound, the presence or absence of white turbidity in the resulting cured product, etc., R ³⁰⁰ and R ⁴⁰⁰ are the above oligomer chain groups, the above C 10 Alkenyl groups of up to 30, the above alkyl groups, the above alkoxy groups, the above substituted amino groups, and the above heterocyclic groups are preferred. The substituent of the group optionally having a substituent is, even in the oligomer chain group A, the alkenyl group having 10 to 30 carbon atoms, or the group having the alkenyl group having 10 to 30 carbon atoms at the end. may be

<Preferred Substitution Position of Preferred Oligomer Chain Group A>
The oligomer chain group A is at the 3-position (R ³⁰⁰ or R ⁴⁰⁰ ), 6-position (R ¹⁰⁰ ), 7-position (R ¹⁰¹ ), 11-position (R ²⁰⁰ ) or 13-position (R ⁵ , or R ⁶ ) is preferable because it can improve the effects of the present invention and the productivity of the chromene compound itself. Further, when present at the 3-position (R ³⁰⁰ or R ⁴⁰⁰ ), the phenyl group having R ³⁰⁰ or the phenyl group having R ⁴⁰⁰ is a phenyl group having the oligomer chain group A at the para position, or " It is preferably a phenyl group having the "terminal alkynyl group" at the para position.

<Suitable substitution position of alkenyl group having 10 to 30 carbon atoms>
The alkenyl group having 10 to 30 carbon atoms is the 3-position (R ³⁰⁰ or R ⁴⁰⁰ ), 6-position (R ¹⁰⁰ ), 7-position (R ¹⁰¹ ), 11-position (R ²⁰⁰ ) or 13-position of the indenonaphthopyran. (R ⁵ or R ⁶ ) is preferable because it can improve the effects of the present invention and the productivity of the chromene compound itself. Further, when present at the 3-position (R ³⁰⁰ or R ⁴⁰⁰ ), a phenyl group having R ³⁰⁰ or a phenyl group having R ⁴⁰⁰ is a phenyl group having "the terminal alkenyl group" at the para position, or A phenyl group having an alkenyl group having 10 to 30 carbon atoms is preferred. From the viewpoint of the effect of the present invention, that the productivity of the chromene compound itself can be further improved, the alkenyl group having 10 to 30 carbon atoms or the terminal alkenyl group, and the oligomer chain group A are each the indenonaphtopyne Substitution at different substitution positions of the run site is particularly preferred.

<Specific examples of particularly suitable chromene compounds>
Specific examples of chromene compounds that are particularly suitable in the present invention include the following compounds.
In the formula, C ₁₈ H ₃₅ , which is one type of alkenyl groups having 10 to 30 carbon atoms, represents an oleyl group.

n in the above formula is preferably 3-200, more preferably 3-170, and even more preferably 15-80. m in the above formula is preferably 0-2.

<Method for producing the photochromic compound of the present invention>
The photochromic compounds of the present invention may be produced by any synthetic method. A representative example of the method for producing a chromene compound is described below, but the photochromic compound of the present invention is not limited to those produced by this method. In the following description, the symbols in each formula have the same meanings as described in the formulas described above, unless otherwise specified.

The production of the chromene compound is the following formula (7)

and a naphthol compound represented by the following formula (8)

A chromene compound can be suitably produced by reacting a propargyl alcohol compound represented by in the presence of an acid catalyst. The reaction ratio between the naphthol compound and the propargyl alcohol compound is preferably selected from the range of 1:10 to 10:1 (molar ratio). As the acid catalyst, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, acidic alumina, etc. are used. The acid catalyst is preferably used in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the total of the naphthol compound and the propargyl alcohol compound. The reaction temperature is preferably 0 to 200°C. The solvent is preferably an aprotic organic solvent such as N-methylpyrrolidone, dimethylformamide, tetrahydrofuran, benzene, toluene and the like. The method for purifying the product obtained by such reaction is not particularly limited. For example, silica gel column chromatography or recrystallization can be used to purify the product.

Examples of production of a chromene compound into which a polyalkylene oxide oligomer chain group A (for example, the oligomer chain group A represented by the formula (5a)) is introduced are shown below. First, a method for substituting a polyalkylene oxide oligomer chain group on the naphthol compound represented by the formula (7) is exemplified below.

First, the following formula (9)

The polyalkylene glycol monoalkyl ether represented by the following formula (10)

Convert to a compound represented by In the above formula (10), Y is a highly eliminable substituent such as a tosyl group or a halogen atom.

As a method for converting to a tosyl group, a method of reacting with p-toluenesulfonyl chloride in the presence of a basic catalyst such as a tertiary amine such as triethylamine can be preferably employed. An Appel reaction or the like can be used as a method for converting to an iodine atom, a bromine atom, or a chlorine atom. Specifically, it is preferable to react with carbon tetrahalide, iodine, methyl iodide, hexahalogenylacetone, triphosgene, or the like in the presence of triphenylphosphine.

Subsequently, a benzophenone compound having a hydroxyl group and the compound represented by the formula (10) are reacted in an aprotic polar solvent such as dimethylformamide or dimethylsulfoxide in the presence of a base such as potassium carbonate to obtain the following Formula (11)

A benzophenone compound represented by can be obtained. In formula (11) above, R is a polyalkylene oxide oligomer chain group.

Subsequently, the benzophenone compound of the formula (11) is converted to the following formula (12) using a known method.

is derived to a carboxylic acid represented by Bn in the formula (12) is a benzyl group.

Specific examples of known methods include Stobbe reaction, cyclization reaction, ester hydrolysis reaction using alkali or acid, benzyl protection of hydroxyl group and carboxylic acid, hydrolysis of benzyl ester using alkali or acid decomposition reaction. A carboxylic acid represented by the above formula (12) is derived into an amine by a method such as Curtius rearrangement, Hofmann rearrangement or Lossen rearrangement. Subsequently, a diazonium salt is prepared from the obtained amine by a known method, and this diazonium salt is converted into a bromide by Sandmeyer reaction or the like. The resulting bromide is reacted with magnesium, lithium or the like to prepare an organometallic compound. This organometallic compound is represented by the following formula (13)

is reacted with a ketone represented by in an organic solvent at -80 to 70°C for 10 minutes to 4 hours to obtain an alcohol compound. The obtained alcohol compound is subjected to Friedel-Crafts reaction. That is, under neutral to acidic conditions, the reaction is carried out at 10 to 120° C. for 10 minutes to 2 hours, and the alcohol moiety is spiro-ized by a nucleophilic substitution reaction to obtain the following formula (14).

A naphthol compound represented by can be synthesized. In such a reaction, the reaction ratio between the organometallic compound and the ketone represented by the formula (13) 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, aprotic organic solvents such as diethyl ether, tetrahydrofuran, benzene, toluene and the like are 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, and acidic alumina. An aprotic organic solvent such as tetrahydrofuran, benzene or toluene is used for this reaction.

By reacting the naphthol compound represented by the formula (14) with the propargyl alcohol represented by the formula (8), the polyalkylene oxide oligomer chain group is at the indeno or naphtho position (R ¹ or R ² ). Substituted photochromic compounds of the invention can be obtained.

Further, as a method for introducing a polyalkylene oxide oligomer chain group into the propargyl alcohol represented by the above formula (8), a benzophenone compound having a polyalkylene oxide oligomer chain group as represented by the above formula (11) is converted to the following Formula (15)

After synthesizing the propargyl alcohol represented by, it is reacted with the naphthol compound of the formula (7) synthesized based on the reaction method described in patents such as International Publication No. WO2001/60881 and International Publication No. WO2005/028465. Thus, the photochromic compound of the present invention in which the polyalkylene oxide oligomer chain group is substituted with R ³ and R ⁴ can be obtained.

In addition to the method of introducing an oligomer chain at the initial stage of synthesis described above (for example, introducing an oligomer chain into a naphthol compound or a benzophenone compound), the photochromic compound of the present invention can be produced by introducing an oligomer chain at the final stage. can also be manufactured. Specifically, a chromene compound having a reactive functional group such as a hydroxyl group, a primary or secondary amino group, or a thiol group is produced at the position where the oligomer chain is to be introduced. After that, the photochromic compound of the present invention is reacted with an oligomer chain group having a substituent capable of reacting with the functional group (this group is preferably a group forming the divalent linking group L). can be manufactured.

For example, L can be formed by performing an esterification reaction with a polyalkylene oxide oligomer having a carboxyl group. Specifically, in the presence of a mineral acid such as sulfuric acid or hydrochloric acid, an organic acid such as an aromatic sulfonic acid, or a Lewis acid such as boron fluoride ether, the mixture is stirred in a solvent such as toluene while heating as necessary, The reaction can be carried out while removing the generated water. In addition, in the esterification reaction, water can be removed by a desiccant such as azeotrope, anhydrous magnesium sulfate, or molecular sieves.

Alternatively, L can be formed by performing an esterification reaction with a polyalkylene oxide oligomer having a carboxylic acid halide. Specifically, in the presence of a base such as pyridine or dimethylaniline, in an ether solvent such as tetrahydrofuran, stirring is performed with heating as necessary, and the resulting hydrogen halide can be removed. .

A polyalkylene oxide oligomer having a carboxyl group or a carboxylic acid halide may be synthesized by a known method. Specifically, a polyalkylene oxide having a carboxyl group is obtained by reacting a polyalkylene oxide oligomer monoalkyl ether of formula (9) with a cyclic acid anhydride such as succinic anhydride in the presence of a base or an acid catalyst. Oligomeric monoalkyl ethers can be obtained. Further, after preparing an organometallic compound by reacting the polyalkylene oxide oligomer monoalkyl ether having a halogen atom of the formula (10) with magnesium, lithium or the like, it is also reacted with carbon dioxide to obtain a poly Alkylene oxide oligomeric monoethers can be obtained. A polyalkylene oxide oligomer monoether having a carboxylic acid halide can be obtained by reacting the obtained polyalkylene oxide oligomer monoether having a carboxyl group with thionyl chloride or oxalyl chloride.

Although the method for producing the photochromic compound of the present invention by introducing a polyalkylene glycol chain group into the indenonaphthopyran site has been described above, the same method can be employed when introducing other oligomer chain groups. . Specifically, instead of a compound having a polyalkylene oligomer chain (group), a compound having a polyester oligomer chain (group) or a polyester polyether oligomer chain (group) may be used and similar operations may be performed. . In addition, by using an alcohol compound having an alkenyl group having 10 to 30 carbon atoms (eg, oleyl group), a group having an alkenyl group having 10 to 30 carbon atoms at the terminal (terminal alkenyl group) can also be converted to indenonaphthalene in the same manner. It is possible to introduce at the topyran site.

<Identification of photochromic compound>
The photochromic compound of the present invention generally exists as a solid or viscous liquid at normal temperature and normal pressure, and can be confirmed by the following means. Specifically, separation operations such as thin-layer chromatography, silica gel column chromatography, high-performance liquid chromatography, gas chromatography, etc., eliminate raw material compounds and by-products such as colored matter other than the polymer photochromic compound. I can confirm that.

The obtained photochromic compound was measured by proton nuclear magnetic resonance spectroscopy ( ¹ H-NMR), and peaks based on aromatic protons and alkene protons were found around δ: 5.0 to 9.0 ppm, δ: A peak derived from the protons of the alkyl group and the alkylene group can be observed around 1.0 to 4.0 ppm. Also, the number of protons of each bonding group can be known by relatively comparing the respective spectral intensities. The chromene compound can also be extracted from the photochromic curable composition and the cured product of the curable composition and confirmed by the same method as described above.

The photochromic compound of the present invention is highly soluble in common organic solvents such as toluene, chloroform and tetrahydrofuran. When the photochromic compound of the present invention represented by the above formula (1) is dissolved in such a solvent, the solution is generally almost colorless and transparent, rapidly develops color when exposed to sunlight or ultraviolet rays, and rapidly when the light is blocked. It returns to the original colorlessness after a period of time, exhibiting a good photochromic effect.

<How to use the photochromic compound of the present invention>
INDUSTRIAL APPLICABILITY The photochromic compound of the present invention can be widely used as a photochromic material (photochromic optical article). It can be used as various memory materials such as materials, photosensitive materials for holography, and the like. In addition, photochromic materials using the photochromic compound of the present invention can be used as photochromic optical articles such as photochromic lens materials, optical filter materials, display materials, photometers, and decorations. The photochromic optical article can be produced, for example, by polymerizing a photochromic curable composition containing a photochromic compound and a polymerizable compound, as will be described later. An optical article may be obtained by coating with a polymer film in which a photochromic compound is dispersed.

Since the photochromic compound of the present invention exhibits excellent photochromic properties even in a polymer solid matrix, it can be used by being dispersed in a polymer solid matrix, and a polymer molded body in which the photochromic compound is dispersed inside. can also As a dispersing method, a method known per se can be used. For example, a method of kneading the photochromic compound of the present invention and a thermoplastic resin in a molten state and dispersing the photochromic compound in the resin, or dissolving the polymer photochromic compound of the present invention in a polymerizable compound, followed by a polymerization catalyst. and polymerizing with heat or light to disperse the photochromic compound in the resin, or by dyeing the surface of the polymer solid matrix with the polymer photochromic compound of the present invention. A dispersing method and the like can be mentioned.

Exemplary polymeric solid matrices are optically preferred such as polyacrylates, polymethacrylates, poly(C ₁ -C 12 )alkyl methacrylates, _polyoxy (alkylene methacrylates), poly(alkoxylated phenol methacrylates), cellulose Acetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, poly(vinyl acetate), poly(vinyl alcohol), poly(vinyl chloride), poly(vinylidene chloride), poly(vinylpyrrolidone), poly((meth ) acrylamide), poly(dimethylacrylamide), poly(hydroxyethyl methacrylate), poly((meth)acrylic acid), thermoplastic polycarbonates, polyesters, polyurethanes, polythiourethanes, poly(ethylene terephthalate), polystyrene, Mention may be made of poly(α-methylstyrene).

For example, when it is used for a photochromic lens, there is no particular limitation as long as it can obtain uniform light control performance. Alternatively, a method in which the photochromic compound of the present invention is dispersed in a polymerizable compound and polymerized by a predetermined method, or a method in which the compound is dissolved in, for example, silicone oil and heated at 150 to 200° C. for 10 to 60 minutes. A method of impregnating the surface of the lens and further coating the surface with a curable substance to form a photochromic lens can be used. Furthermore, a method of applying the polymer film to the lens surface and coating the surface with a curable substance to form a photochromic lens is also used. Furthermore, a coating agent comprising a polymerizable composition containing the photochromic compound of the present invention may be applied to the surface of the lens substrate and the coating film may be cured. At this time, the lens substrate may be subjected in advance to surface treatment with an alkaline solution or surface treatment such as plasma treatment. A primer can also be applied to improve adhesion to the coating.

<Photochromic curable composition>
In the present invention, by blending the photochromic compound of the present invention with the polymerizable compound, it can be used as a photochromic curable composition. The photochromic compound of the present invention may be used alone, but may be used in combination with other photochromic compounds depending on the purpose, for example, in order to obtain various color tones required for photochromic lenses. As the photochromic compound to be combined, any known photochromic compound can be used without any limitation. Examples thereof include fulgide compounds, fulgimide compounds, spirooxazine compounds, chromene compounds and the like. Among them, chromene compounds are particularly preferred from the viewpoint of maintaining a uniform color tone during color development and fading, suppressing color shift during color development due to deterioration of the photochromic compound, and suppressing initial coloration. Further, from the viewpoint of suppressing color shift in color tone due to difference in matrix dependency, the other photochromic compound is also preferably a photochromic compound having an oligomer chain. Furthermore, when a photochromic compound having an oligomer chain is used, the photochromic compound having an oligomer chain is a photochromic compound having at least one alkenyl group having 10 to 30 carbon atoms, from the viewpoint of suppressing cloudiness of the cured product. is preferred. Particularly preferably, a plurality of photochromic compounds of the present invention are used to adjust the color tone.

In the photochromic curable composition of the present invention, the blending amount of the photochromic compound is not particularly limited, and may be appropriately selected in consideration of the color development intensity of the photochromic compound and the thickness of the resulting photochromic cured product. Specifically, the amount of the photochromic compound containing the photochromic compound of the present invention is preferably 0.001 to 10 parts by weight per 100 parts by weight of the polymerizable compound.

In the present invention, since the intensity of color development of the photochromic cured product depends on the thickness of the cured product, it is particularly important to consider the thickness. Details are given below. For example, when forming a thin film of 100 μm or less using the photochromic curable composition of the present invention, 0.001 to 10 mass of the photochromic compound containing the polymer photochromic compound of the present invention is added to 100 parts by mass of the polymerizable compound. It is preferable to adjust the color tone by using a part. When producing a photochromic cured product having a thickness of 1 mm or more, the color tone is adjusted by using 0.001 to 1 part by mass of the photochromic compound containing the polymer photochromic compound of the present invention with respect to 100 parts by mass of the polymerizable compound. is preferred.

<Polymerizable compound>
In the present invention, known polymerizable compounds can be used without limitation, such as radically polymerizable compounds such as (meth)acrylate compounds, epoxy compounds, cationic polymerizable compounds such as oxetane compounds, isocyanate compounds and alcohols. and polymerizable compounds such as compounds.

<Iso(thio)cyanate compound>
A composition containing an iso(thio)cyanate compound and a compound having an active hydrogen can be preferably used. The iso(thio)cyanate compound refers to an isocyanate group or a compound having an isothiocyanate group, and may be a compound having both an isocyanate group and an isothiocyanate group.

As the iso(thio)cyanate compound, known compounds can be used without any particular limitation. It preferably contains polyiso (thio) cyanate compounds having aromatic rings such as m-xylene diisocyanate and 4,4'-diphenylmethane diisocyanate, and aliphatic polyiso (thio) compounds such as norbornane diisocyanate and dicyclohexylmethane-4,4'-diisocyanate. ) containing a cyanate compound is particularly preferred.

<Compound having active hydrogen>
A compound having an active hydrogen can be used without particular limitation, but a compound having a hydroxyl group and/or a thiol group is preferred. In particular, it preferably contains a polyfunctional compound having two or more active hydrogens in one molecule. Specific examples of compounds having active hydrogen include polyfunctional thiol compounds such as pentaerythritol-letetrakis(3-mercaptopropionate) and 4-mercaptomethyl-3,6-dithia-octanedithiol, and trimethylolpropane. , pentaerythritol and other polyfunctional alcohols, and compositions containing these are preferred.

<Suitable combination of polymerizable compounds>
Among the iso(thio)cyanate compound and the active hydrogen-containing compound, a photochromic curable composition in which the resulting photochromic cured product is less cloudy and can exhibit more photochromic properties by combining the following: can be a thing.

In particular,
The polymerizable compound is
(A) a polyiso(thio)cyanate compound having two or more iso(thio)cyanate groups in the molecule (hereinafter sometimes simply referred to as "(A) component");
(B) a polyfunctional compound having two or more active hydrogens in one molecule (hereinafter sometimes simply referred to as "component (B)");
(C) a monofunctional compound having one active hydrogen per molecule (hereinafter sometimes simply referred to as "(C) component"),
The photochromic curable composition preferably contains 1 to 2000 mol of the component (C) per 1 mol of the oligomer chain group A in the photochromic compound.

<(A) Polyiso (thio) cyanate compound>
The (A) polyiso(thio)cyanate compound constituting the photochromic curable composition of the present invention is a compound having two or more iso(thio)cyanate groups in the molecule. In the present invention, the iso(thio)cyanate group refers to an isocyanate group or an isothiocyanate group. And having two or more iso(thio)cyanate groups in the molecule means having two or more isocyanate groups in the molecule, having two or more isothiocyanate groups in the molecule, or isocyanate in the molecule It means that the total number of groups and isothiocyanate groups is 2 or more.

The number of iso(thio)cyanate groups in component (A) is not particularly limited as long as it is two or more. Among them, the number is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2, from the viewpoint of facilitating control of polymerization.

Among the polyiso(thio)cyanate compounds, polyisocyanate compounds (compounds having two or more isocyanate groups in the molecule) include aliphatic isocyanate compounds, alicyclic isocyanate compounds, aromatic isocyanate compounds, sulfur-containing aliphatic Isocyanate compounds, aliphatic sulfide-based isocyanate compounds, aromatic sulfide-based isocyanate compounds, aliphatic sulfone-based isocyanate compounds, aromatic sulfone-based isocyanate compounds, sulfonic acid ester-based isocyanate compounds, aromatic sulfonic acid amide-based isocyanate compounds, sulfur-containing hetero A cyclic isocyanate compound and the like can be mentioned.
<Suitable (A) polyisocyanate compound>
Among the above polyisocyanate compounds (A), compounds suitable for forming optical articles having excellent transparency and mechanical strength, particularly compounds suitable for producing optical articles containing photochromic compounds. Examples include the following compounds.

Preferred examples of the (A) polyisocyanate compound are compounds represented by the following formulas (I) to (VIII).

<Polyisocyanate compound having an alkylene chain>
Formula (I) below

(In the formula,
R ¹⁰⁰ is an alkylene group having 1 to 10 carbon atoms, and may be a group in which part of the methylene groups in the chain of the alkylene group is substituted with a sulfur atom. ) is preferably used.

R ¹⁰⁰ is an alkylene group having 1 to 10 carbon atoms and may be a linear or branched group. Among them, a pentamethylene group, a hexamethylene group, or a linear group of a heptamethylene group or an octamethylene group, or a part of hydrogen atoms of a pentamethylene group, a hexamethylene group, a heptamethylene group or an octamethylene group is methyl A branched group substituted with a group is preferred. Moreover, the alkylene group in which a part of the methylene group is substituted with a sulfur atom is preferably a -CH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ - group.

Specific examples of the compound represented by formula (I) include pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,2-bis( 2-isocyanatoethylthio)ethane and the like. These compounds can be used alone, or two or more kinds of compounds can be used.

<Polyisocyanate compound having a phenyl group or a cyclohexane group (ring)>
Formula (II) below, Formula (III) below

(In the formula,
R ¹⁰¹ is each an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and may be the same group or different groups;
R ¹⁰² is an alkyl group having 1 to 4 carbon atoms, and when a plurality of groups are present, they may be the same group or different groups,
a ¹⁰⁰ is an integer of 2 or 3, b ¹⁰⁰ is an integer of 0 to 4, and c ¹⁰⁰ is an integer of 0 to 4. ) is preferably used. The difference between the compound represented by the formula (II) and the compound represented by the formula (III) is that the compound having a phenyl group (the compound represented by the formula (II)) and the compound having a cyclohexane group (ring) (the compound represented by formula (III)).

In R ¹⁰¹ , the alkyl group having 1 to 4 carbon atoms may be a linear or branched group. Among them, R ¹⁰¹ is particularly preferably a hydrogen atom, a methyl group, or an ethyl group. In R ¹⁰² , the alkyl group having 1 to 4 carbon atoms may be a linear or branched group. Among them, R ¹⁰² is particularly preferably a methyl group or an ethyl group.

Specific examples of the compound represented by formula (II) or formula (III) include isophorone diisocyanate, xylene diisocyanate (o-, m-, p-), 2,4-tolylene diisocyanate, 2, 6-tolylene diisocyanate and the like. These compounds can be used alone, or two or more kinds of compounds can be used.

<Polyisocyanate compound having two phenyl groups or two cyclohexane groups (rings)>
Formula (IV) below, Formula (V) below

(In the formula,
Each R ¹⁰³ is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and may be the same group or different groups, and d ¹⁰⁰ is an integer of 0 to 4. ) is preferably used. The difference between the compound represented by the formula (IV) and the compound represented by the formula (V) is that the compound having two phenyl groups (the compound represented by the formula (IV)) and two cyclohexane groups (rings) This is the difference from the compound (the compound represented by the above formula (V)).

In R ¹⁰³ , the C 1-4 alkyl group may be a linear or branched group. Among them, R ¹⁰³ is particularly preferably a hydrogen atom, a methyl group or an ethyl group.

Specific examples of the compound represented by formula (IV) or formula (V) include 4,4′-diphenylmethane diisocyanate and dicyclohexylmethane-4,4′-diisocyanate. These compounds can be used alone, or two or more kinds of compounds can be used.

<Polyisocyanate compound having a norbornane ring>
Formula (VI) below

(In the formula,
Each R ¹⁰⁴ is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and may be the same group or different groups, and e ¹⁰⁰ is an integer of 0 to 4. ) is a compound represented by

In R ¹⁰⁴ , the alkyl group having 1 to 4 carbon atoms may be a linear or branched group. Among them, R ¹⁰⁴ is particularly preferably a hydrogen atom, a methyl group or an ethyl group.

Specific examples of the compound represented by the formula (VI) include norbornane diisocyanate, 2,5-bis(isocyanatomethyl)-bicyclo[2,2,1]-heptane, 2,6-bis(isocyanatomethyl) -bicyclo[2,2,1]-heptane. These compounds can be used alone, or two or more kinds of compounds can be used.

<Polyisocyanate Compound Having Thiophene Ring or Sulfur-Containing Heterocycle>
Formula (VII) below, Formula (VIII) below

(In the formula,
R ¹⁰⁵ is each an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and may be the same group or different groups;
R ¹⁰⁶ is a methylene group or a sulfur atom, R ¹⁰⁷ is an alkylene group having 1 to 6 carbon atoms, or part of the carbon atoms in the chain of the alkylene group having 1 to 6 carbon atoms is an —S— bond and ^f100 is an integer of 0 to 2. ) is preferably used.
Specific examples of compounds represented by formula (VII) or formula (VIII) include 2,5-bis(isocyanatomethyl)thiophene, 2,5-bis(isocyanatomethyl)-1,4 -dithiane, 3,4-bis(isocyanatomethyl)tetrahydrothiophene, 4,5-bis(isocyanatomethyl)-1,3-dithiolane and the like. These compounds can be used alone, or two or more kinds of compounds can be used.

Furthermore, halogen-substituted, alkyl-substituted, alkoxy-substituted, and nitro-substituted polyisocyanates, prepolymer-type modified products with polyhydric alcohols, carbodiimide-modified products, urea-modified products, biuret-modified products, dimerization or trimers Chemical reaction products and the like can also be used.

<Suitable (A) polyiso (thio) cyanate compound (compound having two or more isothiocyanate groups in the molecule)
Examples of the polyisothiocyanate compound include polyisocyanate compounds represented by the above formulas (I) to (VIII) in which isocyanate groups are replaced with isothiocyanate groups. More specifically, aliphatic isothiocyanate compounds, alicyclic isothiocyanate compounds, aromatic isothiocyanate compounds, heterocyclic isothiocyanate compounds, sulfur-containing aliphatic isothiocyanate compounds, sulfur-containing aromatic isothiocyanate compounds, sulfur-containing Heterocyclic isothiocyanate compounds and the like are included.

Examples of polyisocyanate compounds having an alkylene chain include hexamethylene diisothiacinate, 1,2-diisothiocyanatoethane, 1,3-diisothiocyanatopropane, 1,4-diisothiocyanatobutane, 1,6-di Isothiocyanatohexane, 2,4,4-trimethylhexanemethylene diisothiacinate, thiobis(3-isothiocyanatopropane), thiobis(2-isothiocyanatoethane), dithiobis(2-isothiocyanatoethane) and the like are preferred. be done.

Polyisocyanate compounds having a phenyl group or a cyclohexane group (ring) include p-phenylenediisopropylidene diisothiocyanate, 1,2-diisothiocyanatobenzene, 1,3-diisothiocyanatobenzene, 1,4-diisothiocyanate Isothiocyanatobenzene, 2,4-diisothiocyanatotoluene, isophorone diisothiocyanate, xylene diisothiocyanate (o-, m-, p-), 2,4-tolylene diisothiocyanate, 2,6-tolylene diisothiocyanate , cyclohexane diisothiocyanate, and the like.

Polyisocyanate compounds having two phenyl groups or two cyclohexane groups (rings) include 1,1′-methylenebis(4-isothiocyanatobenzene), 1,1′-methylenebis(4-isothiocyanate 2-methylbenzene ), 1,1′-methylenebis(4-isothiocyanate-3-methylbenzene), and the like.

Polyisocyanate compounds having a norbornane ring include 2,4-bis(isothiocyanatomethyl)norbornane, 2,5-bis(isothiocyanatomethyl)norbornane, 2,6-bis(isothiocyanatomethyl)norbornane, 3 , 5-bis(isothiocyanatomethyl)norbornane, norbornane diisocyanate, and the like are preferable.

Polyisocyanate compounds having a thiophene ring or a sulfur-containing heterocyclic ring include thiophene-2,5-diisothiocyanate, 1,4-dithiane-2,5-diisothiocyanate, and 2,5-bis(isothiocyanatomethyl). -1,4-dithiane, 4,5-bis(isothiocyanatomethyl)-1,3-dithiolane and the like are preferred.

<(A) component; polyisocyanate compound having an isocyanate group and an isothiocyanate group>
In the present invention, the compound having both an isocyanate group and an isothiocyanate group as the component (A) includes the following compounds. For example, among the polyisocyanate compounds specifically exemplified above, at least one isocyanate group is an isothiocyanate group. Further, in the polyisothiocyanate compounds specifically exemplified above, at least one isothiocyanate group is a compound having an isocyanate group.

<Preferred example of component (A)>
Preferred examples of the polyiso(thio)cyanate compound of component (A) include pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, and 2,5-bis(isocyanatomethyl)-bicyclo [2,2,1]-heptane, 2,6-bis(isocyanatomethyl)-bicyclo[2,2,1]-heptane, 1,2-bis(2-isocyanato-ethylthio)ethane, xylene diisocyanate (o- , m-, p-), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and 4,4'-diphenylmethane diisocyanate, which can be used alone or can be You may use it as a mixture.
Next, (B) a polyfunctional compound having two or more active hydrogens in one molecule will be described.

<(B) Polyfunctional Compound Having Two or More Active Hydrogens in One Molecule>
The polyfunctional compound having two or more active hydrogens in one molecule constituting the photochromic curable composition of the present invention is a compound having two or more hydroxyl groups (OH groups) or thiol groups (SH groups) in the compound. Preferably. Polymerization can be easily controlled by using a compound having a hydroxyl group or a thiol group.

Among the polyfunctional compounds, a compound having two or more hydroxyl groups or thiol groups may be simply referred to as "(B) poly(thiol) compound". In the poly(thio)ol compound (B), a compound having two or more active hydrogens (active hydrogen-containing groups) in the molecule means having two or more hydroxyl groups in the molecule or a thiol group in the molecule. or the total number of hydroxyl groups and thiol groups in the molecule is 2 or more. In addition, in the component (B), the number of active hydrogens (active hydrogen-containing groups) is not particularly limited as long as it is two or more. Among them, the number is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2, from the viewpoint of facilitating control of polymerization.

Specific (B) poly(thiol) compounds include aliphatic poly(thiol) compounds, aromatic poly(thiol) compounds, and the like. More specifically, the following compounds can be mentioned.

<(B) component; suitable multifunctional compound of poly(thiol compound)>
Among the above (B) poly(thiol) compounds, compounds suitable for forming optical articles having excellent transparency and mechanical strength, particularly suitable for producing optical articles containing photochromic compounds. The following compounds are mentioned as the compound which has. Specific examples include compounds represented by the following formulas (IX) to (XI), (XIII) to (XV), and (XVII) to (XXII).

((B) component; poly(thiol) compound having an alkylene chain, etc.)
Formula (IX) below

(In the formula,
B ¹⁰⁰ is an alkylene or alkenyl group having 2 to 30 carbon atoms,
Each R ¹⁰⁸ is a hydroxyl group or an SH group, and may be the same group or different groups. ) is preferably used.

B ¹⁰⁰ is an alkylene or alkenyl group having 2 to 30 carbon atoms, and may be linear or branched. A linear alkylene group having 2 to 15 carbon atoms is preferred. Specific examples of the compound represented by formula (IX) include polyethylene polyol (having 2 to 15 carbon atoms), 1,10-decanedithiol, and 1,8-octanedithiol.

<(B) Component; Polyfunctional Compound Having Two or More Ether Bonds or Ester Bonds>
The following formula (X), or the following formula (XI)

{In the formula,
D ¹⁰⁰ is an alkylene group or alkenyl group having 2 to 15 carbon atoms,
R ¹⁰⁹ is each a hydrogen atom or the following formula (XII)

(In the formula,
R ¹¹⁰ is an alkylene group having 1 to 6 carbon atoms. )
is a group represented by, and may be the same group or a different group,
l ¹⁰⁰ is an integer from 1 to 100 on average. } is preferably used.

D ¹⁰⁰ is an alkylene or alkenyl group having 2 to 15 carbon atoms, and may be a linear or branched group. A linear alkylene group having 2 to 6 carbon atoms is preferred. R ¹¹⁰ is an alkylene group having 1 to 6 carbon atoms and may be a linear or branched group. Among them, R ¹¹⁰ is particularly preferably a methylene group, ethylene group, trimethylene group or propylene group.

Specific examples of the compound represented by the formula (X) or the compound represented by the formula (XI) include polyethylene glycol (l = 1 to 100), polycaprolactone polyol (l = 1 to 100), tetraethylene Glycol bis(3-mercaptopropionate), 1,4-butanediol bis(3-mercaptopropionate), 1,6-hexanediol bis(3-mercaptopropionate) and the like.

<(B) component; suitable carbonate polyol compound (polyfunctional compound)>
Formula (XIII) below

(In the formula,
E ¹⁰⁰ and E ¹⁰⁰ ' are each an alkylene group having 2 to 15 carbon atoms, and may be the same group or different groups;
g ¹⁰⁰ is a number from 1 to 20 on average. ) is preferably used.

E ¹⁰⁰ and E ¹⁰⁰ ′ are alkylene groups having 2 to 15 carbon atoms and may be linear or branched groups. Among them, E ¹⁰⁰ and E ¹⁰⁰ ' are trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, nonamethylene group, dodecamethylene group, pentadecamethylene group, 1-methyltriethylene group, 1 -Ethyltriethylene group and 1-isopropyltriethylene group are particularly preferred. Specific examples of the compound represented by the formula (XIII) include polycarbonate polyols (E ¹⁰⁰ and E ¹⁰⁰ ′ are pentamethylene group and hexamethylene group, g ¹⁰⁰ =4 to 10).

<(B) component; polyfunctional polyol compound (polyfunctional compound)>
Formula (XIV) below

(In the formula,
R ¹¹¹ is an alkyl group having 1 to 6 carbon atoms, and when there are more than one, they may be the same or different,
R ¹¹² is a hydrogen atom, or the same as in formula (XII) above, which may be the same or different; R ¹¹³ is each a hydrogen atom, a methyl group, an ethyl group, or a hydrogen atom, and may may be
o ¹⁰⁰ is 0-2, q ¹⁰⁰ is 2-4, o ¹⁰⁰ +q ¹⁰⁰ is 4, p ¹⁰⁰ is 0-10 and r ¹⁰⁰ is 1-6. ) is preferably used.

R ¹¹¹ is an alkyl group having 2 to 15 carbon atoms and may be a linear or branched group. Among them, R ¹¹¹ is particularly preferably a methyl group, an ethyl group, a trimethyl group, or a propyl group.

Specific examples of the compound represented by the formula (XIV) include trimethylolpropane tripolyoxyethylene ether (TMP-30 manufactured by Nippon Nyukazai Co., Ltd.), trimethylolpropane, pentaerythritol, trimethylolpropane tris (3-mercapto propionate), pentaerythritol tetrakis (3-mercaptopropionate), and the like.

<(B) component; polyol compound having an ether bond (polyfunctional compound)>
Formula (XV) below

{In the formula,
F ¹⁰⁰ is each an alkyl group of 1 to 6, or the following formula (XVI)

(In the formula,
R ¹¹⁴ is a hydrogen atom or a group as defined in formula (XII) above, and may be the same group or a different group;
R ¹¹⁵ is each a methyl group, an ethyl group, or a hydrogen atom, and may be the same group or different groups,
s ¹⁰⁰ is 0-10 and t ¹⁰⁰ is 1-6. ) and
However, at least two or more of the groups F ¹⁰⁰ are groups represented by the formula (XVI). } is preferably used.

At least two of F ¹⁰⁰ are groups represented by the above formula (XVI). Other groups include 1 to 6 alkyl groups, which may be chain or branched groups. Among them, F ¹⁰⁰ is particularly preferably a methyl group, an ethyl group, a trimethyl group, or a propyl group. In addition, as long as two or more of F ¹⁰⁰ are groups represented by the formula (XVI), they may be the same group or different groups. Specific examples of the compound represented by the formula (XV) include ditrimethylolpropane, dipentaerythritol-hexakis(3-mercaptopropionate) and the like.

<(B) component; polyol compound having two hydroxyl groups (polyfunctional compound)>
Formula (XVII) below

(In the formula,
R ¹¹⁶ is an alkyl or alkenyl group having 1 to 30 carbon atoms. ) is preferably used.

R ¹¹⁶ is an alkyl group having 1 to 30 carbon atoms or an alkenyl group having 1 to 30 carbon atoms, and may be a linear or branched group. Since the above formula (XVII) can be obtained from the condensation reaction of fatty acid and glycerin, specific examples of R ¹¹⁶ include the alkyl and alkenyl group moieties of fatty acid. Fatty acids include capric acid, lauric acid, myristic acid, pentadecyl acid, palmitic acid, margaric acid, stearic acid, oleic acid, linoleic acid, arachidic acid, behenic acid, and lignoceric acid.

Specific examples of the compound represented by the formula (XVII) include glyceryl monooleate (monoolein manufactured by Tokyo Chemical Industry Co., Ltd.), monoelaidin, glyceryl monolinoleate, and glyceryl monobehenate.

<(B) component; polyfunctional polythiol compound (polyfunctional compound)>
Formula (XVIII) below

(In the formula,
R ¹¹⁷ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a group in which some of the methylene groups of the alkyl group having 1 to 6 carbon atoms are -S- bonds, and when there are multiple R ¹¹⁷ may be the same group or different groups,
R ¹¹⁸ is an alkylene group having 1 to 10 carbon atoms, a group in which some of the methylene groups in the chain of the alkylene group having 1 to 10 carbon atoms are -S- bonds, or the 1 to 10 carbon atoms is a group in which some of the hydrogen atoms of the alkylene group of is substituted with an SH group, and when there are a plurality of R ¹¹⁸ , they may be the same group or different groups,
u ¹⁰⁰ is an integer from 2 to 4 and v ¹⁰⁰ is an integer from 0 to 2. ) is preferably used.

In R ¹¹⁷ , the alkyl group having 1 to 6 carbon atoms may be a linear or branched group, and R ¹¹⁷ is preferably a hydrogen atom, a methyl group or an ethyl group. Specific examples of groups in which some of the methylene groups in the chain of an alkyl group having 1 to 6 carbon atoms are -S- bonds include -CH ₂ SCH ₃ and the like.

In R ¹¹⁸ , the alkylene group having 1 to 10 carbon atoms may be a linear or branched group. Among them, R ¹¹⁸ is particularly preferably a methylene group, an ethylene group, a trimethylene group or a propylene group. Specific groups in which some of the methylene groups in the chain of an alkylene group having 1 to 10 carbon atoms are -S- bonds include -CH ₂ S-, -CH ₂ CH ₂ S-, and -CH ₂ CH ₂ CH ₂ S— and the like. Further, examples of the group in which some of the hydrogen atoms of the alkyl group having 1 to 6 carbon atoms are substituted with SH groups include groups such as —CH ₂ SCH(SCH ₂ SH)—.

Specific examples of the compound represented by the formula (XVIII) include 1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane, 2,2-bis(mercaptomethyl)-1,4 -butanedithiol, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 1,1,1,1-tetrakis(mercaptomethyl)methane, 1,1,3,3-tetrakis(mercaptomethylthio)propane , 1,1,2,2-tetrakis(mercaptomethylthio)ethane and the like.

<(B) component; cyclic polythiol compound (polyfunctional compound)>
The following formula (XIX)

(In the formula,
R ¹¹⁹ is a methylene group or a sulfur atom, at least two of the three R ¹¹⁹ are sulfur atoms,
R ¹²⁰ is an alkylene group having 1 to 6 carbon atoms, or a group in which some of the methylene groups in the chain of the alkylene group having 1 to 6 carbon atoms are -S- bonds. ) is preferably used.

In R ¹²⁰ , the alkylene group having 1 to 6 carbon atoms may be a linear or branched group. Among them, R ¹²⁰ is preferably a methylene group, ethylene group, trimethylene group or propylene group. Further, the group in which some of the methylene groups in the chain of the alkylene group having 1 to 6 carbon atoms are -S- bonds are specifically -CH ₂ S-, -CH ₂ CH ₂ S-, etc. is mentioned. Specific examples of the compound represented by the formula (XIX) include 2,5-bis(mercaptomethyl)-1,4-dithiane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, and the like. mentioned.

<(B) component; phenyl group-containing polythiol compound (polyfunctional compound)>
Formula (XX) below

(In the formula,
R ¹²¹ is an alkylene group having 1 to 6 carbon atoms, or a group in which some of the methylene groups in the chain of the alkylene group having 1 to 6 carbon atoms are -S- bonds, and w ¹⁰⁰ is 2 to 3. ) can be used.

In R ¹²¹ , the alkylene group having 1 to 6 carbon atoms may be a linear or branched group. Among them, R ¹²¹ is preferably a methylene group, an ethylene group, a trimethylene group, or a propylene group. Further, the groups in which some of the methylene groups in the chain of the alkylene group having 1 to 6 carbon atoms are -S- bonds are specifically -CH ₂ CH ₂ CH ₂ SCH ₂ -, -CH ₂ CH ₂ SCH ₂ -, -CH ₂ SCH ₂ - and the like. A specific example of the compound represented by the formula (XX) is 1,4-bis(mercaptopropylthiomethyl)benzene.

<Component (B); Poly(thiol) compound having a triazine ring (polyfunctional compound)>
The following formula (XXI)

{In the formula,
R ¹²² is each an alkyl group having 1 to 6 carbon atoms, or the following formula (XXII)

(In the formula,
R ¹²³ and R ¹²⁴ are alkylene groups having 1 to 6 carbon atoms,
R ¹²⁵ is an oxygen atom or a sulfur atom)
wherein at least two of the R ¹²² are groups represented by the formula (XXII), and the R ¹²² may be the same group or different groups. } is preferably used.

In R ¹²³ and R ¹²⁴ , the C 1-6 alkylene group may be a linear or branched group. Among them, R ¹²³ and R ¹²⁴ are preferably methylene group, ethylene group, trimethylene group and propylene group. A specific example of the compound represented by the formula (XXI) is tris-{(3-mercaptopropionyloxy)-ethyl}-isocyanurate.

<(B) component; compound having a silsesquioxane structure (polyfunctional compound)>
A compound having a silsesquioxane structure can be used as the component (B). The silsesquioxane polymerizable compound has various molecular structures such as cage-like, ladder-like and random-like, and is a compound represented by the following formula (XXIII).

In the formula, a plurality of R ⁵⁰⁰ may be the same or different, and may be a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a phenyl group, and at least two hydroxyl groups in one molecule, and/ or an organic group containing a thiol group, and the degree of polymerization ⁿ¹⁰⁰ is an integer of 3-100.

<Preferred example of component (B)>
In the present invention, the component (B) can be used without any particular limitation, and can be used alone or in combination. Considering the photochromic properties of the resulting photochromic cured product, preferred examples of the poly(thio)ol compound of component (B) include polyethylene polyol, polycaprolactone polyol, polycarbonate polyol, trimethylolpropane, and pentaerythritol. trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), 1,4-butanediol bis(3-mercaptopropionate), 1,6-hexanediol bis(3-mercaptopropionate), 1,2-bis[(2- mercaptoethyl)thio]-3-mercaptopropane, 2,2-bis(mercaptomethyl)-1,4-butanedithiol, 1,4-bis(mercaptopropylthiomethyl)benzene, 2,5-bis(mercaptomethyl) -1,4-dithiane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 1,1,1,1-tetrakis(mercaptomethyl)methane, 1,1,3,3-tetrakis(mercapto methylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-mercaptomethanol, tris-{(3-mercaptopropionyl Oxy)-ethyl}-isocyanurate is preferred.
Next, the (C) monofunctional compound having one active hydrogen per molecule will be described.

<(C) Monofunctional Compound Having One Active Hydrogen in One Molecule>
In the present invention, component (C) is a monofunctional compound having one active hydrogen per molecule, which means a compound having one hydroxyl group (OH group) or one thiol group (SH group) in the compound. Preferably. Polymerization can be easily controlled by using a compound having a hydroxyl group or a thiol group. Hereinafter, a compound having one active hydrogen-containing group such as a hydroxyl group or a thiol group in the molecule may be simply referred to as (C) mono(thiol) compound. One of the characteristics of the present invention is to use a specific amount of this component (C).

The photochromic cured product obtained by the method of the present invention is obtained, for example, by reacting the (A) polyiso(thio)cyanate compound and (B) the poly(thio)ol compound, and thus has a (thio)urethane bond. It becomes a rigid hardened body with a network structure. The photochromic compound used in the present invention has an oligomer chain group as described above. By having the oligomer chain group A, the photochromic compound exhibits excellent photochromic properties even in the photochromic cured product. In some cases, the obtained photochromic cured product became cloudy.

In the present invention, by using the component (C), the compatibility between the photochromic compound having the oligomer chain group A and the polymer matrix is considered to be improved, and cloudiness of the obtained photochromic cured product can be suppressed. Conceivable. Furthermore, by adjusting the amount of component (C) added, the mechanical properties of the resulting cured product can be easily controlled. Further, when comparing (B) a photochromic curable composition containing only a poly(thio)ol compound and (C) a photochromic curable composition containing a mono(thio)ol compound, the latter composition exhibits hydrogen bonding. can be reduced. Therefore, it is considered that the viscosity of the photochromic curable composition could be reduced, and the handling performance and moldability during casting could be improved.

In the present invention, as described above, a photochromic cured product obtained by curing a photochromic curable composition containing a photochromic compound by introducing an alkenyl group having 10 to 30 carbon atoms into a photochromic compound having an oligomer chain group A. Cloudiness is suppressed. Furthermore, by including the above component (C) in the photochromic curable composition, cloudiness of the photochromic cured body is more effectively suppressed.

<(C) component; mono(thiol) compound (monofunctional compound)>
In the present invention, examples of (C) monool compounds (compounds having one hydroxyl group) include linear or branched saturated or unsaturated alkyl alcohols.

Specifically, the following compounds can be exemplified as monool compounds.

Polyoxyethylene monoalkyl ether compounds, polyoxypropylene compounds, and polyoxyethylene polyoxypropylene monoalkyl ether compounds can be preferably used, and the alkyl group is a hydrocarbon group having 1 to 50 carbon atoms. Due to the availability of compounds, methyl, ethyl, propyl, butyl, lauryl, cetyl, stearyl, oleil, myristyl, octyldodecyl, decyl, isodecyl, and behenyl groups , 2-ethylhexyl group, nonyl group, isodecyl group, tridecyl group, isostearyl group and cholesteryl group.

polyoxyethylene alkylphenyl ether compounds such as polyoxyethylene octylphenyl ether, nonylphenyl ether, dodecylphenyl ether chain polyoxyethylene phenyl ether, polyoxyethylene benzyl ether, polyoxyethylene bisphenol A ether, polyoxyethylene bisphenol F ether; mentioned.

Examples include polyoxyethylene monoalkyl ester compounds such as polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene monooleate, polyoxyethylene monomyristate, and polyoxyethylene monoisostearate.

Polyoxypropylene monoalkyl ester compounds such as polyoxypropylene monolaurate, polyoxypropylene monooleate, and polyoxypropylene monoisostearate are included.

Examples include glycerol bisester compounds such as glyceryl dioleate, glyceryl distearate, glyceryl dilaurate, and glyceryl diisostearate.

<(C) component; mono(thiol) compound (monofunctional compound)>
In the present invention, among (C) mono(thio)ol compounds, monothiol compounds (compounds having one thiol group) include 3-methoxybutyl thioglycolate, 2-ethylhexyl thioglycolate, 2-octoate Mercaptoethyl, 3-methoxybutyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, 2-octyl 3-mercaptopropionate, n-octyl 3-mercaptopropionate, methyl 3-mercaptopropionate, 3-mercapto Examples include tridecyl propionate, stearyl 3-mercaptopropionate, and saturated or unsaturated alkylthiols having a linear or branched structure having 5 to 30 carbon atoms.

<(C) component; suitable compound (monofunctional compound)>
In the present invention, from the viewpoint that cloudiness of the obtained photochromic cured product can be suppressed by adding a small amount, polyoxyethylene monoalkyl ether substituted with an alkyl group having 3 to 50 carbon atoms, polyoxypropylene monoalkyl ether, poly Oxyethylene polyoxypropylene monoalkyl ethers are preferred, and polyoxyethylene monoalkyl ethers are most preferred.

<Mixing ratio of component (A), component (B), and component (C)>
In the present invention, when the photochromic curable composition containing the components A), (B), and (C) is used, the resulting photochromic cured product has a (thio)urethane resin as a base. do. Therefore, the photochromic properties, durability, and mechanical properties of the resulting photochromic cured product can be appropriately adjusted by adjusting the blending amounts of the components (A), (B), and (C). Let n1 be the total number of moles of iso(thio)cyanate groups in component (A), n2 be the total number of moles of active hydrogen in component (B), and n3 be the total number of moles of active hydrogen in component (C). In order to improve the photochromic properties, durability, and mechanical properties of the resulting photochromic cured product,
n1: (n2 + n3) = 0.9 to 1.5: 1, more preferably n1: (n2 + n3) = 0.95 to 1.3: 1, n1: (n2 + n3) = 1 0 to 1.15:1 is more preferable.

At this time, n2:n3=1 to 300:1 is preferable, n2:n3=3 to 200:1 is more preferable, and n2:n3=5 to 150:1 is further preferable. preferable.

Furthermore, in order to improve moldability during production of a photochromic cured product, it is effective to cure a low-viscosity photochromic curable composition. Therefore, the high-molecular-weight component (C) can be used alone, but the high-molecular-weight component (C) and the low-viscosity, low-molecular-weight component (C) can be used in combination to improve moldability.

<Suitable Blending Ratio of Photochromic Curable Composition Using Component (A), Component (B), and Component (C)>
In the present invention, from the viewpoint of further suppressing the cloudiness of the photochromic cured product, it is preferable that the mixing ratio of the photochromic compound and the component (C) is as follows.

Specifically, the component (C) is preferably in the range of 1 to 2000 mol per 1 mol of the oligomer chain group in the photochromic compound. When the amount of component (C) to be blended satisfies the above range, not only excellent properties are exhibited, The ratio can be easily adjusted. As a result, mechanical properties and the like can be improved. If the amount of component (C) is less than 1 mol, the effect of suppressing cloudiness tends to be reduced. On the other hand, when it exceeds 2000 mol, the mechanical properties of the obtained cured product tend to deteriorate. Considering the effect of suppressing white turbidity and the mechanical properties of the resulting cured product, it is more preferably blended in the range of 10 to 1500 mol, most preferably in the range of 50 to 1300 mol.

<Preparation of Photochromic Curable Composition Containing Component (A), Component (B), and Component (C)>
In the present invention, the photochromic curable composition can be prepared by mixing the components (A), (B), (C) and the photochromic compound. However, since the reaction (polymerization) of components (A), (B), and (C) proceeds relatively quickly, the mixing order can also be as follows.

For example, the photochromic curable composition may consist of a mixture of premix 1 of component (A) and photochromic compound and premix 2 of component (B) and component (C). Then, these pre-mixtures may be mixed together.

The photochromic curable composition can also be composed of a combination of the component (B), the component (C), the premixture 3 of the photochromic compound, and the mixture of the component (A). Then, these pre-mixtures may be mixed together.

<Polymerizable compound <iso(thio)cyanate compound> and <photochromic curable composition when compound having active hydrogen is used; other ingredients>
In the present invention, the photochromic curable composition contains various compounding agents known per se, such as (E) a resin modifier, (F) a polymerization curing accelerator, (G) an internal release agent, an ultraviolet absorber, Antistatic agents, infrared absorbers, ultraviolet stabilizers, antioxidants, anti-coloring agents, antistatic agents, fluorescent dyes, dyes, pigments, various stabilizers such as fragrances, additives, solvents, leveling agents, and t - A thiol such as dodecyl mercaptan can be blended as a polymerization modifier, if necessary. These compounding components can be compounded at the same time when the photochromic curable composition is produced. In addition, for example, the premixture 1, the premixture 2, or the premixture 3 can be blended depending on the respective performance so as not to adversely affect the reaction.

<(E) resin modifier>
In the present invention, a resin modifier can be added for the purpose of improving the refractive index of the obtained cured product and adjusting the hardness. Examples thereof include episulfide compounds, thietanyl compounds, polyamine compounds, epoxy compounds, and olefin compounds including (meth)acrylate compounds. Specific examples are described below.

<(E) resin modifier; episulfide compound>
In the present invention, the episulfide compound is a compound having two or more episulfide groups in one molecule, and the episulfide groups undergo ring-opening polymerization, so that a cured product can be produced. The compound can be added for the purpose of increasing the refractive index of the photochromic cured product. Specific examples of the compound include the following.

bis(1,2-epithioethyl)sulfide, bis(1,2-epithioethyl)disulfide, bis(2,3-epithiopropyl)sulfide, bis(2,3-epithiopropylthio)methane, bis(2,3 -epithiopropyl)disulfide, bis(2,3-epithiopropyldithio)methane, bis(2,3-epithiopropyldithio)ethane, bis(6,7-epithio-3,4-dithiaheptyl)sulfide, bis (6,7-epithio-3,4-dithiaheptyl) disulfide, 1,4-dithiane-2,5-bis(2,3-epithiopropyldithiomethyl), 1,3-bis(2,3-epithio propyldithiomethyl)benzene, 1,6-bis(2,3-epithiopropyldithiomethyl)-2-(2,3-epithiopropyldithioethylthio)-4-thiahexane, 1,2,3-tris( 2,3-epithiopropyldithio)propane, 1,1,1,1-tetrakis(2,3-epithiopropyldithiomethyl)methane, 1,3-bis(2,3-epithiopropyldithio)-2 -thiapropane, 1,4-bis(2,3-epithiopropyldithio)-2,3-dithiabutane, 1,1,1-tris(2,3-epithiopropyldithio)methane, 1,1,1- tris(2,3-epithiopropyldithiomethylthio)methane, 1,1,2,2-tetrakis(2,3-epithiopropyldithio)ethane, 1,1,2,2-tetrakis(2,3-epi thiopropyldithiomethylthio)ethane, 1,1,3,3-tetrakis(2,3-epithiopropyldithio)propane, 1,1,3,3-tetrakis(2,3-epithiopropyldithiomethylthio)propane, 2-[1,1-bis(2,3-epithiopropyldithio)methyl]-1,3-dithietane, 2-[1,1-bis(2,3-epithiopropyldithiomethylthio)methyl]-1 , 3-dithiethane.

<(E) resin modifier; thietanyl-based compound>
In the present invention, the thietanyl-based compound is a thietane compound having two or more thietanyl groups in one molecule and is cured by ring-opening polymerization. These compounds can be added for the purpose of increasing the refractive index of the photochromic cured product. Some of the thietanyl-based compounds have multiple thietanyl groups as well as episulfide groups, which are listed above in the episulfide-based compounds section. Other thietanyl-based compounds include metal-containing thietane compounds having metal atoms in the molecule and non-metallic thietane compounds containing no metal. Specific examples of such thietanyl-based compounds include the following.

Non-metallic thietane compounds; bis(3-thietanyl) disulfide, bis(3-thietanyl) sulfide, bis(3-thietanyl) trisulfide, bis(3-thietanyl) tetrasulfide, 1,4-bis(3-thietanyl) -1,3,4-trithibutane, 1,5-bis(3-thietanyl)-1,2,4,5-tetrathiapentane, 1,6-bis(3-thietanyl)-1,3,4,6 -tetrathiahexane, 1,6-bis(3-thietanyl)-1,3,5,6-tetrathiahexane, 1,7-bis(3-thietanyl)-1,2,4,5,7-penta Thiaheptane, 1,7-bis(3-thietanylthio)-1,2,4,6,7-pentathiaheptane, 1,1-bis(3-thietanylthio)methane, 1,2-bis(3-thietanylthio) ethane, 1,2,3-tris(3-thietanylthio)propane, 1,8-bis(3-thietanylthio)-4-(3-thietanylthiomethyl)-3,6-dithiaoctane, 1,11-bis( 3-thietanylthio)-4,8-bis(3-thietanylthiomethyl)-3,6,9-trithiundecane, 1,11-bis(3-thietanylthio)-4,7-bis(3-thietani thiomethyl)-3,6,9-trithiundecane, 1,11-bis(3-thietanylthio)-5,7-bis(3-thietanylthiomethyl)-3,6,9-trithiundecane, 2 , 5-bis(3-thietanylthiomethyl)-1,4-dithiane, 2,5-bis[[2-(3-thietanylthio)ethyl]thiomethyl]-1,4-dithiane, 2,5-bis( 3-thietanylthiomethyl)-2,5-dimethyl-1,4-dithiane, bisthietanylsulfide, bis(thietanylthio)methane, 3-[<(thietanylthio)methylthio>methylthio]thietane, bisthietanyldisulfide, bis thietanyl trisulfide, bisthietanyl tetrasulfide, bisthietanyl pentasulfide, 1,4-bis(3-thietanyldithio)-2,3-dithibutane, 1,1,1-tris(3-thietanyldithio)methane, 1, 1,1-tris(3-thietanyldithiomethylthio)methane, 1,1,2,2-tetrakis(3-thietanyldithio)ethane, 1,1,2,2-tetrakis(3-thietanyldithiomethylthio)ethane.

<(E) resin modifier; metal-containing thietane compound>
This thietane compound contains, in the molecule, as metal atoms, group 14 elements such as Sn atoms, Si atoms, Ge atoms and Pb atoms; group 4 elements such as Zr atoms and Ti atoms; group 13 elements such as Al atoms; element; or group 12 element such as Zn atom;

Alkylthio(thietanylthio)tins include methylthiotris(thietanylthio)tin, ethylthiotris(thietanylthio)tin, propylthiotris(thietanylthio)tin, isopropylthiotris(thietanylthio)tin and the like.

Bis(alkylthio)bis(thietanylthio)tin includes bis(methylthio)bis(thietanylthio)tin, bis(ethylthio)bis(thietanylthio)tin, bis(propylthio)bis(thietanylthio)tin, bis(isopropylthio)bis(thietanylthio)tin. ) tin and the like.

Alkylthio(alkylthio)bis(thietanylthio)tin includes ethylthio(methylthio)bis(thietanylthio)tin, methylthio(propylthio)bis(thietanylthio)tin, isopropylthio(methylthio)bis(thietanylthio)tin, ethylthio(propylthio)bis(thietanylthio)tin. ) tin, ethylthio(isopropylthio)bis(thietanylthio)tin, isopropylthio(propylthio)bis(thietanylthio)tin and the like.

Bis(thietanylthio)cyclic dithiotin compounds include bis(thietanylthio)dithiastanetan, bis(thietanylthio)dithiastanenolan, bis(thietanylthio)dithiastanninan, bis(thietanylthio)trithiastanenocane, and the like. .

Alkyl(thietanylthio)tin compounds include methyltris(thietanylthio)tin, dimethylbis(thietanylthio)tin, butyltris(thietanylthio)tin, tetrakis(thietanylthio)tin, tetrakis(thietanylthio)germanium, and tris(thietanylthio)bismuth.

<(E) resin modifier; polyamine compound>
In the present invention, the polyamine compound is a compound having two or more _NH2 groups in one molecule, and forms a urea bond by reaction with polyisocyanate and a thiourea bond by reaction with polyisothiocyanate. do. These polyamine compounds can be added for adjusting the hardness of the cured product. Specific examples thereof include the following compounds.

ethylenediamine, hexamethylenediamine, isophoronediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, metaxylenediamine, 1,3-propanediamine, putrescine, 2-(2-aminoethylamino)ethanol, diethylenetriamine, p-phenylenediamine, m-phenylenediamine, melamine, 1,3,5-benzenetriamine.

<(E) resin modifier; epoxy compound>
In the present invention, the epoxy-based compound has an epoxy group in the molecule and is cured by ring-opening polymerization of the epoxy group. The compound can be added for the purpose of adjusting the refractive index and adjusting the lens hardness. Such epoxy compounds are classified into aliphatic epoxy compounds, alicyclic epoxy compounds, and aromatic epoxy compounds, and specific examples thereof include the following.

Aliphatic epoxy compounds include ethylene oxide, 2-ethyloxirane, butyl glycidyl ether, phenyl glycidyl ether, 2,2′-methylenebisoxirane, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, and diethylene glycol diglycidyl ether. ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, nonaethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, tetrapropylene glycol diglycidyl ether, Nonapropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, diglycerol tetraglycidyl ether, pentaerythritol tetraglycidyl ether, tris(2-hydroxyethyl) isocyanurate triglycidyl ether and the like.

Alicyclic epoxy compounds include isophoronediol diglycidyl ether, bis-2,2-hydroxycyclohexylpropane diglycidyl ether, and the like.

Aromatic epoxy compounds include resol syndiglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, orthophthalic acid diglycidyl ester, phenol novolac polyglycidyl ether, cresol novolac polyglycidyl ether, and the like. is mentioned.

In addition to the above, an epoxy-based compound having a sulfur atom in the molecule can also be used together with the epoxy group. Such sulfur-containing epoxy compounds particularly contribute to improving the refractive index, and include linear aliphatic compounds and cycloaliphatic compounds. Specific examples thereof are as follows.

Examples of chain aliphatic sulfur-containing epoxy compounds include bis(2,3-epoxypropyl) sulfide, bis(2,3-epoxypropyl) disulfide, bis(2,3-epoxypropylthio)methane, 1, 2-bis(2,3-epoxypropylthio)ethane, 1,2-bis(2,3-epoxypropylthio)propane, 1,3-bis(2,3-epoxypropylthio)propane, 1,3- Bis(2,3-epoxypropylthio)-2-methylpropane, 1,4-bis(2,3-epoxypropylthio)butane, 1,4-bis(2,3-epoxypropylthio)-2-methylbutane , 1,3-bis(2,3-epoxypropylthio)butane, 1,5-bis(2,3-epoxypropylthio)pentane, 1,5-bis(2,3-epoxypropylthio)-2- Methylpentane, 1,5-bis(2,3-epoxypropylthio)-3-thiapentane, 1,6-bis(2,3-epoxypropylthio)hexane, 1,6-bis(2,3-epoxypropyl) thio)-2-methylhexane, 3,8-bis(2,3-epoxypropylthio)-3,6-dithiaoctane, 1,2,3-tris(2,3-epoxypropylthio)propane, 2,2 -bis(2,3-epoxypropylthio)-1,3-bis(2,3-epoxypropylthiomethyl)propane, 2,2-bis(2,3-epoxypropylthiomethyl)-1-(2, 3-epoxypropylthio)butane and the like.

Cycloaliphatic sulfur-containing atom epoxy compounds include 1,3-bis(2,3-epoxypropylthio)cyclohexane, 1,4-bis(2,3-epoxypropylthio)cyclohexane, 1,3-bis (2,3-epoxypropylthiomethyl)cyclohexane, 1,4-bis(2,3-epoxypropylthiomethyl)cyclohexane, 2,5-bis(2,3-epoxypropylthiomethyl)-1,4-dithiane , 2,5-bis[<2-(2,3-epoxypropylthio)ethyl>thiomethyl]-1,4-dithiane, 2,5-bis(2,3-epoxypropylthiomethyl)-2,5- Examples include dimethyl-1,4-dithiane.

<(E) Resin Modifier; Compound Having a Radically Polymerizable Functional Group>
A compound having a radically polymerizable group can be cured by radical polymerization, and therefore can be used to adjust the hardness of the lens. Examples of the radically polymerizable group include compounds having an acrylate group and a methacrylate group (hereinafter referred to as (meth)acrylate compounds), allyl compounds, and vinyl compounds.

(Meth) acrylate compounds include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di ( meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene glycol Bisglycidyl (meth)acrylate, bisphenol A di(meth)acrylate, 2,2-bis(4-(meth)acryloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxy diethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(3,5-dibromo-4-(meth)acryloyloxyethoxyphenyl)propane, 2, 2-bis(4-(meth)acryloyloxydipropoxyphenyl)propane, bisphenol F di(meth)acrylate, 1,1-bis(4-(meth)acryloxyethoxyphenyl)methane, 1,1-bis (4-(meth)acryloxydiethoxyphenyl)methane, dimethyloltricyclodecane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerol di(meth)acrylate, Pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, methylthio(meth)acrylate, phenylthio(meth)acrylate, benzylthio(meth)acrylate, xylylenedithiol di(meth)acrylate, mercaptoethylsulfide di(meth)acrylate meth)acrylates, bifunctional urethane (meth)acrylates, and the like.

Allyl compounds include allyl glycidyl ether, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate, diethylene glycol bisallyl carbonate, methoxy polyethylene glycol allyl ether, polyethylene glycol allyl ether, methoxy polyethylene glycol-polypropylene glycol allyl ether, butoxy polyethylene glycol-polypropylene glycol allyl ether, methacryloyloxy polyethylene glycol-polypropylene glycol allyl ether, phenoxy polyethylene glycol allyl ether, methacryloyloxy polyethylene glycol allyl ether, and the like.

Examples of vinyl compounds include α-methylstyrene, α-methylstyrene dimer, styrene, chlorostyrene, methylstyrene, bromostyrene, dibromostyrene, divinylbenzene, 3,9-divinylspirobi (m-dioxane) and the like.

<(F) Polymerization curing accelerator>
In the photochromic curable composition of the present invention, various polymerization curing accelerators can be used in order to accelerate the polymerization curing according to the type of the above compound. In the present invention, a reaction catalyst for urethane or urea can be suitably used as a polymerization curing accelerator because the reaction between hydroxyl groups and thiol groups and isocyanate groups and isothiacyanate groups proceeds. When the photochromic curable composition of the present invention contains an episulfide-based compound, a thietanyl-based compound, or an epoxy-based compound, an epoxy curing agent or cationic polymerization catalyst, which will be described later, can be used as a polymerization curing accelerator. When using a compound having a radically polymerizable group such as a (meth)acrylate group, a radical polymerization initiator, which will be described later, can be used as a polymerization curing accelerator.

<(F) Polymerization Curing Accelerator; Reaction Catalyst for Urethane or Urea>
In the present invention, a photochromic cured product having poly(thio)urethane bonds can be produced by reacting polyiso(thia)cyanate with polyol or polythiol. Although this reaction can proceed under non-catalytic conditions, the reaction rate can be improved by using a catalyst. Examples of catalysts include inorganic bases, organic bases such as tertiary amines and phosphines, quaternary ammonium salts, quaternary phosphonium salts, and Lewis acids.

Tertiary amines include triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, triethylenediamine, hexamethylenetetramine, N,N-dimethyloctylamine, N,N,N ',N'-tetramethyl-1,6-diaminohexane, 4,4'-trimethylenebis(1-methylpiperidine), 1,8-diazabicyclo-(5,4,0)-7-undecene and the like. be done.

Phosphines include trimethylphosphine, triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tribenzylphosphine, 1,2-bis(diphenylphosphino)ethane, 1 , 2-bis(dimethylphosphino)ethane and the like.

Quaternary ammonium salts include tetramethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide and the like.

Quaternary phosphonium salts include tetramethylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide and the like.

Lewis acids include triphenylaluminum, dimethyltin dichloride, dimethyltin bis(isooctylthioglycolate), dibutyltin dichloride, dibutyltin dilaurate, dibutyltin maleate, dibutyltin maleate polymer, dibutyltin diricinolate, dibutyltin bis(dodecyl mercad). dibutyltin bis(isooctylthioglycolate), dioctyltin dichloride, dioctyltin maleate, dioctyltin maleate polymer, dioctyltin bis(butyl maleate), dioctyltin dilaurate, dioctyltin diricinolate, dioctyltin dichloride Oleate, dioctyltin di(6-hydroxy)caproate, dioctyltin bis(isooctylthioglycolate), didodecyltin diricinolate, various metal salts such as copper oleate, copper acetylacetonate, iron naphthenate, Iron lactate, iron citrate, iron gluconate, potassium octanoate, 2-ethylhexyl titanate. Depending on the Lewis acid used, the high catalytic activity may make it impossible to control the curing reaction, impairing the mechanical properties of the cured photochromic product. In that case, the above amines can be used together in order to suppress the catalytic activity.

<(F) Polymerization Curing Accelerator; Epoxy Curing Agent>
Examples of epoxy curing agents include amine compounds and salts thereof, quaternary ammonium salts, organic phosphine compounds, metal carboxylates, and acetylacetone chelate compounds. Specific examples thereof include the following.

Amine compounds and salts thereof include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1,8-diaza-bicyclo(5,4,0)undecene-7-trimethylamine, benzyldimethylamine, triethylamine, 2, 4,6-tris(dimethylaminomethyl)phenol, 2-(dimethylaminomethyl)phenol and the like. Quaternary ammonium salts include tetramethylammonium chloride, benzyltrimethylammonium bromide, tetrabutylammonium bromide and the like. Examples of organic phosphine compounds include tetra-n-butylphosphonium benzotriazolate and tetra-n-butylphosphonium-0,0-diethylphosphorodithioate. Metal carboxylates include chromium (III) tricarboxylate, tin octoate, and the like. Acetylacetone chelate compounds include chromium acetylacetonate and the like.

<(F) Polymerization Curing Accelerator; Cationic Polymerization Catalyst>
Examples of cationic polymerization catalysts include Lewis acid catalysts, thermosetting cationic polymerization catalysts, and UV-curable cationic polymerization catalysts. Specific examples of these can include the following. Examples of Lewis acid catalysts include BF ₃ ·amine complexes, PF ₅ , BF ₃ , AsF ₅ and SbF ₅ . Examples of thermosetting cationic polymerization catalysts include phosphonium salts, quaternary ammonium salts such as benzylammonium salts and benzylpyridinium salts, sulfonium salts, benzylsulfonium salts, hydrazinium salts, carboxylic acid esters, sulfonic acid esters, and amine imides. be done. Examples of UV-curable cationic polymerization catalysts include diaryliodonium hexafluorophosphate and bis(dodecylphenyl)iodonium hexafluoroantimonate.

<(F) Polymerization Curing Accelerator; Radical Polymerization Initiator>
A thermal polymerization initiator can be preferably used as the radical polymerization initiator, and specific examples thereof are as follows. Diacyl peroxides include benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide, acetyl peroxide and the like. Peroxyesters include t-butylperoxy-2-ethylhexanate, t-butylperoxyneodecanate, cumylperoxyneodecanate, t-butylperoxybenzoate and the like. Percarbonates include diisopropyl peroxydicarbonate, di-s-butyl peroxydicarbonate and the like. Azo compounds include azobisisobutyronitrile, 2,2′-azobis(2,4-dimethylvaleronitrile) and the like.

The above polymerization curing accelerator (F) can be used alone or in combination of two or more. The amount used may be a so-called catalytic amount. ) may be in the range of 0.001 to 10 parts by weight, particularly 0.01 to 5 parts by weight, relative to the total 100 parts by weight.

<(G) Internal release agent>
In the present invention, the internal mold release agent can be used without limitation as long as it exhibits an effect on releasability. A surfactant can be preferably used in consideration of compatibility with the photochromic compound. Among these surfactants, phosphorus compound surfactants are preferred, and (thio)phosphate, (thio)phosphonate and (thio)phosphinate surfactants are more preferred. The internal mold release agent as used herein includes those exhibiting a mold release effect among the various catalysts described above, and may also include, for example, quaternary ammonium salts and quaternary phosphonium salts. These internal release agents can be appropriately selected in consideration of compatibility with the photochromic curable composition, polymerization conditions, economy, and ease of handling. Specific examples of the (thio)phosphate-based, (thio)phosphonate-based, (thio)phosphinate-based, and phosphite-based internal mold release agents are as follows.

mono-n-butyl phosphate, mono-2-ethylhexyl phosphate, mono-n-octyl phosphate, mono-n-butyl phosphate, bis(2-ethylhexyl) phosphate, di(2-ethylhexyl) phosphate , di-n-octyl phosphate, di-n-butyl phosphate, O,O-dimethyl dithiophosphate, O,O-diethyl dithiophosphate, O,O-bis(2-ethylhexyl) dithiophosphate, O thiophosphate, O-dimethyl, O,O-diethyl thiophosphate, O,O-bis(2-ethylhexyl) thiophosphate, thiomethone, disulfotone, O,O-diethyl S-methyl dithiophosphate, dipropylphosphinic acid, etc. are Chelex H-8, Chelex H-12, Chelex H-18D, Phoslex A-8, Phoslex A-10, Phoslex A-12, Phoslex A-13, Phoslex A- 18, Phoslex DT-8, Chelex TDP, Chelex H-OL, JP-506H, JP-512, JP-524R, JP-312L, JP-333E, JP-318-O sold by Johoku Chemical Industry Co., Ltd. etc.

The various internal mold release agents (G) described above can be used alone or in combination of two or more. It is sufficient to use 0.001 to 10 parts by mass with respect to 100 parts by mass in total.

<Photochromic curable composition; when the polymerizable compound is a radically polymerizable compound>
When using a radically polymerizable compound as the polymerizable compound,
The radically polymerizable compound can be classified into a polyfunctional radically polymerizable compound and a monofunctional radically polymerizable compound, each of which can be used alone or in combination. Radically polymerizable groups include groups having unsaturated double bonds, ie, vinyl groups (including styryl groups, (meth)acrylic groups, allyl groups, etc.).

A polyfunctional radically polymerizable compound refers to a compound having two or more radically polymerizable groups in the molecule. This polyfunctional radically polymerizable compound is divided into a first polyfunctional radically polymerizable compound having 2 to 10 radically polymerizable groups and a second polyfunctional radically polymerizable compound having more than 10 radically polymerizable groups. can be done.

The first radically polymerizable compound is not particularly limited, but preferably has 2 to 6 radically polymerizable groups. Specifically, the first polyfunctional radically polymerizable compound includes 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) polyfunctional (meth)acrylic acid ester compounds such as propane; Polyfunctional allyl compounds such as carbonate, allyl diglycol carbonate, trimethylolpropane triallyl carbonate; 1,2-bis(methacryloylthio)ethane, bis(2-acryloylthioethyl)ether, 1,4-bis(methacryloylthiomethyl) ) polyfunctional thio(meth)acrylate compounds such as benzene; and vinyl compounds such as divinylbenzene.

Examples of the second polyfunctional radically polymerizable compound include compounds having a relatively large molecular weight, such as a silsesquioxane compound having a radically polymerizable group and a polyrotaxane compound having a radically polymerizable group.

A monofunctional radically polymerizable compound refers to a compound having one or more radically polymerizable groups in the molecule. Examples of monofunctional radically polymerizable compounds include unsaturated carboxylic acids such as acrylic acid, methacrylic acid and maleic anhydride; methyl (meth)acrylate, benzyl methacrylate, phenyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl (meth)acrylate, ) acrylate, β-methylglycidyl (meth)acrylate, bisphenol A-monoglycidyl ether-methacrylate, 4-glycidyloxy methacrylate, 3-(glycidyl-2-oxyethoxy)-2-hydroxypropyl methacrylate, 3-(glycidyloxy- (Meth)acrylic acid ester compounds such as 1-isopropyloxy)-2-hydroxypropyl acrylate, 3-glycidyloxy-2-hydroxypropyloxy)-2-hydroxypropyl acrylate; fumaric acid such as diethyl fumarate and diphenyl fumarate Ester compounds; thioacrylic acid and thiomethacrylic acid ester compounds such as methylthioacrylate, benzylthioacrylate, and benzylthiomethacrylate; and vinyl compounds such as styrene, chlorostyrene, methylstyrene, vinylnaphthalene, α-methylstyrene dimer, and bromostyrene. be done.

A radically polymerizable compound can be used alone, or a mixture of a plurality of types can be used. In this case, per 100 parts by mass of the total radical polymerizable compound, 80 to 100 parts by weight of the polyfunctional radically polymerizable compound, preferably 0 to 20 parts by weight of the monofunctional radically polymerizable compound, polyfunctional radically polymerizable It is more preferable to use 90 to 100 parts by mass of the compound and 0 to 10 parts by mass of the monofunctional radically polymerizable compound. Further, per 100 parts by mass of the total radical polymerizable compounds, 80 to 100 parts by mass of the first multifunctional radically polymerizable compound, 0 to 20 parts by mass of the second radically polymerizable compound, and 0 to 20 parts by mass of the monofunctional radically polymerizable compound. Parts by mass are preferable, and the first polyfunctional radically polymerizable compound is 85 to 100 parts by mass, the second polyfunctional radically polymerizable compound is 0 to 10 parts by mass, and the monofunctional radically polymerizable compound is 0 to 10 parts by mass. It is more preferable that

<Combination of Suitable Stabilizers to be Mixed in Photochromic Curable Composition>
<Ultraviolet stabilizer>
In the present invention, an ultraviolet stabilizer can be used in order to improve the durability of the photochromic cured product. Hindered amine light stabilizers, hindered phenol antioxidants, sulfur-based antioxidants, and the like are known as UV stabilizers, and may be appropriately selected and used in consideration of compatibility with the photochromic curable composition. can be done. From the viewpoint of the photochromic properties and durability of the resulting photochromic cured product, particularly suitable UV stabilizers are as follows.

Bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, ADEKA STAB LA-52, LA-57, LA-62, LA-63, LA-67 sold by ADEKA Corporation , LA-77, LA-82, LA-87, 2,6-di-t-butyl-4-methyl-phenol, ethylenebis(oxyethylene)bis[3-(5-t-butyl-4-hydroxy- ｍ－トリル）プロピオネート］、ＢＡＳＦから販売されているＩＲＧＡＮＯＸ１０１０、ＩＲＧＡＮＯＸ１０３５、ＩＲＧＡＮＯＸ１０７５、ＩＲＧＡＮＯＸ１０９８、ＩＲＧＡＮＯＸ１１３５、ＩＲＧＡＮＯＸ１１４１、ＩＲＧＡＮＯＸ１２２２、ＩＲＧＡＮＯＸ１３３０、ＩＲＧＡＮＯＸ１４２５、ＩＲＧＡＮＯＸ１５２０、ＩＲＧＡＮＯＸ２５９、ＩＲＧＡＮＯＸ３１１４、ＩＲＧＡＮＯＸ３７９０、ＩＲＧＡＮＯＸ５０５７、ＩＲＧＡＮＯＸ５６５等を好適に使用できる。

The amount of the ultraviolet stabilizer to be used is not particularly limited as long as it does not impair the effects of the present invention. It ranges from 0.01 part by mass to 1 part by mass. In particular, when using a hindered amine light stabilizer, the effect of improving durability may differ depending on the type of photochromic compound, and color shift may occur in the adjusted color tone. From the viewpoint of suppressing color shift, the amount of the hindered amine light stabilizer used is preferably 0.5 to 30 mol, more preferably 1 to 20 mol, and still more preferably 2 to 15 mol, per 1 mol of the photochromic compound.

EXAMPLES Next, the present invention will be described in detail using Examples and Comparative Examples, but the present invention is not limited to these Examples. First, the measuring apparatus used in the present invention, the manufacturing method of each component, and the like will be described.

Examples 1 to 5 (synthesis of photochromic compounds of the present invention)
<Example 1>
First Step Polyethylene glycol monooleyl ether (36.7 g, 100 mmol) having a number average molecular weight of 357 and toluenesulfonyl chloride (21.0 g, 110 mmol) were dissolved in pyridine (400 mL) and stirred. 1,4-Diazabicyclo[2.2.2]octane (2.2 g, 20 mmol) was added dropwise thereto, and the mixture was stirred at room temperature for 12 hours. After completion of the reaction, the reaction solution was added to ice water and extracted with dichloromethane. The extracted organic layer is washed with 10% hydrochloric acid, and then the solvent is distilled off to give the following formula (16)

A compound represented by was obtained.

Step 2 4-Hydroxybenzoic acid (6.2 g, 45 mmol), potassium carbonate (18.7 g, 135 mmol) were dissolved in DMF (450 mL). The mixture was heated with stirring to bring the liquid temperature to 80°C. After that, the compound of formula (16) (48.6 g, 95 mmol) was added dropwise over 1 hour. After dropping, the mixture was stirred at a liquid temperature of 80°C for 3 hours. Thereafter, the reaction solution was cooled to room temperature, toluene and water were added, liquid separation was performed, the organic layer was recovered, and the solvent was distilled off. Ethanol (500 mL) and sodium hydroxide (4.5 g, 112.5 mmol) were added to the residue obtained after distilling off the solvent, and the mixture was refluxed for 3 hours. After cooling to room temperature, water was added to the reaction solution, and the pH was adjusted to around 5 using 10% hydrochloric acid under ice-cooling. Liquid separation was then carried out using dichloromethane. After distilling off the solvent, the obtained crude product was purified by silica gel column chromatography (developing solvent: ethyl acetate), and the following formula (17)

A compound represented by was obtained.

Step 3 The compound of formula (17) (17.1 g, 36 mmol) was dissolved in dichloromethane (360 mL) and cooled with ice. Then oxalyl chloride (18.3 g, 144 mmol) was added, followed by DMF (2 drops) and stirring. After reacting for 5 hours, the solvent is distilled off, and the following formula (18)

A compound represented by was obtained.

Fourth Step After dissolving the product of the above formula (18) in dichloromethane (300 mL), 2-phenoxyethyl acetate (7.21 g, 40 mmol) was added and stirred under water cooling. Tetrachlorotin (1 M dichloromethane solution, 54 mL) was slowly added dropwise thereto over 1 hour, and the reaction was allowed to proceed for 5 hours after dropping. After the reaction, the reaction solution was slowly poured into ice water to separate the organic layer. After liquid separation, the organic solvent was distilled off, ethanol (300 mL) and sodium hydroxide (2.4 g, 60 mmol) were added to the resulting residue, and the mixture was refluxed for 3 hours. After cooling the reaction solution to room temperature, water was added. Under ice-cooling, the pH of the reaction solution was adjusted to around 5 using 10% hydrochloric acid. After that, using dichloromethane, liquid separation was performed, and the solvent was distilled off from the obtained organic layer. The obtained crude product is purified by silica gel column chromatography (developing solvent: chloroform-ethyl acetate mixed solvent), and the following formula (19)

A compound represented by was obtained.

Fifth Step The compound of formula (19) (12.0 g, 20 mmol) and imidazole (5.1 g, 75 mmol) were dissolved in DMF (200 mL) and cooled with ice. A DMF solution (50 mL) of t-butyldimethylchlorosilane (4.5 g, 30 mmol) was added dropwise thereto over 30 minutes. After completion of the dropwise addition, the reaction was stirred for 2 hours. was used to perform liquid separation. By performing solvent distillation of the obtained organic layer, the following formula (20)

A compound represented by was obtained.

Step 6 DMF (200 mL) was added to the compound of formula (20), and the mixture was stirred under ice-cooling. A suspension of sodium acetylide in xylene was added dropwise. After the dropwise addition, the temperature was raised to room temperature, the reaction was carried out for 1.5 hours, and then the reaction solution was added to ice water. A 10% ammonium chloride aqueous solution and toluene were added thereto, and liquid separation was performed. The resulting organic layer is subjected to solvent distillation, and the following formula (21)

A compound represented by was obtained.

Seventh step Formula (22) below

The compound represented by (1.6 g, 3.0 mmol) and the product of formula (21) (2.6 g, 3.5 mmol) were dissolved in toluene (30 ml). Furthermore, pyridinium p-toluenesulfonate (0.08 g, 0.3 mmol) was added, and the mixture was stirred and refluxed for 1 hour. After that, the reaction solution was cooled to room temperature, water was added, and liquid separation was performed. The solvent of the organic layer was evaporated, and THF (30 mL) was added to dissolve the resulting residue. After cooling with ice, a solution of tetrabutylammonium fluoride in THF (1 mM, 3.5 mL) was added dropwise to the resulting reaction solution. After raising the temperature to room temperature, the reaction was carried out for 2 hours. After completion of the reaction, the mixture was added to ice water and liquid separation was performed. The obtained organic layer was washed with 10% saline, and the organic solvent was distilled off. The obtained crude product is purified by silica gel column chromatography (developing solvent: chloroform-ethyl acetate mixed solvent), and the following formula (23)

A chromene compound precursor represented by was obtained.

Eighth step Polypropylene glycomonobutyl ether (number average molecular weight 3500, 35 g, 10 mmol), succinic anhydride (2.0 g, 20 mmol), triethylamine (2.5 g, 25 mmol), dichloromethane (50 mL) were added, and the mixture was stirred at room temperature for 12 hours. reacted. After completion of the reaction, the pH of the reaction solution was adjusted to 5 using 10% hydrochloric acid under ice-cooling, followed by liquid separation. The obtained organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off. Dichloromethane (50 mL) was added to the resulting residue and ice-cooled, oxalyl chloride (5.1 g, 40 mmol) was added to the reaction solution, DMF (2 drops) was further added, and stirring was performed. After reacting for 5 hours, the solvent is distilled off, and the following formula (24)

A compound represented by was obtained.

Ninth step The compound of formula (23) (2.5 g, 2.2 mmol) was dissolved in dichloromethane (25 mL). After stirring and dissolving, triethylamine (2.4 g, 2.2 mmol) was added and ice-cooled. A dichloromethane solution of the compound of formula (24) (8.3 g, 2.3 mmol) was added dropwise thereto over 30 minutes. After completion of dropping, the temperature was raised to room temperature and stirring was performed for 12 hours. After that, while cooling with ice, the pH of the reaction solution was adjusted to 5 using 10% hydrochloric acid. After that, the obtained reaction solution was subjected to liquid separation, and the organic solvent was distilled off. By purifying the obtained crude product by column chromatography (developing solvent: chloroform-ethyl acetate mixed solvent), the following formula (25)

A chromene compound (photochromic compound of the present invention) represented by was obtained. Yield was 85%.

In addition, when the proton nuclear magnetic resonance spectrum was measured, a cyclohexane ring, a butyl group, a succinic acid site, a propyleneoxy site, a peak of about 240H based on the protons of the oleyl group in the vicinity of 1.0 to 3.0 ppm, δ 3.0 to About 205H peak based on methoxy group, ethylene glycol moiety, butoxy group, oleyl group, propyleneoxy moiety around 5.2ppm, 21H peak based on aromatic proton and alkene proton around δ5.2~9.0ppm and was confirmed to have a structure consistent with the above formula (25).

<Example 2>
Step 1 The eighth step of Example 1, except that polypropylene glycol (number average molecular weight of 2500) was used instead of the polypropylene glycomonobutyl ether (number average molecular weight of 3500) used in the eighth step of Example 1. The reaction is performed in the same manner, and the following formula (26)

A compound represented by was obtained.

2nd step In the 7th step of Example 1, the following formula (27) was used instead of the naphthol compound of the formula (22).

in the same manner except that a naphthol compound represented by the following formula (28)

A chromene precursor represented by was obtained.

Third Step In the ninth step of Example 1, the chromene precursor of the formula (28) is used instead of the chromene compound precursor of the formula (23), and the chromene precursor of the formula (24) is replaced with the formula (26). ) in the same manner except that the compound of the following formula (29) was used.

A chromene compound (photochromic compound of the present invention) represented by was obtained. Yield was 80%.

In addition, when the proton nuclear magnetic resonance spectrum was measured, a cyclohexane ring, a methyl group, a succinic acid site, a propyleneoxy site, a peak of about 247H based on the protons of the oleyl group near 1.0 to 3.0 ppm, δ 3.0 ~ A peak of about 157H based on an ethylene glycol site, an oleyl group, and a propyleneoxy site near 5.2 ppm, and a peak of 36H based on protons of aromatic protons and alkene near δ 5.2 to 9.0 ppm, and the formula ( 29).

<Example 3>
Step 1 Add 4,4-dihydroxybenzophenone (1.0 g, 4.5 mmol), potassium carbonate (1.9 g, 13.5 mmol) and DMF (45 mL), stir, and heat until the internal temperature reaches 80°C. did. After heating, the compound of formula (16) (4.6 g, 9.1 mmol) was added dropwise over 1 hour. After dropping, reaction was carried out at a liquid temperature of 80° C. for 4 hours. After the reaction, the reaction solution was cooled to room temperature, water was added, and liquid separation was performed using toluene. After evaporating the organic solvent, the resulting residue was purified by silica gel column chromatography (developing solvent: chloroform-ethyl acetate mixed solvent), and the following formula (30)

A compound represented by was obtained.

Step 2 The compound represented by the formula (30) was used in place of the compound represented by the formula (20) used in the sixth step of Example 1, except that the compound represented by the formula (30) was used. Perform the same operation, the following formula (31)

A compound represented by was obtained.

Third step Formula (32) below

The compound represented by (0.9 g, 3.0 mmol) and the compound of formula (31) (3.2 g, 3.5 mol) were dissolved in methyl isobutyl ketone (50 ml). Further p-toluenesulfonic acid (0.06 g, 0.3 mmol) was added and refluxed for 1 hour. After the reaction, the mixture was cooled to room temperature, water was added, and liquid separation was performed using toluene. The organic solvent was distilled off from the resulting organic layer to obtain a crude product. The obtained crude product is purified by silica gel column chromatography (developing solvent: chloroform-ethyl acetate mixed solvent), and the following formula (33)

A compound represented by was obtained.

Step 4 The compound of formula (33) (2.4 g, 2.0 mmol) was dissolved in THF (24 mL) and cooled to -78°C. Methyllithium (1.0 M, 2.4 mL) was slowly added dropwise thereto. After that, the temperature was slowly raised to -10°C. After adding water, the reaction solution was warmed to room temperature. After extraction with toluene, the resulting organic layer was washed with 10% saline and the organic solvent was distilled off. The obtained crude product is purified by silica gel column chromatography (developing solvent: chloroform-ethyl acetate mixed solvent), and the following formula (34)

A compound represented by was obtained.

Fifth step Instead of the polypropylene glymonobutyl ether (number average molecular weight 3500) used in the eighth step of Example 1, the following formula (35)

In the same manner as in the eighth step of Example 1, except that a polydimethylsiloxane (number average molecular weight of 1000) having a hydroxyl group terminal represented by the following formula (36)

A compound represented by was obtained.

Sixth step Instead of the compound represented by the formula (28) used in the third step of Example 2, the compound represented by the formula (34) is used, and the compound represented by the formula (26) is replaced by the formula (36) except for using the compound represented by the following formula (37)

A chromene compound (photochromic compound of the present invention) represented by was obtained. Yield was 65%.

In addition, when the proton nuclear magnetic resonance spectrum was measured, a peak of about 236H based on protons of dimethylsiloxane, methyl group, succinic acid site, propoxy group, and oleyl group was found near 0 to 3.0 ppm, and δ 3.0 to 5.2 ppm. A peak of about 64H based on an ethylene glycol moiety, an oleyl group, a methoxy group, and a propoxy group in the vicinity, a 40H peak based on the protons of aromatic protons and alkene in the vicinity of δ 5.2 to 9.0 ppm, and the formula (37 ) was confirmed to be a structure consistent with

<Example 4>
First Step Polypropylene glycol (number average molecular weight 2500, 50.0 g, 20 mmol) and imidazole (5.1 g, 75 mmol) were dissolved in DMF (200 mL) and cooled with ice. A solution of t-butyldimethylchlorosilane (2.9 g, 19.5 mmol) in DMF (50 mL) was added dropwise over 1 hour. After stirring for 2 hours after dropping, the reaction solution was added to ice water. Liquid separation was performed using ethyl acetate, and the solvent was distilled off from the obtained organic layer. The obtained crude product is purified by silica gel column chromatography (developing solvent: acetone-ethyl acetate mixed solvent), and the following formula (38)

A compound represented by was obtained.

2nd Step Sodium hydride (0.8 g, 33.3 mmol) dispersed in liquid paraffin was stirred in heptane and the heptane was decanted off. DMF (20 mL) was added thereto, and the compound of formula (38) (46.2 g, 17.5 mmol) was slowly added dropwise. After stirring at room temperature for 1 hour, the compound represented by the formula (16) (9.2 g, 18.0 mmol) was added and stirred at room temperature for 12 hours. The reaction solution was added to ice water, and liquid separation was performed using ethyl acetate. The obtained organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off. THF (300 mL) was added to the obtained residue and dissolved by stirring. After cooling with ice, a THF solution (1 M, 25 mL) of tetrabutylammonium fluoride was added dropwise. After raising the temperature to room temperature, the reaction was carried out for 2 hours. After that, the reaction solution was added to ice water, and liquid separation was performed with ethyl acetate. The organic layer was washed with 10% saline and the solvent was distilled off. The obtained crude product is purified by silica gel column chromatography (developing solvent: acetone-ethyl acetate mixed solvent), and the following formula (39)

A compound represented by was obtained.

Third step The eighth step of Example 1, except that the compound represented by the above formula (39) was used instead of the polypropylene glymonobutyl ether (number average molecular weight: 3500) used in the eighth step of Example 1. Perform the same operation as the following formula (40)

A compound represented by was obtained.

Fourth step Instead of the compound represented by the above formula (23) used in the ninth step of Example 1, the following formula (41)

Using the compound represented by the formula (24), except that the compound represented by the formula (40) was used in the same manner as in the ninth step of Example 1, and the following Equation (42)

A chromene compound (photochromic compound of the present invention) represented by was obtained. Yield was 80%.

Further, when the proton nuclear magnetic resonance spectrum was measured, a cyclohexane ring site, a methyl group, a succinic acid site, a polypropylene glycol site, a peak of about 188H based on protons of an oleyl group, and a peak of δ3.0 were found near 1.0 to 3.0 ppm. A peak of about 154H based on ethylene glycol sites, oleyl groups, methoxy groups, polypropylene glycol sites, and morpholino groups around ~5.2ppm, 21H peaks based on aromatic protons and alkene protons around δ5.2-9.0ppm A peak was shown, and the structure was confirmed to be consistent with the above formula (42).

<Example 5>
Step 1 Add 4,4-dihydroxybenzophenone (1.0 g, 4.5 mmol), potassium carbonate (0.6 g, 4.5 mmol) and DMF (45 mL), stir, and heat until the internal temperature reaches 80°C. did. After heating, the product of formula (16) (2.2 g, 4.4 mmol) was added dropwise over 2 hours. After dropping, reaction was carried out at an internal temperature of 80° C. for 4 hours. After the reaction, the mixture was cooled to room temperature, toluene and water were added, and liquid separation was performed. After concentration of the solvent, purification was performed by chromatography on silica gel with a mixed solvent of chloroform-ethyl acetate, and the following formula (43) was obtained.

A compound represented by was obtained.

Second step Example 1 In the first step, instead of polyethylene glycol monooleyl ether, the following formula (44) having a number average molecular weight of 1100

The same operation is performed except that a compound represented by the following formula (45)

The tosyl group was substituted to obtain a compound of formula (45).

Step 3 The compound of formula (43) (2.2 g, 3.9 mmol), potassium carbonate (1.2 g, 9.0 mmol) and DMF (40 mL) are added and stirred until the internal temperature reaches 80°C. heated. After heating, the compound represented by the formula (45) (7.3 g, 5.9 mmol) was added dropwise over 1 hour. After dropping, reaction was carried out at an internal temperature of 80° C. for 4 hours. After the reaction, the mixture was cooled to room temperature, toluene and water were added, and liquid separation was performed. After concentration of the solvent, purification was performed by chromatography on silica gel with a mixed solvent of chloroform-ethyl acetate, and the following formula (46) was obtained.

A compound represented by was obtained.

Step 4 Example 1 In the sixth step, the same operation was performed except that the compound of the formula (46) obtained in the first step was used instead of the formula (20), and the following formula (47) was obtained. )

A compound represented by was obtained.

Fifth step Example 3 In the third step, instead of the naphthol compound represented by the above formula (32), the following formula (48)

Using a naphthol compound represented by the following formula (49)

A chromene compound represented by (photochromic compound of the present invention) was obtained with a yield of 67%.

In addition, when the proton nuclear magnetic resonance spectrum was measured, a peak of about 168H based on the protons of dimethylsiloxane, isopropyl group, butyl group, and oleyl group was observed around 0 to 3.0 ppm, and ethylene glycol was found around δ 3.0 to 5.2 ppm. A peak of about 16H based on a site, an oleyl group, and a propoxy group, and a peak of 18H based on an aromatic proton and an alkene proton near δ 5.2 to 9.0 ppm. I confirmed.

Examples 6 to 10 (Preparation and Evaluation of Photochromic Cured Body (Molded Body))
In Examples 5 to 8, the photochromic properties of the above chromene compounds were evaluated as follows. A photochromic curable composition was prepared by mixing each component according to the following recipe. Each compounding amount is shown below. Table 1 shows the results of photochromic properties.

(Blending composition of polymerizable compound)
<A component>
m-xylene diisocyanate; 48.0 parts by mass.
<B component>
Pentaerythritol-letetrakis(3-mercaptopropionate); 25.5 parts by mass.
4-mercaptomethyl-3,6-dithia-octanedithiol; 25.5 parts by mass.
<Other ingredients>
Dimethyldichlorotin; 0.1 part by mass.
JP-506H (manufactured by Johoku Chemical Industry Co., Ltd.); 0.1 part by mass.
The photochromic curable composition is obtained by adding a chromene compound (photochromic compound) to 100 parts by mass of the compounded composition obtained by mixing the above components A, B, and other components so that the indenonaphthopyran moiety is 48 μmol, It was adjusted. Using the photochromic curable composition thus obtained, a photochromic cured body (polymer molded body) was obtained by a kneading method. The polymerization method is as follows.

(Polymerization method)
Using a glass mold and an ethylene-vinyl acetate copolymer gasket, a mold with a thickness of 2 mm was produced. Subsequently, the sufficiently defoamed photochromic curable composition was cast into a mold. Then, while gradually raising the temperature from 20° C. to 120° C., the polymerization reaction was allowed to proceed, and the photochromic curable composition was cured. After curing for 20 hours, the cured photochromic body was removed from the mold.

(Evaluation method for photochromic cured product)
The obtained photochromic cured product was evaluated for (1) photochromic properties, (2) L-scale Rockwell hardness, and (3) transparency. Evaluation methods are as follows.

(1) Photochromic properties Using a xenon lamp L-2480 (300 W) SHL-100 manufactured by Hamamatsu Photonics Co., Ltd., the photochromic cured product is irradiated with light through an air mass filter 2.0 (manufactured by Koyo Co., Ltd.). Various photochromic properties were evaluated by color development of the photochromic cured product. The irradiation conditions are as follows.
Irradiation temperature; 23±0.1°C
Emission intensity: 50,000lux in the range of 300-500nm
Irradiation time: 120 seconds As the photochromic properties of the photochromic cured product, the maximum absorption wavelength, color density, and color fading speed were evaluated. For the measurement, a spectrophotometer (instantaneous multichannel photodetector MCPD1000) manufactured by Otsuka Electronics Co., Ltd. was used.
・Maximum absorption wavelength (λmax):
It is the maximum absorption wavelength in the visible light region of the photochromic cured product after color development. The maximum absorption wavelength is related to the color tone during color development.
・ Color density {ε (120) - ε (0)}:
The color density was evaluated by the difference between the absorbance {ε(120)} after light irradiation for 120 seconds and the absorbance ε(0) before light irradiation at the maximum absorption wavelength. The higher this value, the better the photochromic properties.
- Fading speed [t1/2 (sec.)]:
The photochromic cured body is irradiated with light for 120 seconds, and after the light irradiation is stopped, the time required for the absorbance at the maximum absorption wavelength to decrease to half of {ε(120)−ε(0)}, which is the time required for fading. Evaluated speed. The shorter this time, the better the photochromic properties.
・ Residual rate (A ₂₀₀ /A ₀ × 100):
The resulting photochromic cured product was acceleratedly degraded for 200 hours using a xenon weather meter X25 (manufactured by Suga Test Instruments Co., Ltd.). Thereafter, the color density was evaluated before and after the test, and the color density (A ₀ ) before the test and the color density (A ₂₀₀ ) after the test were measured, and the ratio (A ₂₀₀ /A ₀ ) was defined as the residual rate. , as an index of durability of color development. It can be said that the higher the residual rate, the higher the durability of the color development.

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

(3) Transparency of Photochromic Cured Body The photochromic cured body was visually evaluated for white turbidity under crossed Nicols.
1: At a level that does not pose a problem as a product, there is no cloudiness, or it is hardly visible.
2: The product is at a level that does not pose a problem, but is slightly cloudy.
3: The level is satisfactory as a product, but the cloudiness is stronger than that of 2.
4: There is cloudiness and cannot be used as a product.

Comparative Examples 1-2
For comparison, the compounds represented by the following formulas (A) and (B) were used to obtain photochromic cured products in the same manner as in Examples 5 to 8, and their properties were evaluated.

As is evident from Table 1, the photochromic compounds of the present invention have superior photochromic properties in high hardness matrices when compared to conventional photochromic compounds. That is, it was shown that the photochromic compound of the present invention has excellent photochromic properties in a high-hardness matrix due to having an oligomer chain. It was also shown that by introducing an oleyl group into the photochromic compound, it is possible to suppress cloudiness of the cured product, which has been difficult to solve in the past.

<Example 11>
Step 1 Example Steps 1 to 5 were carried out in the same manner, except that cis-4-decen-1-ol was used instead of polyethylene glycol monooleyl ether having a number average molecular weight of 357. 50)

A compound represented by was obtained.

2nd step Example 1 In the 7th step, instead of the above formula (22), the following formula (51)

Using a naphthol compound represented by the following formula (52)

A chromene precursor represented by was obtained.

3rd step Example 1 The same operation was performed except that polyoxyethylene polyoxypropylene monobutyl ether (number average molecular weight 3300) was used instead of polypropylene glycmonobutyl ether (number average molecular weight 3500) in steps 8 and 9. and the following formula (53)

A chromene compound (photochromic compound of the present invention) represented by was obtained. Yield was 65%.

In addition, when the proton nuclear magnetic resonance spectrum was measured, a peak of about 145H based on the protons of the cyclohexane ring, butyl group, succinic acid site, polyoxypropylene site, and cis-4-decene site was found around 1.0 to 3.0 ppm. , a peak of about 225H based on the ethylene glycol site, butoxy group, cis-4-decene site, polyoxypropylene site, and polyoxyethylene site around δ3.0 to 5.2ppm, aroma around δ5.2 to 9.0ppm It showed a 20H peak based on a tick proton and an alkene proton, and was confirmed to have a structure consistent with the above formula (53).

Examples 12-14
A photochromic curable composition was prepared by mixing each component according to the following recipe. Table 2 shows the amount of each compound.

The photochromic curable composition was prepared by adding a chromene compound (photochromic compound) to 100 parts by mass of the compounded composition so that the amount of indenonaphthopyran moieties was 48 μmol. In addition, 100 parts by mass of the compounded composition means 100 parts by mass of the total amount of A component, B component, C component and other components.

Abbreviations for the compounds used in Table 2 are specified below.
Bicyclo[2.2.1]heptane-2,5(2,6)-diyl)bismethylene diisocyanate; NBDI.
m-xylylene diisocyanate; XDI.
Pentaerythritol-letetrakis(3-mercaptopropionate); PEMP.
Pentaerythritol-letetrakis(3-mercaptopropionate); MTODT.
Dipentaerythritol hexakis (3-mercaptopropionate); DPMP.
Polyethylene glycol monooleil ether (ethylene glycol repeat number about 2, Mn=357); PGME2.
Polyethylene glycol monooleil ether (ethylene glycol repeat number about 10, Mn=709); PGME10.

The photochromic curable composition was polymerized in the same manner as in Example 6 to obtain a photochromic cured product. The obtained photochromic cured product was evaluated in the same manner as in Example 6.
Table 3 shows the results.

Claims (12)

having an indenonaphthopyran moiety,
The indenonaphthopyran moiety includes
an alkenyl group having 10 to 30 carbon atoms;
A photochromic compound having an oligomer chain group A having 3 or more repeating units selected from a polyalkylene oxide oligomer chain group, a polyester oligomer chain group, a polysiloxane chain group and a polyester polyether oligomer chain group. The photochromic compound according to claim 1, represented by the following formula (1).

A chromene compound having an indenonaphthopyran moiety represented by the formula (1),
During the ceremony,
R ¹ and R ² each independently represent the oligomer chain group A, the alkenyl group having 10 to 30 carbon atoms, a group having an alkenyl group having 10 to 30 carbon atoms at its end, a hydroxyl group, an alkyl group, or a haloalkyl group. , optionally substituted cycloalkyl group, alkoxy group, amino group, substituted amino group, optionally substituted heterocyclic group, cyano group, halogen atom, alkylthio group, substituted arylthio group, nitro group, formyl group, hydroxycarbonyl group, alkylcarbonyl group, alkoxycarbonyl group, optionally substituted aralkyl group, optionally substituted aralkoxy group, optionally substituted optionally substituted aryloxy group, optionally substituted heteroaryl group, optionally substituted heteroaryl group, thiol group, alkoxyalkylthio group, haloalkylthio group, or optionally substituted a cycloalkylthio group,
a is an integer from 0 to 4, b is an integer from 0 to 4,
When a is 2 to 4, multiple R ¹ may be the same or different,
When b is 2 to 4, multiple R ² may be the same or different,
Further, when a is 2 to 4 and there are adjacent R ¹ 's, the two adjacent R ¹ 's together with the carbon atoms bonded to those R ¹ 's, oxygen atoms, carbon atoms, sulfur may form a ring that may contain an atom or a nitrogen atom, and the ring may have a substituent,
In addition, when b is 2 to 4 and adjacent R ² is present, the two adjacent R ² together with the carbon atom bonding to those R ² , oxygen atom, carbon atom, sulfur may form a ring that may contain an atom or a nitrogen atom, and the ring may have a substituent,
R ³ and R ⁴ are each independently an optionally substituted aryl group or an optionally substituted heteroaryl group,
R ⁵ and R ⁶ each independently represents the alkenyl group having 10 to 30 carbon atoms, the oligomer chain group A 1 , a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group; , formyl group, hydroxycarbonyl group, alkylcarbonyl group, alkoxycarbonyl group, halogen atom, optionally substituted aralkyl group, optionally substituted aralkoxy group, optionally substituted aryl an oxy group, an optionally substituted aryl group, an optionally substituted heterocyclic group,
R ⁵ and R ⁶ together are an aliphatic ring having 3 to 20 ring carbon atoms together with the carbon atom at position 13 of the indenonaphthopyran moiety to which they are bonded; a condensed polycyclic ring in which an aromatic ring or aromatic heterocyclic ring is condensed, a heterocyclic ring having 3 to 20 ring member atoms, or a condensed polycyclic ring in which an aromatic ring or aromatic heterocyclic ring is condensed to the above heterocyclic ring provided that these rings may have substituents. or an aliphatic hydrocarbon ring having 3 to 20 ring member carbon atoms together with the carbon atom at the 13th position of the indenonaphthopyran moiety to which they are bonded, and an aromatic ring or aromatic heterocyclic ring in the aliphatic hydrocarbon ring A condensed condensed polycyclic ring, a heterocyclic ring having 3 to 20 ring member atoms, or a condensed polycyclic group obtained by condensing an aromatic hydrocarbon ring or an aromatic heterocyclic ring to the above heterocyclic ring may be formed,
The substituent of the group optionally having a substituent may be a group having a terminal alkenyl group having 10 to 30 carbon atoms, the alkenyl group having 10 to 30 carbon atoms, or the oligomer chain group A. ,
also,
The substituents of the groups optionally having substituents are such that the alkenyl groups having 10 to 30 carbon atoms are 1 to 12 per oligomer chain group A contained in one molecule. It may be an alkenyl group having 10 to 30 carbon atoms or a group having an alkenyl group having 10 to 30 carbon atoms at the end ,
at least one of R ¹ , R ² , R ⁵ , R ⁶ and the substituents of the optionally substituted group is the oligomer chain group A;
At least one of R ¹ , R ² , R ⁵ , R ⁶ and the substituents of the optionally substituted group is the alkenyl group having 10 to 30 carbon atoms . The photochromic compound according to claim 1 or 2, represented by the following formula (2).

R ¹ , R ² , R ⁵ and R ⁶ have the same definitions as in formula (1);
a'' is an integer of 0 to 2, b'' is an integer of 0 to 3,
when a″ is 2, a plurality of R ¹ may be the same or different,
When b'' is 2 or 3, a plurality of R ² may be the same or different,
R ¹⁰⁰ and R ¹⁰¹ each independently represent the oligomer chain group A, the alkenyl group having 10 to 30 carbon atoms, a group having an alkenyl group having 10 to 30 carbon atoms at its end, a hydrogen atom, a hydroxyl group, or a carbon number 1 to 6 alkyl group, haloalkyl group having 1 to 6 carbon atoms, cycloalkyl group having 3 to 8 carbon atoms, alkoxy group having 1 to 6 carbon atoms, amino group, substituted amino group, optionally having a substituent heterocyclic group, cyano group, halogen atom, alkylthio group having 1 to 6 carbon atoms, arylthio group having 6 to 10 carbon atoms which may have a substituent, nitro group, formyl group, hydroxycarbonyl group, 2 to 2 carbon atoms 7 alkylcarbonyl group, an alkoxycarbonyl group having 2 to 7 carbon atoms, an aralkyl group having 7 to 11 carbon atoms which may have a substituent, an aralkoxy group having 7 to 11 carbon atoms which may have a substituent, optionally substituted C6-12 aryloxy group, optionally substituted C6-12 aryl group, optionally substituted C3-12 hetero an aryl group, a thiol group, an alkoxyalkylthio group having 2 to 9 carbon atoms, a haloalkylthio group having 1 to 6 carbon atoms, or a cycloalkylthio group having 3 to 8 carbon atoms,
Further, R ¹⁰⁰ and R ¹⁰¹ are together represented by the following formula (3)

[Wherein, * refers to the carbon atom at the 6- or 7-position of the indenonaphthopyran moiety, and one or both of X and Y are a sulfur atom, a methylene group, an oxygen atom, or the following formula (4)

(In the formula,
R ⁹ is the alkenyl group having 10 to 30 carbon atoms, the oligomer chain group A, a group having an alkenyl group having 10 to 30 carbon atoms at its end, a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, carbon haloalkyl groups of 1 to 6 carbon atoms, cycloalkyl groups of 3 to 8 carbon atoms, alkoxy groups of 1 to 6 carbon atoms, aryl groups of 6 to 12 carbon atoms optionally having substituents, optionally having substituents It is a good heteroaryl group having 3 to 12 carbon atoms. ) is a group represented by
R ⁷ and R ⁸ each independently represent an alkenyl group having 10 to 30 carbon atoms, the oligomer chain group A 1 , a group having an alkenyl group having 10 to 30 carbon atoms at its end, a hydroxy group, or a group having 1 to 6 carbon atoms. alkyl group, haloalkyl group having 1 to 6 carbon atoms, cycloalkyl group having 3 to 8 carbon atoms, alkoxy group having 1 to 6 carbon atoms, amino group, substituted amino group, optionally substituted heterocyclic group, cyano group, nitro group, formyl group, hydroxycarbonyl group, alkylcarbonyl group having 2 to 7 carbon atoms, alkoxycarbonyl group having 2 to 7 carbon atoms, halogen atom, optionally substituted 7 to 11 carbon atoms aralkyl group, optionally substituted aralkoxy group having 7 to 11 carbon atoms, aryl group having optionally substituted carbon atoms of 6 to 12, thiol group, alkylthio group having 1 to 6 carbon atoms, carbon an alkoxyalkylthio group having 2 to 9 carbon atoms, a haloalkylthio group having 1 to 6 carbon atoms, a cycloalkylthio group having 3 to 8 carbon atoms, or an optionally substituted arylthio group having 6 to 10 carbon atoms ,
In addition, R ⁷ and R ⁸ may form an optionally substituted aliphatic ring together with the carbon atom to which they are attached, and c is an integer of 1-3. ] may form a ring as shown in
R ²⁰⁰ is the oligomer chain group A, the alkenyl group having 10 to 30 carbon atoms, a group having an alkenyl group having 10 to 30 carbon atoms at its end, a hydrogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, carbon haloalkyl group having 1 to 6 carbon atoms, cycloalkyl group having 3 to 8 carbon atoms, alkoxy group having 1 to 6 carbon atoms, amino group, substituted amino group, optionally substituted heterocyclic group, cyano group, nitro group, formyl group, hydroxycarbonyl group, alkylcarbonyl group having 2 to 7 carbon atoms, alkoxycarbonyl group having 2 to 7 carbon atoms, halogen atom, optionally substituted aralkyl group having 7 to 11 carbon atoms, substitution optionally substituted aralkoxy groups having 7 to 11 carbon atoms, aryl groups having 6 to 12 carbon atoms which may have substituents, thiol groups, alkylthio groups having 1 to 6 carbon atoms, and 2 to 9 carbon atoms. an alkoxyalkylthio group, a haloalkylthio group having 1 to 6 carbon atoms, a cycloalkylthio group having 3 to 8 carbon atoms, or an arylthio group having 6 to 10 carbon atoms which may have a substituent,
R ³⁰⁰ and R ⁴⁰⁰ each independently represent the oligomer chain group A, the alkenyl group having 10 to 30 carbon atoms, a group having an alkenyl group having 10 to 30 carbon atoms at its end, a hydroxyl group, or 1 to 6 carbon atoms. Alkyl groups of 1 to 6 haloalkyl groups, cycloalkyl groups of 3 to 8 carbon atoms, alkoxy groups of 1 to 6 carbon atoms, amino groups, substituted amino groups, optionally substituted heterocyclic groups , a cyano group, a halogen atom, an alkylthio group having 1 to 6 carbon atoms, or an arylthio group having 6 to 10 carbon atoms which may have a substituent,
a' is an integer of 0 to 5, and when a' is 2 or more, R ³⁰⁰ may be the same or different groups; b' is an integer of 0 to 5; When it is 2 or more, R ⁴⁰⁰ may be the same or different groups,
The substituent of the group optionally having a substituent may be the alkenyl group having 10 to 30 carbon atoms, a group having an alkenyl group having 10 to 30 carbon atoms at the end, or the oligomer chain group A. ,
also,
The substituents of the groups optionally having substituents are such that the alkenyl groups having 10 to 30 carbon atoms are 1 to 12 per oligomer chain group A contained in one molecule. It may be an alkenyl group having 10 to 30 carbon atoms or a group having an alkenyl group having 10 to 30 carbon atoms at the end ,
R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰⁰ , R ¹⁰¹ , R ²⁰⁰ , R ³⁰⁰ , R ⁴⁰⁰ , and substitution of the group optionally having the substituent at least one of the groups is the oligomer chain group A;
R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰⁰ , R ¹⁰¹ , R ²⁰⁰ , R ³⁰⁰ , R ⁴⁰⁰ , and substitution of the group optionally having the substituent At least one of the groups is the alkenyl group having 10 to 30 carbon atoms . The oligomer chain group A is represented by the following formulas (5a) to (5d)

{In formulas (5a) to (5d),
R ¹⁰ is a linear or branched alkylene group having 1 to 20 carbon atoms, and when multiple R ¹⁰ are contained in the same molecule, R ¹⁰ may be the same or different. Often,
n refers to the repeating unit of the oligomer chain group A and is an integer of 3 to 200, and the divalent groups of the plurality of repeating units may be the same or different,
L is a divalent linking group, the following formula (6)

(In the formula,
R ¹³ is a divalent group, a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms forming a ring and optionally having a substituent , an optionally substituted arylene group having 6 to 12 carbon atoms forming a ring, or an optionally substituted heterocyclic group having 3 to 12 ring atoms. , R ¹⁴ is a divalent group, a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms forming a ring and optionally having a substituent or an arylene group optionally having substituents having 6 to 12 carbon atoms forming a ring,
R ¹⁵ is a divalent group, a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms forming a ring and optionally having a substituent , or an arylene group optionally having substituents having 6 to 12 carbon atoms forming a ring,
X ¹ and X ² are divalent groups, each independently a direct bond, O, S, an amino group, a substituted amino group, a (thio)amide group, or a (thio)ester group,
d is an integer from 0 to 50, e is an integer from 0 to 50, f is an integer from 0 to 50,
When d is 2 or more, multiple R ¹³ may be the same or different,
When e is 2 or more, the divalent groups of the multiple e units may be the same or different,
When f is 2 or more, the divalent groups of the multiple units of f may be the same or different,
The substituent of the group which may have a substituent may be the alkenyl group having 10 to 30 carbon atoms or a group having an alkenyl group having 10 to 30 carbon atoms at its end. ) is a group represented by
Multiple L may be the same or different,
The dashed line represents the bond with the indenonaphthopyran moiety,
t refers to the number of oligomer chain groups A and is an integer from 1 to 10;
when t is 1, R ¹¹ is an alkenyl group having 10 to 30 carbon atoms, a hydrogen atom, or an alkyl group having 1 to 20 carbon atoms;
when t is 2, R ¹¹ is a bond or a divalent organic residue,
when t is 3 to 10, R ¹¹ is an organic residue with the same valence as the number of t;
In the above formula (5d), R ¹² is a linear or branched alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 14 carbon atoms, and multiple R ¹² are contained in the same molecule. , R ¹² may be the same or different from each other. } or a combination of these groups, the photochromic compound according to any one of claims 1 to 3. The linking group L that binds to the indenonaphthopyran moiety is represented by the following formula

5. The photochromic compound according to claim 4, which is a group selected from (in the formula, the dashed line represents binding to the indenonaphthopyran moiety). R ⁵ and R ⁶ together are an aliphatic ring having 3 to 20 carbon atoms together with the carbon atom at position 13 of the indenonaphthopyran moiety to which they are bonded; a condensed polycyclic ring in which an aromatic ring or aromatic heterocyclic ring is condensed, a heterocyclic ring having 3 to 20 ring member atoms, or a condensed polycyclic ring in which an aromatic ring or aromatic heterocyclic ring is condensed to the above heterocyclic ring with the proviso that these rings may have substituents,
Any one of claims 2 to 5, wherein the substituent may be the oligomer chain group A, the alkenyl group having 10 to 30 carbon atoms, or a group having an alkenyl group having 10 to 30 carbon atoms at its end. A photochromic compound according to the above paragraph . having a group forming an aliphatic hydrocarbon ring together with the carbon atom at the 13-position of the indenonaphthopyran moiety, wherein the group forming the aliphatic hydrocarbon ring is
A ring selected from a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cycloundecane ring, a cyclododecane ring, and a spirodicyclohexane ring,
The group forming the aliphatic hydrocarbon 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 photochromic compound according to any one of claims 1 to 6, wherein the group forming the aliphatic hydrocarbon ring is a group to which a cycloalkyl group having 5 to 7 carbon atoms may be condensed. The alkenyl group having 10 to 30 carbon atoms or the group having the alkenyl group having 10 to 30 carbon atoms at its end and the oligomer chain group A are present at different substitution positions of the indenonaphthopyran moiety, respectively. Item 8. The photochromic compound according to any one of Items 1 to 7. A photochromic curable composition comprising the photochromic compound according to any one of claims 1 to 8 and a polymerizable compound. A photochromic optical article obtained by polymerizing the photochromic curable composition according to claim 9 . A polymer molded body in which the photochromic compound according to any one of claims 1 to 8 is dispersed. An optical article coated with a polymer film in which the photochromic compound according to any one of claims 1 to 8 is dispersed.