JP2005187420A - Chromene compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new photochromic compound coloring to neutral color without carrying out tone adjustment by using other photochromic compound, having low initial coloring, high coloring sensitivity, fast discoloration rate and good photochromic endurance when used in order to impart a photochromic property e.g. to a plastic lens for glasses. <P>SOLUTION: The chromene compound has an indeno(2,1-f)naphtho(1,2-b)pyran structure as a basic skeleton like a compound represented by formula 1 and has a specific organic group such as a methyl group, an ethyl group, a cyclobutyl group, a cyclopentyl group, a phenyl group, naphthyl group, a methoxyphenyl group, a dimethoxyphenyl group, a fluorine atom, a carboxyl group or an acetyl group on a carbon atom at 12-position of the indeno(2,1-f)naphtho(1,2-b)pyran structure. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a novel chromene compound useful as a photochromic compound for photochromic eyeglass lenses.

Photochromism is a reversible action that quickly changes color when a compound is exposed to light containing ultraviolet light, such as sunlight or mercury lamp light, and returns to its original color when the light is turned off and left in the dark. . A compound having this property is called a photochromic compound and is used as a material for a photochromic plastic lens.
In photochromic compounds used for such applications, (1) the degree of coloring in the visible light region (hereinafter referred to as initial coloring) before irradiation with ultraviolet rays is low, (2) coloring when irradiated with ultraviolet rays Degree (hereinafter referred to as the color density) is high, (3) the speed from the start of UV irradiation until the color density reaches saturation (hereinafter also referred to as high color sensitivity), (4) The speed from the end of irradiation to the return to the original state (hereinafter referred to as the fading speed) is fast, (5) the repetitive durability of this reversible action is good, and (6) the dispersibility in the host material used is high. In order to increase the viscosity, there is a demand for the property of being dissolved at a high concentration in the monomer composition that becomes the host material after curing.
As a photochromic compound that can satisfy such requirements, a chromene compound having an indeno (2,1-f) naphtho (1,2-b) pyran structure as a basic skeleton is known (see Patent Documents 1 and 2). ).

On the other hand, in photochromic plastic lenses, it is preferred to develop colors such as gray or brown, and these intermediate colors are developed in several types of photochromic compounds having different color tones, specifically 430 to 530 nm. It is obtained by mixing a yellow to red compound having a maximum absorption at the time and a purple to blue compound having a maximum absorption at the time of color development at 550 to 650 nm.
However, when the color tone is adjusted by such a method, various problems occur due to the difference in the photochromic properties of the mixed compounds. For example, when the durability of a compound that develops yellow color is lower than that of a compound that develops blue color, the color tone will gradually change to a strong blue tone when used over a long period of time. In addition, when the color development sensitivity and fading speed of the yellow compound are lower than those of the blue compound, the color tone in the middle of color development is strong blue, and the color tone in the middle of color fading becomes a color tone with strong yellowness, etc. Will occur.

It is considered that such a problem can be solved by using a compound that has two or more absorption maximums at the time of color development and develops a neutral color with a single compound. To date, compounds as shown in the following formulas (A) to (C) are known as photochromic compounds having an absorption maximum of 2 or more at the time of color development. There is no known photochromic compound that satisfies such requirements.
That is, the following formula (I)

The chromene compound represented by (see Patent Document 3) has a lower absorption at 430 to 530 nm than that at 550 to 650 nm, and does not show an intermediate color as the color tone.

  In addition, the following formula (II)

The chromene compound represented by (see Patent Document 4) has a problem of high initial coloration and low repetition durability.

  In addition, the following formula (III)

Although the chromene compound represented by (see Patent Document 5) develops an intermediate color, it has a problem that the fading speed is slow and the repetition durability is still low.

International Publication No. 99/15518 International Publication No. 2001/60811 Pamphlet International Publication No. 96/14596 Pamphlet International Publication No. 2000/35902 Pamphlet International Publication No. 2001/19813 Pamphlet

  Therefore, the present invention shows an intermediate color as the color tone, further improves the photochromic characteristics as compared with the above-mentioned compounds, has less initial coloring, high color development sensitivity, high color fading speed, and little coloration at the time of deterioration. It is an object of the present invention to provide a chromene compound that has a low decrease in color density when used, that is, a chromene compound having excellent photochromic durability, and that can be dissolved in a monomer composition as a base material to be used at a high concentration. And

The present inventors have intensively studied to solve the above problems. As a result, in a chromene compound having an indeno (2,1-f) naphtho (1,2-b) pyran structure as a basic skeleton, which is known to give excellent photochromic properties, indeno (2,1-f) A compound having a specific substituent introduced at the 12-position of the naphtho (1,2-b) pyran structure develops a neutral color without impairing its excellent photochromic properties, and the compound has little initial coloration and a fading rate. The present invention was completed by obtaining the knowledge that it is fast.
That is, the first present invention has the following formula:

(In the formula, the numbers represent the positions of carbon atoms and oxygen atoms.)
A chromene compound having an indeno (2,1-f) naphtho (1,2-b) pyran structure as a basic skeleton, the indeno (2,1-f) naphtho (1,2-b) pyran The chromene compound characterized by having one group selected from the groups belonging to any one of the following groups (I) and (II) at the 12th position of the structure.

Group (I): (i-1) hydroxy group; (i-2) substituted or unsubstituted alkyl group; (i-3) substituted or unsubstituted cycloalkyl group; (i-4) substituted or unsubstituted An aryl group; and (i-5) a halogen atom group (II): (ii-1) a group represented by C (O) W (W is a hydroxy group, an alkyl group having 1 to 6 carbon atoms, a carbon number 1-6 alkoxy group, phenyl group, mono-substituted phenyl group, amino group, monoalkylamino group having 1 to 6 carbon atoms as a substituent, or 2 alkyl groups having 1 to 6 carbon atoms are substituted (Ii-2) a group represented by —OR ⁸ (wherein R ⁸ is an alkyl group having 1 to 6 carbon atoms and 1 phenyl group having one phenyl group as a substituent). An alkyl group having 3 to 3 carbon atoms (not including the carbon number of the phenyl group). An alkyl group having 1 to 3 carbon atoms (not including the carbon number of the substituent in the carbon number) having a monoalkyl-substituted phenyl group to which one alkyl group is bonded, and an alkoxy having 1 to 6 carbon atoms An alkyl group having 1 to 3 carbon atoms (not including the carbon number of the substituent in the carbon number) having a monoalkoxy-substituted phenyl group to which one group is bonded as a substituent, and 1 to 6 carbon atoms as a substituent An alkyl group having 2 to 4 carbon atoms (not including the carbon number of the substituent in the carbon number), a cycloalkyl group having 3 to 7 carbon atoms, and an alkyl group having 1 to 4 carbon atoms as a substituent A monoalkyl-substituted cycloalkyl group having 3 to 7 carbon atoms, a chloroalkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, an allyl group, -CH (R ⁹⁾ a group represented by X { And, ^{R 9} is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X is -CN, a group represented by -CF ₃ or -COOR ^{10 (where, R 10} is hydrogen or 1 to 3 carbon atoms An alkyl group.). And a group represented by (ii-3) -C (O) Y (where Y is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an unsubstituted aryl group) A mono- or di-substituted aryl group, a phenoxy group, a mono- or dialkyl-substituted phenoxy group having 1 or 2 alkyl groups having 1 to 6 carbon atoms as a substituent, and 1 or 2 an alkoxy group having 1 to 6 carbon atoms as a substituent Mono- or dialkoxy-substituted phenoxy group, amino group, mono- or dialkylamino group having 1 or 2 alkyl groups having 1 to 6 carbon atoms as a substituent, phenylamino group, 1 alkyl group having 1 to 6 carbon atoms or A mono- or dialkoxy-substituted group having one or two substituted amino groups or C1-C6 alkoxy groups having a mono- or dialkyl-substituted phenyl group as a substituent. A substituted amino group having an alkenyl group as a substituent.)
Moreover, 2nd this invention is a photochromic composition containing the chromene compound of the said invention. Furthermore, the third aspect of the present invention is a photochromic optical article having, as a constituent member, a polymer molded body in which the chromene compound of the present invention is dispersed, and the fourth aspect of the present invention includes all or one of at least one surface. An optical article having, as a constituent member, an optical substrate coated with a polymer film in which a chromene compound of the present invention is dispersed.

  The chromene compound of the present invention exhibits an intermediate color tone, low initial coloration, high color development sensitivity, high color density, and fast discoloration rate even when dispersed in a solution or a polymer solid matrix. In addition to exhibiting excellent photochromic properties, it also exhibits excellent durability. Therefore, for example, when a photochromic lens is made using the chromene compound of the present invention, it quickly darkens when it goes outdoors, and it becomes dark and neutral, and when it returns from the outdoors to the room, it fades quickly to the original color tone. By returning, a highly durable photochromic lens that can be used for a long time can be obtained. Further, the photochromic lens has a feature that no color shift occurs even when the color is emitted or faded or after long-term use.

  The chromene compound of the present invention has the above-described indeno (2,1-f) naphtho (1,2-b) pyran structure as a basic skeleton, and the indeno (2,1-f) naphtho (1,2-b) It has a specific organic group at the 12th carbon atom of the pyran structure. A chromene compound having an indeno (2,1-f) naphtho (1,2-b) pyran structure as a basic skeleton is known to exhibit excellent photochromic properties, but has a specific substituent at the 12-position. By having it, while maintaining its excellent photochromic characteristics, it is possible to develop a dark intermediate color with a single compound, reduce initial coloration, and increase the fading speed.

  In the chromene compound of the present invention, the substituent bonded to the 12-position carbon atom of the indeno (2,1-f) naphtho (1,2-b) pyran structure is a group belonging to the following group (I) and the following group (II): One group selected from the group consisting of groups belonging to.

[Group (I)]
(i-1) a hydroxy group; (i-2) a substituted or unsubstituted alkyl group; (i-4) a substituted or unsubstituted cycloalkyl group; (i-4) a substituted or unsubstituted aryl group; i-5) A halogen atom.

[Group (II)]
(ii-1) a group represented by -C (O) W (W is a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a mono-substituted phenyl group, amino A monoalkylamino group having one alkyl group having 1 to 6 carbon atoms as a substituent or a dialkylamino group having two alkyl groups having 1 to 6 carbon atoms as a substituent.
(ii-2) a group represented by —OR ^{8 wherein} R ⁸ is an alkyl group having 1 to 6 carbon atoms and 1 to 3 carbon atoms having one phenyl group as a substituent (the carbon number of the phenyl group is A carbon number of 1 to 3 (the number of carbons of the substituent in addition to the number of carbon atoms) having a monoalkyl-substituted phenyl group to which one alkyl group of 1 to 6 carbon atoms is bonded. Is not included), a C1-C3 having a monoalkoxy-substituted phenyl group to which one alkoxy group having 1 to 6 carbon atoms is bonded as a substituent (the carbon number of the substituent is the carbon number) (Not including) an alkyl group having 2 to 4 carbon atoms having a C 1-6 alkoxy group as a substituent (not including the carbon number of the substituent in the carbon number), 3 to 7 carbon atoms A cycloalkyl group, an alkyl group having 1 to 4 carbon atoms as a substituent Constitutes a ring having number, monoalkyl-substituted cycloalkyl group having a carbon number of 3-7, a chloroalkyl group having 1 to 6 carbon atoms, fluoroalkyl group having 1 to 6 carbon atoms, an allyl group, -CH (R ⁹ ) X is a group represented by X (provided that R ⁹ is hydrogen or an alkyl group having 1 to 3 carbon atoms, and X is a group represented by —CN, —CF ₃ or —COOR ¹⁰ (provided that R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.) }〕;as well as
(ii-3) a group represented by -C (O) Y (wherein Y is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an unsubstituted aryl group, mono- or di-) A substituted aryl group, a phenoxy group, a mono- or dialkyl-substituted phenoxy group having 1 or 2 alkyl groups having 1 to 6 carbon atoms as a substituent, and a mono or di having 1 or 2 alkoxy groups having 1 to 6 carbon atoms as a substituent An alkoxy-substituted phenoxy group, an amino group, a mono- or dialkylamino group having 1 or 2 alkyl groups having 1 to 6 carbon atoms as a substituent, a phenylamino group, or one or two alkyl groups having 1 to 6 carbon atoms are bonded. A mono- or dialkoxy-substituted phenyl group to which one or two substituted amino groups or C1-C6 alkoxy groups having a mono- or dialkyl-substituted phenyl group as a substituent are bonded. A substituted amino group as a substituent.

  As for the groups belonging to the groups (I) and (II), the following groups may be mentioned as examples of suitable groups for groups whose structures are not uniquely determined.

  That is, for the group (I), among the substituted or unsubstituted alkyl groups in (i-2), methyl, ethyl, n-propyl, isopropyl, n-butyl, sec- Examples thereof include a butyl group and a t-butyl group. Preferred examples of the substituted or unsubstituted cycloalkyl group of (i-3) include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Moreover, as a suitable thing among the substituted or unsubstituted aryl groups of (i-4), a phenyl group, a naphthyl group, a methoxyphenyl group, a dimethoxyphenyl group etc. can be mentioned. Further, among the halogen atoms of (i-5), preferred are a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Moreover, about group (II), a carboxyl group, an acetyl group, an ethylcarbonyl group etc. can be mentioned as a suitable thing among the groups shown by -C (O) W of (ii-1). Further, preferred examples of the group represented by —OR ⁸ in (ii-2) include a methyl ether group, an ethyl ether group, a propyl ether group, and a phenyl methyl ether group. Further, preferred examples of the group represented by -C (O) Y in (ii-3) include an aldehyde group, a carboxyl group, and a phenylcarbonyl group.

  Among the chromene compounds of the present invention, from the viewpoints that the color tone at the time of color development shows an intermediate color, the color development sensitivity is high, the initial coloration is low, the color fading speed is fast, and the photochromic durability is good. The chromene compound shown by these is suitable.

R ¹ and R ² in the above formula (1) are each independently one group selected from the group consisting of a hydrogen atom, a group belonging to the group (I) and a group belonging to the group (II). Or a ring in which R ¹ and R ² are bonded to each other to form a spiro bond at position 13 of the indeno (2,1-f) naphtho (1,2-b) pyran structure and belong to the following group (III): It is a group forming one kind of ring.

[Group (III)]
(iii-1) a substituted or unsubstituted aliphatic ring having 3 to 20 carbon atoms constituting the ring;
(iii-2) a condensed polycyclic ring in which a substituted or unsubstituted aromatic ring or a substituted or unsubstituted aromatic heterocyclic ring is condensed to the aliphatic ring;
(iii-3) a substituted or unsubstituted heterocycle having 3 to 20 atoms constituting the ring; and
(iii-4) A condensed polycyclic ring in which a substituted or unsubstituted aromatic ring or a substituted or unsubstituted aromatic heterocyclic ring is condensed to the above heterocyclic ring.

  Illustrative of suitable groups, among the substituted or unsubstituted aliphatic rings of (iii-1), preferred are cyclopentane ring, cyclohexane ring, cyclooctane ring, cycloheptane ring, norbornane ring, bicyclononane ring, And adamantane ring. Moreover, a phenanthrene ring etc. can be mentioned as a suitable thing among the condensed polycycles of (iii-2). Further, preferred examples of the substituted or unsubstituted heterocyclic ring of (iii-3) include a thiophene ring, a furan ring, a pyridine ring and the like. In addition, preferred examples of the condensed polycycle of (iii-4) include a phenylfuran ring and a biphenylthiophene ring.

R ¹ and R ² are preferably (iii-1) or (iii-2) from the viewpoint that the fading speed is particularly high among these groups. Further, from the viewpoint of reducing initial coloring, (iii-1) is preferred. Specific examples of particularly preferable groups as R ¹ and R ² include a group that gives a monocycle by bonding to each other, a group that gives a cyclohexane ring, a cyclooctane ring, a cycloheptane ring, etc., and a group that gives a bicyclo ring, such as norbornane Examples of the group that gives a ring, a bicyclononane ring, and the group that gives a tricyclo ring include a group that gives an adamantane ring. In addition, when the aliphatic hydrocarbon ring is a spiro ring, any carbon of the aliphatic hydrocarbon ring may be a spiro carbon. Examples of the most preferable R ¹ and R ² in the form of a ring formed by combining them include the following. In the formula, 13 represents a carbon atom at the 13th position of the indeno (2,1-f) naphtho (1,2-b) pyran structure.

R ³ and R ⁴ in the formula (1) are each independently a group represented by the following formula (2), a group represented by the following formula (3), a substituted or unsubstituted aryl group, a substituted or unsubstituted group Or an aryl group, or R ³ and R ⁴ are bonded to each other to form an aliphatic hydrocarbon ring or an aromatic hydrocarbon ring.

R ¹¹ in the formula (2) is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.

  The substituted or unsubstituted aryl group is not particularly limited. However, if the group becomes too bulky, it becomes difficult to develop color, and therefore a non-substituted group having 6 to 10 carbon atoms such as a phenyl group or a naphthyl group. A substituted aryl group; or 1 to 7, particularly 1 to 4, hydrogen atoms of the unsubstituted aryl group are (s1) alkyl groups, (s2) alkoxy groups, (s3) aralkoxy groups, (s4) substituted An amino group, (s5) aryl group, (s6) a substituted or unsubstituted heterocyclic group having a nitrogen atom as a heteroatom and bonded to the aryl group at the nitrogen atom, or (s7) aromatic carbonization on the heterocyclic group From the group consisting of a condensed heterocyclic group condensed with a hydrogen ring or an aromatic heterocyclic ring, (s8) halogen atom, (s9) cyano group, (s10) nitro group, (s11) hydroxy group and (s12) trifluoromethyl group A group substituted with at least one selected substituent. It is preferred that.

  The alkyl group (s1) is not particularly limited, but an alkyl group having 1 to 4 carbon atoms is preferable. Examples of suitable alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl and the like. The alkoxy group (s2) is not particularly limited, but an alkoxy group having 1 to 5 carbon atoms is preferable. Specific examples of suitable alkoxy groups include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, t-butoxy group and the like. The aralkoxy group (s3) is not particularly limited, but an aralkoxy group having 6 to 10 carbon atoms is preferable. Specific examples of suitable aralkoxy groups include phenoxy groups and naphthoxy groups. The substituted amino group of (s4) is not particularly limited, but an alkylamino group, a dialkylamino group, an arylamino group, or a diarylamino group substituted with an alkyl group or an aryl group is preferable. Specific examples of suitable substituted amino groups include methylamino group, ethylamino group, phenylamino group, dimethylamino group, diethylamino group, and diphenylamino group. The aryl group of (s5) is not particularly limited, but an aryl group having 6 to 10 carbon atoms is preferable. Examples of suitable aryl groups include a phenyl group and a naphthyl group. A substituted or unsubstituted heterocyclic group having the nitrogen atom of (s6) and (s7) as a heteroatom and bonded to the aryl group at the nitrogen atom, and an aromatic hydrocarbon ring or aromatic heterocyclic ring to the heterocyclic group Specific examples of preferred condensed heterocyclic groups in which are condensed include morpholino group, piperidino group, pyrrolidinyl group, piperazino group, N-methylpiperazino group, indolinyl group and the like. Examples of the halogen atom in (s8) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Specific examples of suitable groups among the substituted aryl groups include methylphenyl group, ethylphenyl group, methoxyphenyl group, ethoxyphenyl group, dimethoxyphenyl group, trimethoxyphenyl group, morpholinophenyl group, methoxybiphenyl group, dimethyl group. An aminophenyl group etc. can be mentioned.

The substituted or unsubstituted heteroaryl group in the case where R ¹¹ is a substituted or unsubstituted heteroaryl group is not particularly limited. However, if the group becomes too bulky, color development becomes difficult. An unsubstituted heteroaryl group having 4 to 12 carbon atoms such as thienyl group, furyl group, pyrrolinyl group, pyridyl group, benzothienyl group, benzofuranyl group, benzopyrrolinyl group or the like, or 1 of the hydrogen atoms of the unsubstituted heteroaryl group ~ 9, especially 1-4 are alkyl groups, alkoxy groups, aralkoxy groups, substituted amino groups, aryl groups, substituted or unsubstituted with a nitrogen atom as a heteroatom and bonded to the heteroaryl group at the nitrogen atom Or a condensed heterocyclic group obtained by condensing an aromatic hydrocarbon ring or an aromatic heterocyclic ring to the heterocyclic group, halogen A group substituted with at least one substituent selected from the group consisting of an atom, a cyano group, a nitro group, a hydroxy group and a trifluoromethyl group is preferred. In addition, the said substituent in a substituted heteroaryl group is the same as the substituent in a substituent aryl group. Specific examples of suitable groups among the substituted heteroaryl groups include methylthienyl group, methoxythienyl group, dimethylthienyl group, dimethoxythienyl group, dimethylaminothienyl group, biphenylaminothienyl group, methylfuryl group, methoxyfuryl group. , Dimethylfuryl group, dimethoxyfuryl group, dimethylaminofuryl group, biphenylaminofuryl group, methylpyrrolinyl group, methoxypyrrolinyl group, dimethylpyrrolinyl group, dimethoxypyrrolinyl group, dimethylaminopyrrolinyl group, biphenylaminopyrrolinyl group , Methylpyridyl group, methoxypyridyl group, dimethylpyridyl group, dimethoxypyridyl group, dimethylaminopyridyl group, biphenylaminopyridyl group, methylbenzothienyl group, methoxybenzothienyl group, dimethylbenzothienyl group Dimethoxy benzothienyl group, dimethylamino benzofuranyl group include biphenyl aminobenzoyl pylori sulfonyl group.

R ¹² in the formula is a hydrogen atom, an alkyl group, or a halogen atom. Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Moreover, n is an integer of 1 to 3, but n is preferably 1 from the viewpoint of obtaining raw materials.

  Examples of suitable groups among the groups represented by the formula (2) include phenyl-ethylenyl group, (4- (N, N-dimethylamino) phenyl) -ethenyl group, (4- (N, N-diethylamino) Phenyl) -ethenyl group, (4-morpholinophenyl) -ethenyl group, (4-piperidinophenyl) -ethenyl group, (4-eurolidinophenyl) -ethenyl group, (4-methoxyphenyl) -ethenyl group, (4-methylphenyl) -ethenyl group, (2- (N, N-dimethylamino) phenyl) -ethenyl group, (2-methoxyphenyl) -ethenyl group, phenyl-1-methylethenyl group, (4- (N, N-dimethylamino) phenyl) -1-methylethenyl group, (4-methoxyphenyl) -1-methylethenyl group, phenyl-1-fluoroethenyl group, (4- (N, -Dimethylamino) phenyl) -1-fluoroethenyl group, 2-thienyl-ethenyl group, 2-furyl-ethenyl group, 2- (N-methyl) pyrrolinyl-ethenyl group, 2-benzothienyl-ethenyl group, 2- Examples thereof include a benzofuranyl-ethenyl group and a 2- (N-methyl) indolyl-ethenyl group.

In the formula (3), R ¹³ is the same substituted or unsubstituted aryl group as the R ¹¹ , or a substituted or unsubstituted heteroaryl group. M is an integer of 1 to 3, and m is preferably 1 from the viewpoint of easy availability of raw materials. Examples of suitable groups among the groups represented by formula (3) include phenyl-ethylinyl group, (4- (N, N-dimethylamino) phenyl) -ethynyl group, (4- (N, N-diethylamino) Phenyl) -ethynyl group, (4-morpholinophenyl) -ethynyl group, (4-piperidinophenyl) -ethynyl group, (4-eurolidinophenyl) -ethynyl group, (4-methoxyphenyl) -ethynyl group, (4-methylphenyl) -ethynyl group, (2- (N, N-dimethylamino) phenyl) -ethynyl group, (2-methoxyphenyl) -ethynyl group, 2-thienyl-ethynyl group, 2-furyl-ethynyl group 2- (N-methyl) pyrrolinyl-ethynyl group, 2-benzothienyl-ethyl group, 2-benzofuranyl-ethynyl group, 2- (N-methyl) indolyl-ethynyl And the like can be given.

As the substituted or unsubstituted aryl group or the substituted or unsubstituted heteroaryl group as R ³ and R ⁴ , the same groups as those in the group R ¹¹ are applied.

Further, the alkyl group as R ³ and R ⁴ has the same meaning as the unsubstituted alkyl group of (i-3) described as R ¹ described above.

In addition, when R ³ and R ⁴ together form an aliphatic hydrocarbon ring, the aliphatic hydrocarbon ring is not particularly limited, but specific examples of suitable rings include An adamantane ring, a bicyclononane ring, a norbornane ring, and the like can be given. The aromatic hydrocarbon ring in the case where R ³ and R ⁴ together form an aromatic hydrocarbon ring is not particularly limited, but preferred rings include a fluorene ring and the like. Can be mentioned.

At least one of R ³ and R ⁴ is preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a group having these groups. Furthermore, at least one of R ³ and R ⁴ is particularly preferably any of the groups shown in the following (a) to (i).

(a) a substituted aryl group or substituted heteroaryl group having a substituted amino group as a substituent;
(b) a substituted aryl group or a substituted heteroaryl group having a nitrogen atom as a heteroatom and a substituted or unsubstituted heterocyclic group to which the nitrogen atom and an aryl group or heteroaryl group are bonded as a substituent;
(c) a substituted aryl group or a substituted heteroaryl group having, as a substituent, a condensed heterocyclic group obtained by condensing an aromatic hydrocarbon ring or an aromatic heterocyclic ring to the substituted or unsubstituted heterocyclic group in (b);
(d) a group represented by the formula (2), wherein R ¹¹ is a substituted aryl group or substituted heteroaryl group having a substituted amino group as a substituent;
(e) R ¹¹ is a substituted aryl group or a substituted heteroaryl group having a nitrogen atom as a hetero atom and a substituted or unsubstituted heterocyclic group to which the nitrogen atom and an aryl group or heteroaryl group are bonded as a substituent. A group of formula (2);
(f) a substituted aryl group or a substituted heteroaryl group in which R ¹¹ has as a substituent a condensed heterocyclic group obtained by condensing an aromatic hydrocarbon ring or an aromatic heterocyclic ring to the substituted or unsubstituted heterocyclic group in the above (e) A group represented by formula (2):
(g) a group represented by the formula (3), wherein R ¹³ is a substituted aryl group or substituted heteroaryl group having a substituted amino group as a substituent;
(h) a substituted aryl group or a substituted heteroaryl group in which R ¹³ has a nitrogen atom as a hetero atom and a substituted or unsubstituted heterocyclic group to which the nitrogen atom and an aryl group or heteroaryl group are bonded as a substituent; A group of formula (3); or
(i) a substituted aryl group or a substituted heteroaryl group in which R ¹³ has a condensed heterocyclic group obtained by condensing an aromatic hydrocarbon ring or an aromatic heterocyclic ring to the substituted or unsubstituted heterocyclic group in the above (h) A group represented by formula (3):

  In the substituted aryl groups in the above (a) to (c), the substitution position of the substituent is not particularly limited, and the total number is not particularly limited, but the substitution position is 3 when the aryl group is a phenyl group. It is preferably substituted at the 4- or 4-position, and the number is preferably 1. Specific examples of suitable substituted aryl groups include 4- (N, N-dimethylamino) phenyl group, 4- (N, N-diethylamino) phenyl group, 4- (N, N-diphenyl). Amino) phenyl group, 4-morpholinophenyl group, 4-piperidinophenyl group, 3- (N, N dimethylamino) phenyl group, 4- (2,6-dimethylpiperidino) phenyl group and the like. it can.

  Further, in the substituted heteroaryl groups in the above (a) to (c), the position at which the substituent is substituted is not particularly limited, and the total number is not particularly limited, but the number is preferably 1. Specific examples of suitable substituted heteroaryl groups include 4- (N, N-dimethylamino) thienyl group, 4- (N, N-diethylamino) furyl group, 4- (N, N-diphenylamino). ) Thienyl group, 4-morpholinopyrrolinyl group, 6-piperidinobenzothienyl group, 6- (N, N dimethylamino) benzofuranyl group and the like.

In the groups represented by the formula (2) in the above (d) to (f), R ¹¹ in the formula (2) has the same meaning as the substituted aryl group or substituted heteroaryl group in the above (a) to (c). It is. In the groups represented by the formula (3) of the above (g) to (i), R ¹³ in the formula (3) has the same meaning as the substituted aryl group or substituted heteroaryl group of the above (a) to (c). is there.

R ⁵ and R ⁶ in the formula (1) are each independently an alkyl group, an alkoxy group, an aralkoxy group, an amino group, a substituted amino group, or a nitrogen atom as a hetero atom, and the nitrogen atom is bonded to the indene ring. A substituted or unsubstituted heterocyclic group, or a condensed heterocyclic group obtained by condensing an aromatic hydrocarbon ring or an aromatic heterocyclic ring to the heterocyclic group, a halogen atom, a cyano group, an aralkyl group, or a substituted or unsubstituted aryl group It is. Among these, an alkyl group, an alkoxy group, an aralkoxy group, a substituted amino group, a substituted or unsubstituted heterocyclic group having a nitrogen atom as a heteroatom and bonded to the benzo ring at the nitrogen atom, and aromatic to the heterocyclic group The condensed heterocyclic group condensed with a hydrocarbon ring or an aromatic heterocyclic ring and a halogen atom are the alkyl group of (s1), the alkoxy group of (s2), the aralkoxy group of (s3), the substituted amino group of (s4), A substituted or unsubstituted heterocyclic group having the nitrogen atom of (s6) as a hetero atom and bonded to the aryl group at the nitrogen atom, and the heterocyclic group of (s7) (the heterocyclic group of (s6)) is aromatic Are the same as the condensed heterocyclic group condensed with the aromatic hydrocarbon ring or the aromatic heterocyclic ring and the (s8) halogen atom. The aralkyl group is not particularly limited, but an aralkyl group having 7 to 11 carbon atoms is preferable. Examples of suitable aralkyl groups include benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl group and the like. The substituted or unsubstituted aryl group has the same meaning as the substituted or unsubstituted aryl group in R ¹⁵ .

Further, the p indicating the number of substituents for ^{R 5} is an integer of 0 to 3. The position to which R ⁵ is bonded is not particularly limited, but it is preferably substituted at the 6-position and / or 8-position, and the total number is not particularly limited, but is preferably 2 or less. In addition, when p is 2 or 3, each R ⁵ may be different from each other.

As a substituent when R ⁵ is substituted at the 6-position and / or 8-position, among the above-mentioned substituents, a moderate electron-donating group having a Hammett number of −0.49 to −0.20 or a Hammett number A weak electron donating group having −0.19 to −0.01 is preferable because the double peak property can be enhanced while suppressing initial coloring. The Hammett number (σ) is defined based on the Hammett's rule, which uses the dissociation constant Ka of m- and p-substituted benzoic acids as a reference and quantifies the electronic effects of substituents bonded to the π-electron system.

  Specific examples of intermediate electron donating groups having a Hammett number of −0.49 to −0.20 include a methoxy group (σ = −0.28), an ethoxy group (σ = −0.21), and a propoxy group. Alkoxy groups such as (σ = −0.26), p-alkylaminophenyl groups such as p-dimethylaminophenyl group (σ = −0.22), p-diethylaminophenyl group (σ = −0.22), etc. Is mentioned.

  Specific examples of weak electron donating groups having a Hammett number of −0.19 to −0.01 include p-methoxyphenyl group (σ = −0.04), o, p-dimethoxyphenyl group (σ = −0). Aryl groups such as alkoxyphenyl groups such as .08), phenyl groups (σ = −0.01), 1-naphthyl groups (σ = −0.08), 2-naphthyl groups (σ = −0.02), p-nitrogen-containing heterocyclic aryl group such as p-morpholinophenyl group (σ = −0.16), heteroaryl group such as thienyl group (σ = −0.1), methyl group (σ = −0.14) ), An alkyl group such as an ethyl (σ = −0.13) group and a propyl group (σ = −0.12), and a cycloalkyl group such as a cyclohexyl group (σ = −0.16).

Also, the q indicating the number substitution ^{R 6} is an integer of 0-4. The position at which R ⁶ is bonded is not particularly limited, and the total number thereof is not particularly limited, but is preferably 2 or less. In addition, when q is 2 or 3, each R ⁶ may be different from each other.

  In the present invention, a chromene compound represented by the following formula (4) is particularly suitable from the viewpoint of good photochromic properties and easy color development in intermediate colors.

{Wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ¹⁴ , R ¹⁵ and q have the same meanings as those in formula (1), and R ¹⁴ represents the formula ( 1) an electron donating group having a Hammett number of −0.49 to −0.01 among the groups represented by R ⁵ in p), p is an integer of 0 to 2, and R ¹⁵ is substituted or non-substituted. Substituted aryl group substituted or substituted or unsubstituted heteroaryl, represented by the following formula (5)

Are each an aliphatic hydrocarbon ring group that may have at least one substituent selected from an alkyl group, an alkoxy group, an amino group, and a substituted amino group. }
It is a chromene compound shown by.

As the substituted or unsubstituted aryl group or substituted or unsubstituted heteroaryl group of R ¹⁵ in the formula (4), the same groups as those in the group R ¹¹ are applied.

In the present invention, further preferred chromene compounds of the present invention are those in which R ⁴ represents “an aryl group or heteroaryl group having an amino group as a substituent” or “a nitrogen atom as a hetero atom and an aryl group or hetero An aryl group or heteroaryl group having a substituted or unsubstituted heterocyclic group bonded to an aryl group as a substituent "or" substitution having a nitrogen atom as a heteroatom and bonded to the aryl group or heteroaryl group at the nitrogen atom Or a substituted aryl group or substituted heteroaryl group having a condensed heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is fused to an unsubstituted heterocyclic group as a substituent ” A compound.

  Specific examples of the particularly preferred chromene compound in the present invention include the following compounds.

  The chromene compound of the present invention generally exists as a colorless, pale yellow, pale green solid or viscous liquid at ordinary temperature and pressure, and can be confirmed by the following means (a) to (c).

(B) By measuring a proton nuclear magnetic resonance spectrum ( ¹ H-NMR), a peak based on an aromatic proton and an alkene proton in the vicinity of δ 5.0 to 9.0 ppm, and in the vicinity of δ 1.0 to 4.0 ppm. Peaks based on protons of alkyl groups and alkylene groups appear. Moreover, the number of protons of each linking group can be known by relatively comparing the respective spectrum intensities.

  (B) The composition of the corresponding product can be determined by elemental analysis.

(C) ¹³ by measuring the C- nuclear magnetic resonance spectrum ⁽¹³ C-NMR), the peak based on the carbons of an aromatic hydrocarbon group near Deruta110～160ppm, based on the carbon of an alkene and alkyne near δ80~140ppm A peak based on carbon of the alkyl group and the alkylene group appears in the vicinity of δ20 to 80 ppm.

  The method for producing the chromene compound of the present invention is not particularly limited and may be obtained by any synthesis method. For example, the chromene compound represented by the formula (1) can be preferably produced by the following method.

  That is, the following formula (6)

{R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ , R ¹⁵ , p and q in the formula are as defined in the general formula (1). }
And a hydroxy-fluorenone derivative represented by the following formula (7):

{R ³ and R ⁴ in the formula are as defined in the general formula (1). }
Can be suitably produced by a method of reacting with a propargyl alcohol derivative represented by the above in the presence of an acid catalyst.

  The method for synthesizing the hydroxy-fluorene derivative represented by the formula (6) and the propargyl alcohol derivative represented by the formula (7) is not particularly limited. The hydroxy-fluorene derivative represented by the formula (6) is, for example, the following formula (8)

{R ⁵ , R ⁶ , R ⁷ , R ¹⁵ , p and q in the formula are as defined in the general formula (1). }
Is converted to an amine by a method such as Curtius rearrangement, Hofmann rearrangement or Lossen rearrangement, and then converted from a diazonium salt to bromide by a Sandmeyer reaction or the like, and the obtained bromide is converted to magnesium or lithium. To prepare an organometallic reagent, which is represented by the following formula (9)

{Wherein, R ¹ and R ² have the same meanings as in the general formula (1). }
And the following formula (10):

{R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ , R ⁷ , p and q in the formula are as defined in the general formula (1). }
Can be synthesized by reacting the alcohol body under neutral to acidic conditions at 10 to 120 ° C. for 10 minutes to 2 hours to spirodify the alcohol.

  The reaction ratio between the organometallic reagent prepared in the above reaction and the ketone represented by the formula (10) is adopted from a wide range, but generally from the range of 1:10 to 10: 1 (molar ratio). Selected. The reaction temperature is usually preferably from −10 to 70 ° C., and as the solvent, an aprotic organic solvent such as diethyl ether, tetrahydrofuran, benzene, toluene or the like is used.

  Thereafter, the obtained alcohol is spirolated under neutral to acidic conditions. Acetic acid, hydrochloric acid, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, acidic alumina and the like as an acid catalyst at this time are 0.1 to 10 parts by weight with respect to 100 parts by weight of the alcohol body represented by the formula (10). It is preferable to use within a range. The reaction temperature is preferably 10 to 120 ° C., and as the solvent, for example, acetic acid, tetrahydrofuran, benzene, toluene and the like are used.

  The propargyl alcohol derivative represented by the general formula (7) can be synthesized by, for example, reacting a ketone derivative corresponding to the general formula (7) with a metal acetylene compound such as lithium acetylide.

  The reaction of the compound represented by the general formula (6) and the compound represented by the general formula (7) in the presence of an acid catalyst is performed, for example, as follows.

  That is, the reaction ratio of these two compounds is selected from a wide range, but is generally selected from a range of 1:10 to 10: 1 (molar ratio). As the acid catalyst, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, acidic alumina or the like is used, and the sum of the compound represented by the general formula (6) and the compound represented by (7) (reaction substrate) is 100. It is used in the range of 0.1 to 10 parts by weight with respect to parts by weight. The reaction temperature is usually preferably from 0 to 200 ° C., and as the solvent, an aprotic organic solvent such as N-methylpyrrolidone, dimethylformamide, tetrahydrofuran, benzene, toluene or the like is used.

  The method for purifying the product is not particularly limited. For example, the product can be purified by silica gel column purification and recrystallization.

  The chromene compound of the present invention is well soluble in common organic solvents such as toluene, chloroform, and tetrahydrofuran. When the chromene compound represented by the general formula (1) is dissolved in such a solvent, the solution is generally almost colorless and transparent, and quickly develops color when irradiated with sunlight or ultraviolet light, and reversibly and rapidly when light is blocked. It exhibits a good photochromic effect that returns to its original color.

  Moreover, the chromene compound of the present invention exhibits similar photochromic properties even in a polymer solid matrix. Such a polymer solid matrix is not particularly limited as long as the chromene compound of the present invention is uniformly dispersed, and optically preferably, for example, polymethyl acrylate, polyethyl acrylate, polymethyl methacrylate, poly Mention may be made of thermoplastic resins such as ethyl methacrylate, polystyrene, polyacrylonitrile, polyvinyl alcohol, polyacrylamide, poly (2-hydroxyethyl methacrylate), polydimethylsiloxane and polycarbonate.

  Further, ethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A dimethacrylate, 2,2-bis (4-methacryloyloxyethoxyphenyl) propane, 2 , 2-bis (3,5-dibromo-4-methacryloyloxyethoxyphenyl) propane and other polyacrylic acid and polymethacrylate compounds; diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl tartrate, diallyl epoxy succinate, Diallyl fumarate, diallyl chlorendate, diallyl hexaphthalate, diallyl carbonate, allyl diglycol car And polyvalent allyl compounds such as trimethylolpropane triallyl carbonate; 1,2-bis (methacryloylthio) ethane, bis (2-acryloylthioethyl) ether, 1,4-bis (methacryloylthiomethyl) benzene Thioacrylic acid and polyvalent thiomethacrylic acid ester compounds; glycidyl acrylate, glycidyl methacrylate, β-methyl glycidyl methacrylate, bisphenol A-monoglycidyl ether-methacrylate, 4-glycidyloxy methacrylate, 3- (glycidyl-2-oxyethoxy) 2-hydroxypropyl methacrylate, 3- (glycidyloxy-1-isopropyloxy) -2-hydroxypropyl acrylate, 3-glycidyloxy-2-hydroxypropyloxy) Examples include acrylic acid ester compounds such as 2-hydroxypropyl acrylate and methacrylic acid ester compounds; thermosetting resins obtained by polymerizing radical polymerizable polyfunctional monomers such as divinylbenzene.

  These monomers and unsaturated carboxylic acids such as acrylic acid, methacrylic acid and maleic anhydride; acrylic acid such as methyl acrylate, methyl methacrylate, benzyl methacrylate, phenyl methacrylate and 2-hydroxyethyl methacrylate And methacrylic acid ester compounds; fumaric acid ester compounds such as diethyl fumarate and diphenyl fumarate; thioacrylic acid and thiomethacrylic acid ester compounds such as methylthioacrylate, benzylthioacrylate and benzylthiomethacrylate; styrene, chlorostyrene, methylstyrene, Examples thereof include a copolymer with a radically polymerizable monofunctional monomer such as vinyl naphthalene, α-methylstyrene dimer, vinyl compound such as bromostyrene.

  There is no restriction | limiting in particular as a method to disperse | distribute the chromene compound of this invention in the said polymer solid matrix, A general method can be used. For example, the thermoplastic resin and the chromene compound are kneaded in a molten state and dispersed in the resin, or after the chromene compound is dissolved in the polymerizable monomer, a polymerization catalyst is added and polymerization is performed with heat or light. And a method of dispersing in the resin by dyeing a chromene compound on the surface of the thermoplastic resin and the thermosetting resin.

  The chromene compound of the present invention can be widely used as a photochromic material, for example, various kinds of storage materials, copy materials, printing photoreceptors, cathode ray tube storage materials, laser photosensitive materials, and holographic photosensitive materials in place of silver salt photosensitive materials. It can be used as various storage materials. In addition, the photochromic material using the chromene compound of the present invention can also be used as a material such as a photochromic lens material, an optical filter material, a display material, a light meter, and a decoration.

  For example, when used for a photochromic lens, there is no particular limitation as long as it is a method capable of obtaining uniform light control performance, and specifically, a polymer film obtained by uniformly dispersing the photochromic material of the present invention. Or a method in which the chromene compound of the present invention is dispersed in the polymerizable monomer and polymerized by a predetermined method, or this compound is dissolved in, for example, silicone oil. There is a method in which a lens surface is impregnated at 150 to 200 ° C. for 10 to 60 minutes, and the surface is further coated with a curable substance to form a photochromic lens. Furthermore, there is a method of applying the polymer film to the lens surface and coating the surface with a curable substance to form a photochromic lens. Furthermore, a coating agent comprising a polymerization curable composition containing the chromene compound of the present invention may be applied to the surface of the lens substrate to cure the coating film. At this time, the lens substrate may be subjected to surface treatment such as surface treatment with an alkaline solution or plasma treatment in advance, and further (with or without these surface treatments) the substrate and the coating film. Primers can also be applied to improve the adhesion.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

Example 1
The following 5-hydroxy- (7H) benzo (c) fluorene derivatives

1.0 g (0.0020 mol) and the following propargyl alcohol derivative

1.1 g (0.003 mol) was dissolved in 70 ml of toluene, 0.020 g of p-toluenesulfonic acid was further added, and the mixture was stirred for 1 hour with heating under reflux. After the reaction, the solvent was removed and the residue was purified by chromatography on silica gel to obtain 1.1 g of a green powder product. The yield was 83%.

Elemental analysis of the product, C79.76%, H6.92%, N1.70 %, a _О11.59%, C79.78% calculated values of _C 55 _{H 57 NО 5,} H6.94 %, N 1.69% and O 11.59%.

  Further, when a proton nuclear magnetic resonance spectrum was measured, as shown in FIG. 1, a peak of 18H based on methyl and methylene protons of a tetramethylcyclohexane ring in the vicinity of δ1.0 to 3.0 ppm, δ3.0 to 4.0 ppm. A 20H peak based on a morpholino group methylene proton and a methoxy group methyl proton was observed in the vicinity, and a 19H peak based on an aromatic proton and an alkene proton was observed in the vicinity of δ 5.6 to 9.0 ppm.

Further, when the ¹³ C-nuclear magnetic resonance spectrum was measured, it showed a peak based on the aromatic ring carbon in the vicinity of δ110 to 160 ppm, a peak based on the alkene carbon in the vicinity of δ80 to 140 ppm, and a peak based on the carbon of the alkyl in δ20 to 60 ppm. It was.

  From the above results, it was confirmed that the isolated product was a compound represented by the following structural formula.

Examples 2-20
The chromene compounds shown in Tables 1 to 7 were synthesized in the same manner as in Example 1. About the obtained product, as a result of structural analysis using the means for structure confirmation similar to Example 1, it confirmed that it was a compound shown by structural formula shown in Tables 1-7. Table 8 shows elemental analysis values of these compounds and calculated values obtained from the structural formulas of the respective compounds. Further, FIG. 1 shows a characteristic spectrum of ¹ H-NMR spectrum.

Examples 21-40 and Comparative Examples 1-4
The chromene compound obtained in Example 1 was mixed with a polymerizable monomer, applied to the surface of the lens substrate, polymerized, and then evaluated for physical properties. The photochromic polymerizable composition includes a radical polymerizable monomer 2,2-bis (4-methacryloyloxypentaethoxyphenyl) propane / polyethylene glycol diacrylate (average molecular weight 532) / trimethylolpropane trimethacrylate / polyester oligomer. Hexaacrylate (Daicel UCB, EB-1830) / glycidyl methacrylate was blended at a blending ratio of 50 parts by weight / 10 parts by weight / 10 parts by weight / 10 parts by weight / 10 parts by weight, respectively. After adding 1 part by weight of the chromene compound obtained in Example 1 to 90 parts by weight of the radical polymerizable monomer mixture and mixing well, 1-hydroxycyclohexyl phenyl ketone as a polymerization initiator was reduced to 0. 5 parts by weight, 5 parts by weight of bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate as a stabilizer, and 7 parts by weight of γ-methacryloyloxypropyltrimethoxysilane as a silane coupling agent And 3 parts by weight of N-methyldiethanolamine were added and mixed well.

Subsequently, about 2 g of the mixed solution obtained by the above method was spin-coated on the surface of a lens substrate (CR39: allyl resin plastic lens; refractive index = 1.50) using a MIKASA spin coater 1H-DX2. The surface-coated lens is irradiated with a metal halide lamp with an output of 120 mW / cm ^{2 in} a nitrogen gas atmosphere for 3 minutes to cure the coating film, and then heat-treated with a 120 ° C. incubator. A photochromic cured thin film was obtained.

The obtained photochromic cured thin film (film thickness: 30 μm) was used as a sample, and a Xenon lamp L-2480 (300 W) SHL-100 manufactured by Hamamatsu Photonics was added to this at 20 ° C. ± 1 ° C. via an aeromass filter (manufactured by Corning). The sample was irradiated for 120 seconds with a beam intensity of 365 nm = 2.4 mW / cm ² and 245 nm = 24 μW / cm ² on the surface of the polymer to develop a color, and the photochromic characteristics of the sample were measured. The photochromic characteristics were evaluated as follows.

  (1) Maximum absorption wavelength (λmax): This is the maximum absorption wavelength after color development determined by a spectrophotometer (instant multichannel photodetector MCPD1000) manufactured by Otsuka Electronics Co., Ltd. The harmful maximum absorption wavelength is related to the color tone at the time of color development.

  (2) Initial coloration {ε (0)}: Absorbance in a non-irradiated state at the maximum absorption wavelength. For example, in an optical material such as an eyeglass lens, the lower this value, the better the photochromic property.

  (3) Color density {ε (120) −ε (0)}: difference between the absorbance {ε (120)} after light irradiation for 120 seconds and the above ε (0) at the maximum absorption wavelength. It can be said that the higher this value, the better the photochromic properties.

  (4) Yellow / blue ratio: the ratio of the maximum absorption wavelength in the yellow peripheral region to the maximum absorption wavelength in the blue peripheral region in the color density obtained in (3). It can be said that the closer this value is to 1, the higher the double peak property.

  (5) Color development sensitivity (sec.): Time until the absorbance of the sample at the maximum wavelength reaches saturation due to light irradiation. It can be said that the shorter this time, the better the color development sensitivity.

  (6) Fading half-life [t1 / 2 (min.)]: When light irradiation is stopped after 120 seconds of light irradiation, the absorbance of the sample at the maximum wavelength is {ε (120) −ε (0)}. Time required to drop to 1/2 of The shorter the time, the faster the fading speed and the better the photochromic properties.

(7) Residual rate (%) = {(A ₅₀ / A ₀ ) × 100}: In order to evaluate the durability of color development by light irradiation, the following deterioration acceleration test was conducted. That is, the obtained polymer (sample) was accelerated and deteriorated for 50 hours by a Xenon weather meter X25 manufactured by Suga Test Instruments Co., Ltd. Thereafter, the color density was evaluated before and after the test, the color density (A ₀ ) before the test and the color density (A ₅₀ ) after the test were measured, and the value {(A ₅₀ / A ₀ ) × 100} Was the residual rate (%), and was used as an index of color durability. The higher the remaining rate, the higher the durability of coloring.

  (8) Degree of color change (ΔYI) = YI (50) −YI (0): In order to evaluate the durability of the color tone when not irradiated with light, the samples before and after the above-described deterioration acceleration test The color difference was measured using a color difference meter (SM-4) manufactured by KK). The degree of color change due to deterioration was evaluated by obtaining a difference {ΔYI} obtained by subtracting the color value {YI (0)} before the test from the color value {YI (50)} after the test. . The smaller the ΔYI, the higher the durability of the color tone when no light is irradiated.

  Further, a photochromic polymer was obtained in the same manner as described above except that the compounds obtained in Examples 2 to 20 were used as the chromene compound, and the characteristics thereof were evaluated. The results are summarized in Tables 9-10.

Further, for comparison, the following formulas (A), (B), (C), (D)

In the same manner, a photochromic polymer was obtained using the compound represented by formula (1), and its characteristics were evaluated. The results are shown in Table 11.

  In the photochromic polymers in Examples 21 to 40 using the chromene compound of the present invention, compared with the photochromic polymers of Comparative Examples 1, 2, 3 and 4, all of color development sensitivity, fading speed and durability of photochromic properties were obtained. Excellent in terms.

This figure is a proton nuclear magnetic resonance spectrum of the chromene compound of Example 1.

Claims (6)

Following formula

(In the formula, the numbers represent the positions of carbon atoms and oxygen atoms.)
A chromene compound having an indeno (2,1-f) naphtho (1,2-b) pyran structure as a basic skeleton, the indeno (2,1-f) naphtho (1,2-b) pyran The chromene compound having one group selected from the groups belonging to any one of the following groups (I) and (II) on the carbon atom at the 12-position of the structure:
Group (I): (i-1) hydroxy group; (i-2) substituted or unsubstituted alkyl group; (i-3) substituted or unsubstituted cycloalkyl group; (i-4) substituted or unsubstituted An aryl group; and (i-5) a halogen atom group (II): (ii-1) a group represented by C (O) W (W is a hydroxy group, an alkyl group having 1 to 6 carbon atoms, a carbon number 1-6 alkoxy group, phenyl group, mono-substituted phenyl group, amino group, monoalkylamino group having 1 to 6 carbon atoms as a substituent, or 2 alkyl groups having 1 to 6 carbon atoms are substituted (Ii-2) a group represented by —OR ⁸ (wherein R ⁸ is an alkyl group having 1 to 6 carbon atoms and 1 phenyl group having one phenyl group as a substituent). An alkyl group having 3 to 3 carbon atoms (not including the carbon number of the phenyl group). An alkyl group having 1 to 3 carbon atoms (not including the carbon number of the substituent in the carbon number) having a monoalkyl-substituted phenyl group to which one kill group is bonded, and an alkoxy having 1 to 6 carbon atoms An alkyl group having 1 to 3 carbon atoms (not including the carbon number of the substituent in the carbon number) having a monoalkoxy-substituted phenyl group to which one group is bonded as a substituent, and 1 to 6 carbon atoms as a substituent An alkyl group having 2 to 4 carbon atoms (not including the carbon number of the substituent in the carbon number), a cycloalkyl group having 3 to 7 carbon atoms, and an alkyl group having 1 to 4 carbon atoms as a substituent A monoalkyl-substituted cycloalkyl group having 3 to 7 carbon atoms, a chloroalkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, an allyl group, -CH (R ⁹ ) Group represented by X {however R ⁹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X is a group represented by —CN, —CF ₃ or —COOR ¹⁰ (provided that R ¹⁰ is hydrogen or a group having 1 to 3 carbon atoms). An alkyl group.). And a group represented by (ii-3) -C (O) Y (where Y is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an unsubstituted aryl group) A mono- or di-substituted aryl group, a phenoxy group, a mono- or dialkyl-substituted phenoxy group having 1 or 2 alkyl groups having 1 to 6 carbon atoms as a substituent, and 1 or 2 an alkoxy group having 1 to 6 carbon atoms as a substituent Mono- or dialkoxy-substituted phenoxy group, amino group, mono- or dialkylamino group having 1 or 2 alkyl groups having 1 to 6 carbon atoms as a substituent, phenylamino group, one alkyl group having 1 to 6 carbon atoms or A mono- or dialkoxy-substituted group having one or two substituted amino groups or C1-C6 alkoxy groups having a mono- or dialkyl-substituted phenyl group as a substituent. A substituted amino group having an alkenyl group as a substituent.) The chromene compound according to claim 1, which is represented by the following formula (1).

{Wherein R ¹ and R ² are each independently one group selected from the group consisting of a hydrogen atom, a group belonging to the group (I) and a group belonging to the group (II), or A ring in which R ¹ and R ² are bonded to each other to form a spiro bond at position 13 of the indeno (2,1-f) naphtho (1,2-b) pyran structure, and any one of the following groups (III) A group that forms a ring of
Group (III): (iii-1) a substituted or unsubstituted aliphatic ring having 3 to 20 carbon atoms constituting the ring; (iii-2) a substituted or unsubstituted aromatic ring on the aliphatic ring or A condensed polycycle condensed with a substituted or unsubstituted aromatic heterocycle; (iii-3) a substituted or unsubstituted heterocycle having 3 to 20 atoms constituting the ring; and (iii-4) the heterocycle The condensed polycyclic ring R ³ and R ⁴ in which a substituted or non-substituted aromatic ring or a substituted or non-substituted aromatic heterocycle is condensed is a group represented by the following formula (2): A group represented by (3), a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or an alkyl group, or R ³ and R ⁴ are bonded to each other to form an aliphatic hydrocarbon ring or A group constituting an aromatic hydrocarbon ring,

(In the formula, R ¹¹ represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, R ¹² represents a hydrogen atom, an alkyl group, or a halogen atom, and n represents an integer of 1 to 3. is there.)

(In the formula, R ¹³ is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, and m is an integer of 1 to 3.)
R ⁵ and R ⁶ are each independently an alkyl group, an alkoxy group, an aralkoxy group, an amino group, a substituted amino group, a cyano group, a substituted or unsubstituted aryl group, a halogen atom, an aralkyl group, and a nitrogen atom as a hetero atom. A substituted or unsubstituted heterocyclic group in which the nitrogen atom and the benzo ring are bonded, or a condensed heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is condensed to the heterocyclic group, and p is 0 Is an integer of -4, q is an integer of 0-3, and when p or q is an integer of 2 or more, a plurality of R ⁵ or R ⁷⁶ may be different from each other.
R ⁷ is one group selected from the group consisting of the group belonging to the group (I) and the group belonging to the group (II). } The chromene compound of Claim 2 shown by following formula (4).

{In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and q are respectively synonymous with those in the formula (1), and R ¹⁴ is represented by R ⁵ in the formula (1). Among them, an electron donating group having a Hammett number of −0.49 to −0.01, p is an integer of 0 to 2, and R ¹⁵ is a substituted or unsubstituted aryl group or a substituted or non-substituted group. A substituted heteroaryl group represented by the following formula (5):

Is an aliphatic hydrocarbon ring group which may have at least one substituent selected from an alkyl group, an alkoxy group, an amino group, and a substituted amino group. } The photochromic composition containing the chromene compound in any one of Claims 1 thru | or 3. A photochromic optical article having a polymer molded body in which the chromene compound according to claim 1 is dispersed therein as a constituent member. An optical article having, as a constituent member, an optical substrate in which at least one surface is partially or entirely coated with a polymer film in which the chromene compound according to claim 1 is dispersed.

Images