JP2009057300A - Chromene compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a chromene compound that is a photochromic compound to develop a neutral color and has a high color optical density per unit amount. <P>SOLUTION: The chromene compound is represented by formula (1) (A is a condensed ring; and R<SP>1</SP>and R<SP>2</SP>are each a hydrogen atom, a hydroxy group or the like). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel chromene compound and uses of the chromene compound.

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 the photochromic compound used for such applications, the following characteristics are required.
(1) The degree of coloring (initial coloring) in the visible light region before irradiation with ultraviolet rays is low.
(2) High degree of coloring (color density) when irradiated with ultraviolet rays.
(3) The speed from the start of UV irradiation until the color density reaches saturation is high (high color sensitivity).
(4) The speed (fading speed) from when UV irradiation is stopped until it returns to its original state is fast.
(5) The repeated durability of this reversible action is good.
(6) High dispersibility in the host material used (that is, it dissolves in a high concentration in the monomer composition that becomes the host material after curing).
In addition, in photochromic plastic lenses, intermediate colors such as brown and amber are preferred as the color tone of the color development state. Naturally, what kind of color is developed is an extremely important factor for photochromic compounds. Yes.

  When the color tone is to be adjusted by mixing a plurality of photochromic compounds, a change in color tone (color shift) due to a difference in characteristics of each photochromic compound and a change in color tone due to a difference in durability are caused. In order to solve such a problem, a photochromic compound that develops an intermediate color as a single compound is important.

Known photochromic compounds that produce a neutral color with a single compound include chromene compounds represented by the following formula (A) (see Patent Document 1) and chromene compounds represented by the following formula (B) (see Patent Document 2). ing.

  A photocurable plastic lens having good photochromic properties can be obtained by curing (casting) a curable composition obtained by dissolving these photochromic compounds in a radical polymerizable monomer by thermal radical polymerization. (See Patent Documents 1 and 2).

  The method of producing a photochromic plastic lens by casting polymerization employed in the above-mentioned patent document (also referred to as “in mass” method or kneading method) is one of typical photochromic plastic lens production methods, There is a restriction that polymerizable monomers that can be used to obtain good photochromic properties are limited. In recent years, a coating method has attracted attention as a method for producing a photochromic plastic lens without such restrictions (see Patent Document 3). In the coating method, a coating agent made of a polymer curable composition containing a photochromic compound is applied to the surface of the lens substrate, and the coating film is cured to form a photochromic coating layer, thereby providing photochromic properties to the lens substrate. Therefore, if good coating film adhesion is obtained, there is no restriction on the base lens in principle.

International Publication No. WO00 / 15628 Pamphlet US Pat. No. 7,048,876 International Publication No. WO2003 / 011967 Pamphlet

  Although the coating method has such excellent characteristics, the photochromic compound used in the coating method is an in-mass method (kneading method) in order to impart photochromic properties by a thin layer (photochromic coating layer). A higher level of photochromic properties is required than in As a characteristic of the photochromic plastic lens, the color density when irradiated with ultraviolet rays is one of the most important photochromic characteristics, but it is not always easy to obtain a high color density in the coating method. By increasing the concentration of the photochromic compound contained in the photochromic coating layer, the color density can be increased to a certain extent. However, if the photochromic compound concentration is higher than a certain level, the color density is saturated. For this reason, in order to obtain a high color density by the coating method, the photochromic compound itself needs to have a high color density. In other words, a photochromic compound having a high color density per unit amount (for example, per mole or per unit mass) is required.

  The photochromic compounds represented by the formulas (A) and (B) are excellent in that they are colored in a neutral color, but since the color density per unit amount is low, these compounds are used, and the color density is determined by a coating method. It was difficult to make a high photochromic plastic lens.

  Accordingly, an object of the present invention is to provide a photochromic compound that develops a neutral color and has a high color density per unit amount.

式中、
Ａは縮合環を意味し、
Ｒ^１およびＲ^２は、それぞれ、水素原子、ヒドロキシル基、アルキル基、
シクロアルキル基、アルコキシ基、アラルキル基、アラルコキシ基または
アリール基であり、Ｒ^１とＲ^２は互いに連結して環を形成していてもよく、
さらに、Ｒ^１とＲ^２とが一緒になってこれらの基が結合している炭素原子と
ともにカルボニル基を形成していてもよく、
Ｒ^３、Ｒ^４、Ｒ^５およびＲ^６は、それぞれ、ヒドロキシル基、アルキル基、
シクロアルキル基、アルコキシ基、アラルキル基、アラルコキシ基、アリ
ール基、アミノ基、シアノ基、ニトロ基、ハロゲン原子、ハロゲノアルキ
ル基、ハロゲノアルコキシ基、または窒素原子をヘテロ原子として有し且
つ該窒素原子を結合手として結合している複素環基であり、Ｒ^３が複数存
在する場合には、２個のＲ^３が結合して環を形成していてもよく、
ａおよびｂは、それぞれ、０〜４の整数であり、
ｃおよびｄは、それぞれ、０〜５の整数である。 According to the present invention, a chromene compound represented by the following formula (1) is provided.

Where
A means a condensed ring,
R ¹ and R ² are each a hydrogen atom, a hydroxyl group, an alkyl group,
A cycloalkyl group, an alkoxy group, an aralkyl group, an aralkoxy group or an aryl group, R ¹ and R ² may be linked to each other to form a ring;
Further, R ¹ and R ² may be combined together to form a carbonyl group together with the carbon atom to which these groups are bonded,
R ³ , R ⁴ , R ⁵ and R ⁶ are a hydroxyl group, an alkyl group,
A cycloalkyl group, an alkoxy group, an aralkyl group, an aralkoxy group, an aryl group, an amino group, a cyano group, a nitro group, a halogen atom, a halogenoalkyl group, a halogenoalkoxy group, or a nitrogen atom as a heteroatom and A heterocyclic group bonded with a nitrogen atom as a bond, and when a plurality of R ³ are present, two R ³ may be bonded to form a ring;
a and b are each an integer of 0 to 4,
c and d are integers of 0 to 5, respectively.

According to the invention,
(1) A photochromic curable composition containing the chromene compound and a polymerizable monomer;
(2) A photochromic optical article having, as a constituent member, a polymer molded body in which the chromene compound is dispersed;
(3) An optical article comprising, as a component, an optical substrate having a surface at least partially coated with a polymer film, wherein the chromene compound is dispersed in the polymer film. An optical article;
Is provided.

  Since the chromene compound of the present invention is a single compound and develops an intermediate color, it is not necessary to adjust the color tone by mixing a plurality of photochromic compounds, and the color tone change at the time of fading and the color tone change at the time of deterioration hardly occur. In addition, the chromene compound is excellent in durability, and even when the photochromic reversible reaction is repeated, the deterioration of the photochromic properties is small, and furthermore, the color density per unit amount is high, so that the coating method is adopted. In addition, a photochromic lens having a high color density can be obtained.

で表される。 The chromene compound of the present invention has the following formula (1):

It is represented by

(Fused ring A)
In the above formula (1), A means a condensed ring, that is, a condensed ring condensed with a 7-membered ring to which the groups R ¹ and R ² are bonded. The structure of the condensed ring A is not particularly limited, but (I) an aromatic hydrocarbon ring;
(II) An alicyclic hydrocarbon ring or (III) a heterocyclic ring is preferred.

  (I) The aromatic hydrocarbon ring is preferably one having 6 to 10 carbon atoms forming the ring, such as a benzene ring or a naphthalene ring. The aromatic hydrocarbon ring may have a substituent. Examples of such a substituent include an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group; a methoxy group, an ethoxy group, And alkoxy groups such as a propoxy group and an isopropoxy group. Of these substituents, a methyl group and a methoxy group are particularly preferable. Further, the position and number of the substituent bonded to the aromatic hydrocarbon ring are not particularly limited.

  (II) Examples of the alicyclic hydrocarbon ring include those having 4 to 12 carbon atoms forming the ring, such as a cyclopropane ring, a cyclopentane ring, a cyclohexane ring, and a cyclooctane ring. The alicyclic hydrocarbon may have a substituent similarly to the aromatic hydrocarbon ring. Examples of the substituent include those exemplified in the section of the aromatic hydrocarbon ring (I), and among these, a methyl group and a methoxy group are particularly preferable. Further, the position and number of substitution of the substituent on the alicyclic hydrocarbon ring are not particularly limited.

  (III) As the heterocyclic ring, those having at least one heteroatom such as oxygen, sulfur, nitrogen, etc. in the atoms constituting the ring and having 4 to 10 atoms forming the ring are preferable. Suitable heterocycles include furan ring, thiophene ring, pyrrole ring, pyridine ring, pyrrolidine ring, piperidine ring, morpholine ring, indole ring, benzofuran ring, benzothiophene ring, quinoline ring, isoquinoline ring, indoline ring, chroman ring, etc. Is mentioned. Further, when the hetero atom is a nitrogen atom and a hydrogen atom is bonded to the nitrogen atom, the hydrogen atom may be substituted with a methyl group.

  In the chromene compound of the present invention, among the condensed rings A described above, (I) an aromatic hydrocarbon ring is most preferable because the color density is improved.

(Groups R ¹ and R ² )
In the formula (1), R ¹ and R ² are each a hydrogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an aralkyl group, an aralkoxy group, or an aryl group, and R ¹ and R 2 ² may combine to form a ring.

  Here, the alkyl group is not particularly limited, but is generally an alkyl group having 1 to 9 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, s-butyl group, t -A butyl group etc. are preferable.

  The cycloalkyl group is not particularly limited, but generally a cycloalkyl group having 3 to 12 carbon atoms, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like is preferable. is there.

Although it does not specifically limit as an alkoxy group, Generally a C1-C5 thing, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, s-butoxy group, t-butoxy group, pentyl An oxy group, a neopentyloxy group, and the like are preferable.
Among the alkoxy groups, a substituted alkoxy group having an alkoxy group as a substituent, for example, the following general formula:
-O-R ^a -O-R ^b
In the formula, R ^a is a methylene group, an ethylene group or a propylene group,
R ^b is a methyl group, an ethyl group, or a propyl group,
A substituted alkoxy group represented by can also be suitably used. Among such substituted alkoxy groups, methoxymethoxy group, methoxyethoxy group, ethoxyethoxy group and the like are most preferable.

  Although it does not restrict | limit especially as an aralkyl group, Generally C7-C11 thing, Specifically, a benzyl group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group etc. can be mentioned.

  Although it does not specifically limit as an aralkoxy group, A C6-C10 thing, for example, a phenoxy group, a naphthoxy group, etc. can be mentioned.

  The aryl group is not particularly limited, but is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms or an aromatic heterocyclic group having 4 to 12 atoms forming a ring. Specific examples of such an aryl group include phenyl, naphthyl, thienyl, furyl, pyrrolinyl, pyridyl, benzothienyl, benzofuranyl, benzopyrrolinyl and the like. A substituted aryl group in which one or two or more hydrogen atoms of these aryl groups are substituted with a substituent such as an alkyl group, an alkoxy group, an aralkyl group, an aralkoxy group and the like as described above is also suitable.

In addition, the ring formed by connecting the group R ¹ and the group R ² to each other is preferably a ring having 3 to 10 elements forming the ring. Examples of such a ring include an aliphatic hydrocarbon ring and a heterocycle containing a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom. Further, the aliphatic hydrocarbon ring or hetero ring may have an alkyl group or alkoxy group having 1 to 5 carbon atoms as a substituent (there is no particular limitation regarding the number of substituents and the position of substitution). Furthermore, an aromatic hydrocarbon ring such as benzene or naphthalene may be further condensed. Specific examples of the ring formed by the group R ¹ and the group R ² include the following. In the ring shown below, the carbon atom having the two lowest bonds (spiro carbon atom) corresponds to the carbon atom in the seven-membered ring to which the group R ¹ and the group R ² are bonded. .

Further, the group R ¹ and the group R ² described above may be combined to form a carbonyl group together with the carbon atom to which these groups are bonded. That is, the carbon atom in the carbonyl group (> C═O) is a carbon atom in the seven-membered ring, and the oxygen atom in the carbonyl group is represented by the group R ¹ and the group R ² together. is there.

(Group R ³ to Group R ⁶ )
In the formula (1), the groups R ³ , R ⁴ , R ⁵ and R ⁶ are a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an aralkyl group, an aralkoxy group, an aryl group, an amino group, and a cyano group, respectively. , A nitro group, a halogen atom, a halogenoalkyl group, a halogenoalkoxy group, or a heterocyclic group.

Here, preferred examples of the alkyl group, cycloalkyl group, alkoxy group, aralkyl group, aralkoxy group, and aryl group include the same substituents as those described for the group R ¹ and the group R ² described above.

  The amino group is not limited to a primary amino group, and may be a secondary amino group or a tertiary amino group having a substituent. The substituent of such an amino group is not particularly limited, but an alkyl group or an aryl group is typical. Preferable examples of such a substituted amino group (secondary amino group or tertiary amino group) include alkylamino groups such as methylamino group and ethylamino group; dialkylamino groups such as dimethylamino group and diethylamino group; phenyl An arylamino group such as an amino group; a diarylamino group such as a diphenylamino group;

  As the halogen atom, there can be mentioned a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Examples of the halogenoalkyl group include those in which one or two or more hydrogen atoms of the alkyl group shown for the aforementioned groups R ¹ and R ² are substituted with a fluorine atom, a chlorine atom or a bromine atom. Among these, those substituted with a fluorine atom, such as a fluoromethyl group, a difluoromethyl group, and a trifluoromethyl group, are preferable.

  Examples of the halogenoalkoxy group include those in which one or more hydrogen atoms of the aforementioned alkoxy group are substituted with a fluorine atom, a chlorine atom, or a bromine atom. Particularly preferred halogenoalkoxy groups are fluoroalkoxy groups such as fluoromethoxy groups, difluoromethoxy groups, trifluoromethoxy groups and the like.

  Further, the heterocyclic group has a nitrogen atom as a hetero atom, and the nitrogen atom is bonded as a bond. Such a heterocyclic group has an effect of improving the solubility of the chromene compound in the monomer component. It is particularly suitable in that it increases the dispersibility of the chromene compound in the host material. Typical examples of such a heterocyclic group include a morpholino group and a piperidino group. Further, the heterocyclic group may have an alkyl group such as a methyl group as a substituent. Examples of the heterocyclic group having such a substituent include 2,6-dimethylmorpholino group, 2,6-dimethylpiperidino group, 2,2,6,6-tetramethylpiperidino group and the like.

In the present invention, the above-described groups R ³ , R ⁴ , R ⁵ and R ⁶ are preferably an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a heterocyclic group.

(Ad)
In the formula (1), a, b, c and d represent the numbers of groups R ³ , R ⁴ , R ⁵ and R ⁶ , respectively, and a and b are each an integer of 0 to 4 Yes, c and d are integers of 0 to 5, respectively. From the viewpoint that the chromene compound develops an intermediate color tone, a is preferably 0 to 2, and at least one of b, c and d is preferably 0 to 2. When at least one of the numbers b, c and d is 2, the bonding position of the two groups R ⁴ , R ⁵ or R ^{6 is} a position represented by the following formulas (4) to (6). Is preferred.
In the following formulas (4) to (6), the group R ⁸ and the group R ⁹ represent two groups R ⁴ , the group R ¹⁰ and the group R ¹¹ represent two groups R ⁵ , R ¹² and the group R ¹³ represent two groups R ⁶ .

In the present invention, if the group R ⁴ there are a plurality, they may form a ring more groups R ⁴ are bonded to. For example, in the formula (4), the group R ⁸ and the group R ⁹ can be bonded to form a ring B as represented by the following formula (7).

  Examples of the ring B in the formula (7) include an aliphatic ring, an aromatic ring and a heterocyclic ring having 5 to 7 elements forming the ring, and the ring B includes an alkyl such as a methyl group. You may have a group as a substituent. Moreover, as a heterocyclic ring, what contains 1-2 hetero atoms, such as an oxygen atom, a nitrogen atom, or a sulfur atom, can be mentioned. Examples of suitable ring B are as follows.

(Specific examples of chromene compounds)
In the present invention, a particularly suitable chromene compound can be represented by the following formula (2). In the formula (2), the group R ⁷ has the same meaning as the above-described group R ³ , and e represents the number of the groups R ⁷ and is an integer of 0 to 4.

Furthermore, in the chromene compound represented by the formula (2), the bonding position of the group R ⁴ is preferably a position represented by the following formula (3).

  Specific examples of the chromene compound represented by the formula (3) include the following compounds.

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

(A) 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.

(Manufacture of chromene compounds)
The chromene compound represented by the formula (1) of the present invention can be produced, for example, by the following method.

式中、縮合環Ａ、Ｒ^１〜Ｒ^４、ａおよびｂは、前記式（１）における定義と同
義である、
で示されるナフトール誘導体を出発原料とし、このナフトール誘導体を酸触媒存在下でプロパルギルアルコール誘導体と反応させることにより、本発明のクロメン化合物を製造することができる。 That is, the following formula (i);

In the formula, the condensed rings A, R ^{1 to} R ⁴ , a and b are as defined in the formula (1).
The chromene compound of the present invention can be produced by reacting this naphthol derivative with a propargyl alcohol derivative in the presence of an acid catalyst.

The naphthol derivative represented by the above formula (i) can be produced by a process including the following three-step reaction. (In the following reaction step, the condensed rings A, R ^{1 to} R ⁴ , a and b are all as shown in the formula (1).)

  In the first-stage reaction, naphthol derivative (i-2) is synthesized by reacting naphthol derivative (i-1) with a boronic acid derivative having ring A. Such a reaction is performed in the presence of a palladium catalyst and a base. Tetrakistriphenylphosphine palladium is used as the palladium catalyst, and sodium carbonate or potassium carbonate is used as the base. The reaction ratio of the naphthol derivative (i-1) and the boronic acid derivative is selected from the range of 1: 1 to 1: 4 (molar ratio). Further, the addition amount of the palladium catalyst is preferably in the range of 0.1 to 5.0 mol% with respect to the naphthol derivative (i-1), and the addition amount of the base is 1 to 3 with respect to the naphthol derivative (i-1). A molar range is preferred. The reaction temperature is preferably 40 to 100 ° C., and tetrahydrofuran, dimethoxyethane, toluene and the like are used as the solvent.

  In the second-stage reaction, the naphthol derivative (i-3) is synthesized by reacting the naphthol derivative (i-2) obtained in the first-stage reaction with a Grignard reagent. The reaction ratio of the naphthol derivative (i-2) and the Grignard reagent in the reaction step is selected from the range of 1: 2 to 1:10 (molar ratio). The reaction temperature is preferably −78 to 0 ° C., and tetrahydrofuran, diethyl ether, dibutyl ether, toluene or the like is used as the solvent.

In the third-stage reaction, the desired naphthol derivative (i) is synthesized by reacting the naphthol derivative (i-3) obtained in the second-stage reaction in the presence of an acid catalyst.
As the acid catalyst used in the reaction, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid and the like are used. The amount of the acid catalyst used is selected from the range of 4 to 10 mole times the naphthol derivative (i-3). The reaction temperature is preferably 70 to 140 ° C., and tetrahydrofuran, benzene, toluene, methyl ethyl ketone, methyl isobutyl ketone, propanol, butanol and the like are used as the solvent.

  The naphthol derivative (i) obtained by such a process is subjected to a reaction with a propargyl alcohol derivative after being isolated and purified. At this time, as a purification method, a method of further recrystallization after silica gel column purification is preferably employed.

式中、Ｒ^５、Ｒ^６、ｃおよびｄは、前記式（１）における定義と同義である。 Further, the propargyl alcohol derivative to be reacted with the naphthol derivative is represented by the following formula (ii).

In the formula, R ⁵ , R ⁶ , c and d have the same definitions as in the formula (1).

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

  The reaction between the naphthol derivative represented by formula (i) and the propargyl alcohol derivative represented by formula (ii) is carried out in the presence of an acid catalyst. The reaction ratio of these two compounds is generally 1:10 to It is selected from the range of 10: 1 (molar ratio).

  As the acid catalyst, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, acidic alumina and the like are used, and the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the total mass of the naphthol derivative and the propargyl alcohol derivative. Used in 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 obtained by the reaction is not particularly limited. For example, the product can be purified by silica gel column purification and recrystallization.

(Characteristics and uses of chromene compounds)
The chromene compound of the present invention thus obtained is well soluble in common organic solvents such as toluene, chloroform and tetrahydrofuran. When the chromene compound of the present invention 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 quickly returns to the original colorless state when light is blocked. It exhibits a good photochromic effect.

  The chromene compound of the present invention can be applied to optical articles such as plastic lenses. For example, a photochromic curable composition can be prepared by mixing with a polymerizable monomer described later, and a photochromic plastic lens can be produced by a coating method or an in-mass method. In particular, the chromene compound of the present invention has the characteristics that it is not used in combination with other photochromic compounds, but develops a neutral color by itself, and the color density per unit amount is high. Therefore, it was produced by a coating method. Even photochromic plastic lenses exhibit good photochromic properties.

  When a photochromic plastic lens is produced by the coating method using the chromene compound of the present invention, it can be produced in the same manner as the conventional coating method. For example, a photochromic plastic lens can be produced by preparing a photochromic coating agent according to the method described in Patent Document 3 described above, applying it to the lens surface, and curing it.

  The photochromic coating agent does not contain a silanol group or a radical polymerizable monomer (also referred to as a silyl monomer) having a hydrolyzable group that generates a silanol group by hydrolysis, and such a silanol group or hydrolyzable group. It can be prepared by dissolving a photochromic compound in a monomer composition comprising a normal radical polymerization monomer. The amount of radical polymerizable monomer (silyl monomer and normal radical polymerizable monomer) used in such a coating agent is not particularly limited, but is 20 to 90% by mass based on the total mass of all coating agents, In particular, the content is preferably 40 to 80% by mass. Moreover, the compounding quantity of a photochromic compound is 0.01-20 mass% on the basis of the total mass of all the coating agents, Preferably it is 0.05-15 mass%, More preferably, it is the range of 0.1-10 mass%. is there. If the blending amount of the photochromic compound is 0.01% by mass or less, the color density may be low. On the other hand, if it is 20% by mass or more, it will not be sufficiently dissolved in the polymerizable monomer, resulting in non-uniformity and uneven color density. There is.

Examples of the silyl monomer used in the preparation of the photochromic coating agent include the following.
γ-methacryloyloxypropyltrimethoxysilane,
γ-methacryloyloxypropyltriethoxysilane,
γ-methacryloyloxypropylmethyldimethoxysilane,
(3-acryloyloxypropyl) dimethylmethoxysilane,
(3-acryloyloxypropyl) methyldimethoxysilane,
(3-acryloyloxypropyl) trimethoxysilane,
(Methacryloyloxymethyl) dimethylethoxysilane,
Methacryloyloxymethyltriethoxysilane,
Methacryloyloxymethyltrimethoxysilane,
Methacryloyloxypropyldimethylethoxysilane,
Methacryloyloxypropyldimethylmethoxysilane and the like.

  The amount of the silyl monomer used is not particularly limited, but is preferably 0.5 to 20% by mass, particularly 1 to 10% by mass based on the total mass of all coating agents.

Moreover, the following can be mentioned as a normal radically polymerizable monomer which does not contain a silyl group or a hydrolyzable group.
Trimethylolpropane trimethacrylate,
Trimethylolpropane triacrylate,
Tetramethylol methane trimethacrylate,
Tetramethylol methane triacrylate,
Trimethylolpropane triethylene glycol triacrylate,
Pentaerythritol tetramethacrylate,
Dipentaerythritol hexaacrylate,
Urethane oligomer tetraacrylate,
Urethane oligomer hexamethacrylate,
Urethane oligomer hexaacrylate,
Polyester oligomer hexaacrylate,
Diethylene glycol dimethacrylate,
Triethylene glycol dimethacrylate,
Tetraethylene glycol dimethacrylate,
Tripropylene glycol dimethacrylate,
Bisphenol A dimethacrylate,
2,2-bis (4-methacryloyloxyethoxyphenyl) propane,
Glycidyl methacrylate,
2,2-bis (4-acryloyloxypolyethylene glycol phenyl) propane having an average molecular weight of 776,
Methyl ether polyethylene glycol metaacrylate with an average molecular weight of 475.

  In addition to these radical polymerizable monomers, 4,4′-diphenylmethane bismaleimide, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, 2,2-bis [4- (4-maleimide) A radical polymerizable monomer containing a maleimide group such as phenoxy) phenyl] propane, m-maleimidobenzoyl-N-hydroxysuccinimide ester, succinimidyl-4- (N-maleimidomethyl) cyclohexane-1-carboxylate may be used in combination. it can.

As the photochromic compound, the aforementioned chromene compound of the present invention is used. When the chromene compound of the present invention is used in a photochromic lens, the chromene compound of the present invention is not used in combination with other photochromic compounds and has a characteristic that it develops a neutral color by itself and has a high color density per unit amount. In order to obtain a desired color tone, it can be used in combination with other photochromic compounds.
Thus, as the photochromic compound used in combination with the chromene compound of the present invention, known photochromic compounds such as naphthopyran compounds, chromene compounds, spirooxazine compounds, spiropyran compounds, and fulgimide compounds can be used, and these other photochromic compounds. May be used alone or in combination with the chromene compound of the present invention, or two or more thereof may be used in combination. Specific examples of such photochromic compounds include the following photochromic compounds.

  Moreover, a radical polymerization initiator is usually added to the above-mentioned photochromic coating agent. As the radical polymerization initiator, a photopolymerization initiator and / or a thermal polymerization initiator (chemical polymerization initiator) is used. The amount of these radical polymerization initiators used varies depending on the polymerization conditions, the type of initiator, the type and composition of the radical polymerizable monomer, and cannot be generally limited, but is generally 0 based on the total mass of all coating agents. It is suitable to use in the range of 0.01 to 10% by mass.

  In addition, the following can be illustrated as an example of the polymerization initiator used suitably.

Photopolymerization initiator;
Benzoin,
Benzoin methyl ether,
Benzoin butyl ether,
Benzophenol,
Acetophenone 4,4′-dichlorobenzophenone,
Diethoxyacetophenone,
2-hydroxy-2-methyl-1-phenylpropan-1-one,
Benzyl methyl ketal,
1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one,
1-hydroxycyclohexyl phenyl ketone,
2-isopropylthiooxane,
Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide,
Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide,
2,4,6-trimethylbenzoyldiphenyl-phosphine oxide,
2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl)-
Butanone-1 etc.

Thermal polymerization initiator;
Diacyl peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide, acetyl peroxide;
Peroxyesters such as t-butylperoxy-2-ethylhexanoate, t-butylperoxydicarbonate, cumylperoxyneodecanate, t-butylperoxybenzoate;
Percarbonates such as diisopropyl peroxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-sec-butyloxycarbonate;
2,2′-azobisisobutyronitrile, 2,2′-azobis (4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile),
Azo compounds such as 1,1′-azobis (cyclohexane-1-carbonitrile);

  Furthermore, the above-mentioned photochromic coating agent further includes an amine compound such as triethanolamine in order to improve adhesion, improve the durability of the photochromic compound, improve the color development speed, improve the fading speed and improve the moldability. , A silane coupling agent having a silanol group such as γ-aminopropyltriethoxysilane or a group that generates a silanol group by hydrolysis (different from the silyl monomer described above in that it has no polymerizable group), Additives such as antioxidants, radical scavengers, UV stabilizers, UV absorbers, mold release agents, anti-coloring agents, antistatic agents, fluorescent dyes, dyes, pigments, fragrances, and plasticizers may be added. It is also very preferable to add a polymerization initiator in order to cure the photochromic coating agent. As these additives to be added, known compounds are used without any limitation.

  The coating method when applying the photochromic coating agent containing the chromene compound of the present invention to a lens substrate or the like is not particularly limited, and any known coating (coating) method can be applied without any limitation. Specifically, the method of apply | coating this composition by methods, such as spin coating, spray coating, dip coating, dip-spin coating, is illustrated. The thickness of the coating agent layer applied by such a method (corresponding to the thickness of the coating layer after curing) is not particularly limited. 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.

  A method for curing the photochromic coating agent applied to the lens substrate is not particularly limited, and a known polymerization method according to the type of the radical polymerizable monomer to be used can be employed. The polymerization initiating means can be carried out by using radical polymerization initiators such as various peroxides and azo compounds, or irradiating with ultraviolet rays, α rays, β rays, γ rays or the like or using both in combination. A particularly preferable polymerization method is a method in which the curable composition of the present invention containing the photopolymerization initiator is irradiated with ultraviolet rays and cured, and then further heated to complete the polymerization.

  Such a photochromic plastic lens produced by the coating method using the chromene compound of the present invention develops an intermediate color at a high color density and has little color shift during color development or fading, and can be used for a long time. The color tone at the time of color development is difficult to change.

  As a matter of course, the use of the chromene compound of the present invention is not limited to the use of the photochromic lens by the coating method, and shows the same photochromic characteristics 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.

  Moreover, as another polymer solid matrix, the thermosetting resin formed by superposing | polymerizing the following radically polymerizable polyfunctional monomers can be mentioned.

Polyvalent acrylic acid and polymethacrylic acid ester compounds;
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 the like.

Polyvalent allyl compounds;
Diallyl phthalate,
Diallyl terephthalate,
Diallyl isophthalate,
Diallyl tartrate,
Epoxy succinate diallyl,
Diallyl fumarate,
Diallyl chlorendate,
Diallyl hexaphthalate,
Diallyl carbonate,
Allyl diglycol carbonate,
Trimethylolpropane triallyl carbonate and the like.

Polyvalent thioacrylic acid and polyvalent thiomethacrylic acid ester compounds;
1,2-bis (methacryloylthio) ethane,
Bis (2-acryloylthioethyl) ether,
1,4-bis (methacryloylthiomethyl) benzene and the like.

Acrylic ester compounds and methacrylic ester compounds;
Glycidyl acrylate,
Glycidyl methacrylate,
β-methylglycidyl 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) -2-hydroxypropyl acrylate and the like.

Other radical polymerizable polyfunctional monomers;
Divinylbenzene etc.

  A copolymer obtained by copolymerizing a monofunctional monomer with the polyfunctional monomer as described above can also be used as a polymer solid matrix. The following can be illustrated as such a monofunctional monomer.

Unsaturated carboxylic acids;
Acrylic acid, methacrylic acid, maleic anhydride, etc.
(Meth) acrylic acid ester;
Methyl acrylate, methyl methacrylate, benzyl methacrylate, phenyl methacrylate, 2-hydroxyethyl methacrylate and the like.
Fumaric acid ester;
Diethyl fumarate, diphenyl fumarate, etc.
Thio (meth) acrylic acid ester;
Methylthioacrylate, benzylthioacrylate, benzylthiomethacrylate, etc.
Vinyl compounds;
Styrene, chlorostyrene, methylstyrene, vinylnaphthalene, α-methylstyrene dimer, bromostyrene and the like.

  The chromene compound of the present invention can exhibit photochromic properties even in the above-described polymer solid matrix. Accordingly, when the above-described polymer solid matrix is polymerized, the chromene compound can be applied to an in mass “in mass” method in which the chromene compound is uniformly dispersed in the polymer solid matrix. It is also possible to employ a method in which the chromene compound is kneaded in a molten state and dispersed in the resin.

The polymer molding in which the chromene compound of the present invention is dispersed in the polymer solid matrix can be used as a constituent member of a photochromic optical article.
The chromene compound of the present invention can also impart photochromic properties to various substrates by a method of dispersing the chromene compound in the surface of a thermoplastic resin or a thermosetting resin by dispersing the chromene compound in the resin.

  Further, the chromene compound of the present invention can be applied to uses other than photochromic lenses. For example, various storage materials, copying materials, printing photoreceptors, cathode ray tube storage materials, laser photosensitivity substitutes for silver salt photosensitive materials. It can be used as various storage materials such as materials and photosensitive materials for holography. 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.

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

プロパギルアルコール誘導体；

(Example 1)
The following were prepared as a naphthol derivative and a propargyl alcohol derivative.
Naphthol derivatives;

Propargyl alcohol derivatives;

  7.3 g (20 mmol) of the naphthol derivative and 5.9 g (22 mmol) of the propargyl alcohol derivative were dissolved in 400 ml of toluene, 0.15 g of p-toluenesulfonic acid was further added, and the mixture was stirred at reflux temperature for 30 minutes. After the reaction, the solvent was removed and the residue was purified by chromatography on silica gel to obtain 3.5 g of a white powder product.

The elemental analysis values of this product were as follows.
C: 83.65%
H: 5.91%
O: 10.44%
This analytical value agreed well with the calculated value of C ₄₃ H ₃₆ O ₄ (C: 83.74%, H: 5.88%, O: 10.38%).

  Further, when a proton nuclear magnetic resonance spectrum of the above product was measured, a peak of 15H based on an alkylene group was found around δ 1.0 to 4.0 ppm, an aromatic proton was found around δ 5.2 to δ 10.0 ppm, and A 21H peak based on the alkene proton was shown.

Furthermore, when the ¹³ C-nuclear magnetic resonance spectrum was measured, δ110 to 160
A peak based on the carbon of the aromatic ring was shown in the vicinity of 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.

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

(Examples 2 to 21)
The chromene compounds shown in Tables 1 to 5 were synthesized in the same manner as in Example 1.

  The obtained product was subjected to structural analysis using the same structure confirmation means as in Example 1, and confirmed to be a compound represented by the structural formula shown in the table. Tables 6 and 7 show the elemental analysis values of these compounds and the calculated values obtained from the structural formulas of the respective compounds.

(Example 22)
The chromene compound obtained in Example 1 was mixed with a polymerizable monomer composition containing a photopolymerization initiator as described below, and then applied to the surface of the lens substrate and polymerized.

  As the polymerizable monomer composition, a mixture of each radical polymerizable monomer with the following formulation was used.

2,2-bis (4-methacryloyloxypentaethoxyphenyl) propan; 50 parts by mass Polyethylene glycol diacrylate (average molecular weight 532); 10 parts by mass trimethylolpropane trimethacrylate; 10 parts by mass polyester oligomer hexaacrylate (Daicel UCB) EB-1830); 10 parts by mass Glycidyl methacrylate; 10 parts by mass

After adding 1 part by mass of the chromene compound obtained in Example 1 to 90 parts by mass of the above polymerizable monomer composition and thoroughly mixing it, 0.5 parts by mass of a polymerization initiator is a stabilizer. 5 parts by mass of bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 7 parts by mass of γ-methacryloyloxypropyltrimethoxysilane as a silane coupling agent, and 3 parts of N-methyldiethanolamine Part by mass was added and mixed thoroughly.
As a polymerization initiator, a mixture of 1-hydroxycyclohexyl phenyl ketone and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide called CGI1850 (weight ratio 1: 1) is used. Using.

About 2 g of the mixed solution obtained above was used as a lens substrate (CR39: allyl resin plastic lens; refractive index = MIKASA spin coater 1H-DX2).
1.50) surface was spin coated. The surface-coated lens was irradiated for 2 minutes in a nitrogen gas atmosphere using a metal halide lamp with an output of 150 mW / cm ² to cure the coating film, thereby forming a photochromic cured thin film (film thickness: 40 μm).

  The photochromic characteristics of the photochromic lens obtained as described above were evaluated as follows, and the results are shown in Table 8.

(1) Maximum absorption wavelength (λmax):
It is the maximum absorption wavelength after color development determined by a spectrophotometer (instant multichannel photodetector MCPD3000) manufactured by Otsuka Electronics Co., Ltd. This maximum absorption wavelength is related to the color tone during color development.

(2) Color density {ε (120) −ε (0)}:
The 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.

(3) Degradation level = {(A ₀ −A _x ) / A ₀ }:
In order to evaluate the durability of color development by light irradiation, the following deterioration acceleration test was performed and the degree of deterioration was measured.
That is, the obtained sample (photochromic lens) was accelerated and deteriorated for 50 hours by a Xenon weather meter X25 manufactured by Suga Test Instruments Co., Ltd. Before and after the deterioration, the color density is evaluated, the color density (A ₀ ) before the test and the color density (A ₅₀ ) after the test are measured, and the degree of deterioration {(A ₀ -A ₅₀ ) / A ₀ } Was used as an index of color development durability. The lower the degree of deterioration, the higher the durability of coloring.

(Examples 23 to 42)
A photochromic cured thin film was obtained in the same manner as described above except that the compounds obtained in Examples 2 to 21 were used as the chromene compound, and the characteristics thereof were evaluated. The results are summarized in Table 8 and Table 9.

(Comparative Examples 1 and 2)
Further, for comparison, a chromene compound represented by the following formulas (A) and (B) was used, and a photochromic cured thin film was produced in the same manner as in the above Example, and its characteristics were evaluated. The results are shown in Table 10.

  When the comparative compounds (A) and (B) were used, polymerization failure occurred when the coating film was cured, and a uniform cured thin film could not be obtained. Since these compounds with benzylic hydrogen are unstable to radicals, some of the radicals generated during photopolymerization are consumed in the reaction (decomposition) with these compounds. This is probably because no radicals were obtained.

  The chromene compounds of the present invention shown in Examples 1 to 21 have a low degree of deterioration and high repetition durability of photochromic characteristics as compared with the compounds of Comparative Examples 1 and 2. Furthermore, since the chromene compound of the present invention has a high color density per unit amount, when a photochromic plastic lens is produced using the chromene compound of the present invention, excellent photochromic properties are exhibited.

(Example 43, Comparative Examples 3 and 4)
Next, evaluation of the photochromic cured body by the in-mass method was performed as follows. That is, in the following formulation, each component was sufficiently mixed to prepare a photochromic curable composition.

Photochromic curable composition Chromene compound obtained in Example 1; 0.04 parts by mass Tetraethylene glycol dimethacrylate; 13 parts by mass 2,2-bis [4- (methacryloxyethoxy) phenyl] propane; 48 parts by mass Polyethylene Glycol monoallyl ether; 2 parts by mass trimethylolpropane trimethacrylate; 20 parts by mass glycidyl methacrylate; 9 parts by mass t-butylperoxy 2-ethylhexanate (polymerization initiator); 1 part by mass

  Next, the obtained composition was poured into a mold composed of a glass plate and a gasket made of an ethylene-vinyl acetate copolymer, and cast polymerization was performed. The polymerization was performed using an air oven at 30 ° C. to 90 ° C. over 18 hours, and the temperature was gradually maintained at 90 ° C. for 2 hours. After the polymerization, the cured product was removed from the glass mold of the mold. The obtained cured body (thickness 2 mm) was used as a sample, and photochromic properties were evaluated using the same method as described above.

  For further comparison, photochromic weight was similarly determined using the compound represented by the formula (A) (Comparative Example 3) or the compound represented by the formula (B) (Comparative Example 4) instead of the chromene compound of Example 1. A coalescence was obtained and its properties were evaluated. The results are shown in Table 11.

  Also in the evaluation of the photochromic cured body in the in-mass system, the cured body (polymer molded body) obtained in Example 43 using the chromene compound of the present invention has the same unit amount as the photochromic cured body obtained by the coating system. It can be seen that the color density per hit is excellent.

Claims (6)

A chromene compound represented by the following formula (1);

Where
A means a condensed ring,
R ¹ and R ² are each a hydrogen atom, a hydroxyl group, an alkyl group,
A cycloalkyl group, an alkoxy group, an aralkyl group, an aralkoxy group or an aryl group, R ¹ and R ² may be linked to each other to form a ring;
Further, R ¹ and R ² may be combined together to form a carbonyl group together with the carbon atom to which these groups are bonded,
R ³ , R ⁴ , R ⁵ and R ⁶ are a hydroxyl group, an alkyl group,
A cycloalkyl group, an alkoxy group, an aralkyl group, an aralkoxy group, an aryl group, an amino group, a cyano group, a nitro group, a halogen atom, a halogenoalkyl group, a halogenoalkoxy group, or a nitrogen atom as a heteroatom and A heterocyclic group bonded with a nitrogen atom as a bond, and when a plurality of R ³ are present, two R ³ may be bonded to form a ring;
a and b are each an integer of 0 to 4,
c and d are integers of 0 to 5, respectively. The chromene compound according to claim 1 represented by the following formula (2):

Where
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , a, b, c and d are defined by the formula (1)
Is synonymous with
R ⁷ is a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group,
Aralkyl group, aralkoxy group, aryl group, amino group, cyano group, nitro group, halogen atom, halogenoalkyl group, halogenoalkoxy group,
Or a heterocyclic group having a nitrogen atom as a heteroatom and bonded with the nitrogen atom as a bond,
e is an integer of 0-4. The chromene compound according to claim 2 represented by the following formula (3):

Where
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , a, b, c and d are defined by the formula (1)
Is synonymous with
R ⁷ and e have the same meaning as in formula (2),
R ⁸ and R ⁹ are each a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an aralkyl group, an aralkoxy group, an aryl group, an amino group, an amino group, a cyano group, a nitro group, a halogen atom, or a halogenoalkyl group. , A halogenoalkoxy group, or a heterocyclic group having a nitrogen atom as a heteroatom and bonded with the nitrogen atom as a bond,
R ⁸ and R ⁹ may be combined to form a ring. The ring formed by R ⁸ and R ⁹ has 5 to 7 elements, and the ring is a heteroatom. And may contain one or two oxygen atoms, nitrogen atoms or sulfur atoms.   A photochromic curable composition comprising the chromene compound according to claim 1 and a polymerizable monomer.   A photochromic optical article having, as a constituent member, a polymer molded body in which the chromene compound according to claim 1 is dispersed.   An optical article comprising, as a component, an optical substrate having a surface at least partially coated with a polymer film, wherein the chromene compound of claim 1 is dispersed in the polymer film. An optical article.