JP2015137259A - Benzochromene compounds, photochromic agents, and photochromic optical materials - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound, a photochromic agent and a photochromic optical material which exhibit a wide range of colors from blue to yellow while colored, are quickly colored and decolored (particularly, decolored) and have high durability.SOLUTION: There is provided a benzochromene compound represented by the general formula (I). (Rto Rare substituents selected from among amino group derivatives (including amino groups), halogen atoms (excluding F), or H, provided that not all of Rto Rare hydrogen.)

Description

  The present invention changes to a colored or dark form with light containing ultraviolet rays such as sunlight or light from a mercury lamp, and the change is reversible, has a high color density, and returns to a colorless state (hereinafter referred to as `` colorless ''). The present invention relates to a novel benzochromene compound, a photochromic agent and a photochromic optical material exhibiting a fast property of fading.

  In the present specification and claims, the term “benzochromene” means “3H-benzo (f) chromene, also known as (3H-naphtho [2,1-b] pyran)”, unless otherwise specified. The “benzochromene compound” means benzochromene and benzochromene derivatives.

  Photochromism is a phenomenon in which a single chemical species reversibly isomerizes between two states with different absorption spectra without changing the molecular weight due to the action of light, and a compound with this property is a photochromic compound Called.

  A typical example in which a photochromic compound is used industrially is a light control lens. It is a spectacle lens that reduces the glare of sunlight and protects the health of eyes by photoisomerizing into an isomer that absorbs visible light in an environment where sunlight is strong outdoors, and reducing the transmittance of visible light. In indoors where the amount of ultraviolet rays is small, returning to the original isomer quickly fades and becomes nearly colorless.

  Currently, dimming lenses sold as products require several minutes to several tens of minutes to become completely colorless, so research is being conducted to further speed up the photoisomerization (thermal decoloring) reaction. . However, a compound that reacts at high speed at a speed close to that of the human iris has not yet been put into practical use.

  Many studies have been made on photochromic compounds in the past. As chromene, for example, a chromene derivative represented by the following structural formula (A) is disclosed in Patent Document 1, Column 4, Lines 47-62, for example. Which have the same benzochromene skeleton) is colored from colorless to orange (orange) at about −40 ° C. or less when irradiated with ultraviolet light, and becomes colorless at room temperature.

  This benzochromene compound has a low color density and a fading speed, and is not practical as an optical material such as a light control lens. Further, since the color of the color former becomes orange, it has been required to control the absorption wavelength of the color former.

  Many examples of introducing an electron donating group into a benzochromene compound for improving the color density and controlling the color tone of the color have been reported. In particular, when an electron donating group is introduced at the 8-position, the color density is improved and the long wavelength of the colorant is developed. It is known that it becomes possible.

  For example, Patent Document 2, Column 4, Line 64 to Column 5, Line 27 describes that a benzochromene derivative having a benzochromene (3H naphthopyran) skeleton similar to the present invention represented by the following structural formula (B) is desirable. Yes.

The benzochromene compound (Example 1) in which the methoxy group (electron donating group) is introduced at the 8-position is a methoxy group at the 8-position as described in column 8 of column 1 and lines 45 to 61 of the column. In comparison with 3- (4-biphenyl) -3-phenyl-3H-naphtho [2,1b] pyran (Example 2) in which no chlorobenzene is introduced, the maximum absorption wavelength λ _{max of} 454 nm to 484 nm, from yellow Although the wavelength is increased to orange (red), the half-life of the fading rate is about 2 times slower than that of 25 s and 13 s of the unsubstituted chromene compound. For this reason, it cannot be said that it is a photochromic agent suitable for optical materials, such as a light control lens. In addition, the half life of the fading rate of Comparative Example 2 having the same chromene skeleton (3,3-diphenyl-3H-naphtho- [2,1-b] pyran) as in the present invention is 13 s.

  By introducing an electron donating group into the p-position of the 3-position phenyl group of the benzochromene compound, it is possible to increase the absorption wavelength of the color former and to increase the fading speed.

  For example, in Comparative Example 1 on page 11 of Patent Document 3, a chromene compound represented by the following structural formula (C) is described.

This chromene compound is red (λ _max : 490 nm) by introducing an alkoxy group (methoxy group) which is an electron donating group into the p-position of the phenyl group at the 3-position as described in Table 1 on page 13. Color develops and the fading speed increases. Although it is possible with this method to make molecules with a fast fading rate, the introduction of an electron donating group into the phenyl group makes the absorption wavelength of the color former longer than the absorption wavelength of the non-substance, and the color of the color development. Is limited to the red color, so that the optical material is also limited in usage.

  In Table 3 on page 103 of Non-Patent Document 1, as in the present invention, the following structural formula (D) in which a piperidino group as an electron donating group is introduced at the p-position of the phenyl group of 3,3-diphenylbenzochromene Benzochromene compounds represented by) are described.

The Benzokuromen compound as set forth in the table and the page 104 lines 1-3, magenta: fluorescence upon (lambda _max 514 nm), but the half-life of color fading is about 7 seconds, by the influence of piperidino Since the color development is limited to a red color having a wavelength longer than 500 nm, the use as an optical material is limited as in the previous section.

  In Patent Document 4 [0173], an electron donating group (methoxy group) is introduced at the 9-position represented by the following structural formula (E), and an electron-donating group (isopropoxy group) is located at the p-position of the phenyl group. 2H-benzochromene compounds in which are introduced are described.

  As described in [0251] Table II, this benzochromene compound requires several minutes to several tens of minutes to completely fade, and is not suitable for an optical material such as a light control lens.

  That is, Table II shows 1 minute (TF1), 5 minutes (TF5), and 60 minutes (TF60) in the lens transmittance measured in a dark state after irradiation with ultraviolet light. The difference (recF5) in the transmittance (recF5) with respect to the transmittance (TD15) after irradiation for 15 minutes after the lapse of 5 minutes is 42% at the maximum, indicating that the fading speed is slow.

  The benzochromene compounds (derivatives) that have been developed in the past, as in the examples in the above prior art documents, are colored with a slow coloring and fading speed, with a limited wavelength range for reaction, or colored only in specific colors It is not a practical compound as an optical material such as a light control lens.

U.S. Pat.No. 3,567,605 US Patent No. 6337409 JP 9-504003 Publication (International Publication No. 95/05371) Special Table 2006-513276 Publication (International Publication No. 03/089489)

"Sung-Hoon kim" edited by John D. Hepworth and B. Mark Heron "Functional Dyes" Chapter 3 "Photochromic Naft" Piran (Photochromic naphthopyrans) "Elsevier, 2006, p.103-104

  When an electron donating group is substituted on the naphthalene ring of the benzochromene compound, the absorption wavelength of the color former of the compound becomes longer, but the fading speed becomes slower. Further, introduction of an electron donating group into the 3-position phenyl ring makes it possible to increase the absorption wavelength and increase the fading speed, but it is limited to colors having a longer wavelength than red.

  In addition, 2H-benzochromene compounds can produce an intermediate color with one kind of molecule, but have a problem in fading speed (see Patent Document 4). It is difficult to control the color of the colored body and the fading speed at the same time. To that end, it is necessary to mix a plurality of molecules with a fast fading speed, but the fading speed of all the molecules to be mixed is the same. Otherwise, the slow-discolored molecular color will remain at the end.

  Accordingly, an object of the present invention is to provide a benzochromene compound, a photochromic agent, and a photochromic optical material that are colored, faded (especially faded) at high speed and have high durability over a wide range of colors from blue to yellow. There is.

  As a result of diligent development to solve the above-mentioned problems, the present inventors have conceived a benzochromene compound having the following constitution.

In the benzochromene compound according to one aspect of the present invention, in the following general formula (I), R ¹ , R ² and R ³ are an amino group derivative (including an amino group; the same shall apply hereinafter), a halogen atom (excluding F; The same shall apply hereinafter) or H (except for the case where all of R ¹ , R ² and R ³ are hydrogen).

A benzochromene compound according to another embodiment of the present invention is represented by the following general formula (II), wherein R ¹ , R ² and R ³ are an electron donating group, a halogen atom or H (R ¹ , R ² and R ³ And R ⁴ and R ⁴ ′ are electron donating groups or H (except when both R ⁴ and R ⁴ ′ are H). It is.

The present invention further provides
(1) A photochromic agent having a fading half-life (τ1 / 2) of 5 seconds or less by mixing one or more of the benzochromene compounds;
(2) A photochromic optical material (photochromic curable composition) in which one or more of the benzochromene compounds are dispersed in a polymerizable monomer;
(3) a photochromic optical element comprising a polymer molded body in which one or more of the benzochromene compounds are dispersed;
(4) A photochromic optical element comprising, as a component, an optical base material having a surface in which at least a part is coated with a polymer film in which one or more of the benzochromene compounds are dispersed;
Is also provided.

  The chromene compounds of the present invention exhibit a fast fading rate in solution or in a polymeric solid matrix. For example, the photochromic lens using the chromene compound of the present invention quickly returns to the original colorless state when returning from the outdoors to the room, and provides a good field of view to the user. In addition, when a nitrogen-containing heterocyclic group is introduced into a naphtho ring or a phenyl ring, it is possible to increase the wavelength, and various color tone coloring bodies can be obtained. For this reason, it becomes possible to make arbitrary colors by mixing a plurality of photochromic compounds according to the present invention.

It is the graph which put together the fading half-life of the benzochromene compound in each Example and each comparative example, the absorption wavelength of a color development body, and a color development system.

  Hereinafter, the present invention will be described in more detail.

In the general formulas (I) and (II), the “amino group derivative” in R ¹ , R ² and R ⁴ , R ⁴ ′ is monovalent or substituted from the amino group and amino group to a hydrogen atom of a hydrogen atom. A divalent hydrocarbon group (which includes a cyclic group (including aromatics) and a heterocarbon hydrogen group together with a chain) is introduced. The same applies to the claims.

  The amino group derivatives in the general formulas (I) and (II) are not particularly limited, but are preferably an aliphatic group represented by the following general formula (1) or an alicyclic group represented by (2) (Cyclic) type is used.

[However, R ⁵ and R ⁵ ′ are groups represented by a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. ]

[Wherein R ⁶ and R ⁶ ′ are the same or different alkylene groups, and X is an oxygen atom or a sulfur atom. ]

The alkyl group represented by R ⁵ , R ⁵ ′, R ⁶ , R ⁶ ′ in the above general formula generally has 1 to 20 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, and a butyl group. The aryl group preferably has 6 to 10 carbon atoms.

  Specifically, a phenyl group, a tolyl group, a naphthyl group, etc. are mentioned. The aralkyl group preferably has 7 to 14 carbon atoms. Specific examples include a benzyl group, a phenylethyl group, a phenylpropyl group, and a naphthylmethyl group.

The alkylene group represented by R ⁶ or R ⁶ ′ generally has 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms. Specific examples include a methylene group and an ethylene group.

As the amino group derivatives suitable for R ¹ and R ² in the general formulas (I) and (II), the following nitrogen-containing saturated heterocyclic groups and nitrogen-containing aromatic heterocyclic groups can be preferably used.

  Examples of the nitrogen-containing saturated heterocyclic group include a piperidino group, a pyrrolidino group, a piperazino group, a methylpiperazino group, a morpholino group, a thiomorpholino group, and an aziridino group. Among these, by using a piperidino group, piperazino group, methylpiperazino group or morpholino group, the problem of the present invention can be easily solved.

  Examples of the nitrogen-containing aromatic heterocyclic group include a 5-membered ring, a 6-membered ring containing a nitrogen atom, or an aromatic heterocyclic group having 4 to 10 carbon atoms in which a benzene ring is condensed.

  Illustrative examples of suitable aromatic heterocyclic groups include pyrrolyl, imidazolyl, pyrazolyl, oxazole thiazolyl, or indolyl, benzimidazolyl, carbazolyl, and the like in which benzene is condensed to a 5-membered ring.

In R ¹ and R ² , the rate of fading is increased by replacing the nitrogen-containing saturated heterocyclic group with a nitrogen-containing aromatic heterocyclic group (Examples 17 for Example 13 and Example 18 for Example 14).

Suitable halogen atoms for R ¹ and R ² in the general formulas (I) and (II) include Cl, Br, and I.

Examples of the alkoxy group represented by R ⁴ and R ⁴ ′ in the general formula (II) generally include those having 6 or less carbon atoms, preferably 1 to 3 carbon atoms. Specific examples include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group.

Examples of the amino group derivatives represented by R ⁴ and R ⁴ ′ include the nitrogen-containing saturated heterocyclic groups exemplified in the above R ¹ and R ² . The introduction of nitrogen-containing saturated heterocyclic groups facilitates diversification of color formers.

  The benzochromene compound represented by the general formula (I) or (II) of the present invention is well soluble in common organic solvents such as benzene, chloroform, and tetrahydrofuran.

  When the benzochromene 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 rays, and quickly disappears when the light is blocked. It exhibits a good reversible photochromic effect. And such a photochromic effect | action expresses similarly also in a polymer solid matrix.

  The target polymer solid matrix is not particularly limited as long as the benzochromene compounds represented by the general formulas (I) and (II) of the present invention are uniformly dispersed.

  Optically preferably, for example, polymethyl acrylate, polyethyl acrylate, polymethyl methacrylate, polyethyl methacrylate, polystyrene, polyacrylonitrile, polyvinyl alcohol, polyacrylamide, poly (2-hydroxyethyl methacrylate), polydimethylsiloxane And thermoplastic resins such as 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 Polyvalent allyl compounds such as bonate and 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) Acrylic acid ester compounds such as 2-hydroxypropyl acrylate and methacrylic acid ester compounds; obtained by polymerizing a radically polymerizable polyfunctional monomer such as divinylbenzene can be mentioned thermosetting resins.

  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.

  The method for dispersing the benzochromene compound represented by the following general formula (I) or (II) of the present invention in the polymer solid matrix is not particularly limited, and a general method can be used.

  For example, the thermoplastic resin and the benzochromene compound are kneaded in a molten state and dispersed in the resin, or after the benzochromene compound is dissolved in the polymerizable monomer, a polymerization catalyst is added and polymerization is performed by 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. By providing such a manufacturing method, optical products such as photochromic lenses can be produced in large quantities at low cost.

  The benzochromene compound of the present invention can be a photochromic agent comprising a mixture of one or more benzochromene compounds and a fading half-life of 5 seconds or less. In particular, photochromic agents of various colors can be designed by mixing a plurality of types of benzochromene compounds having different maximum absorption wavelengths and similar fading half-lives.

  Moreover, if the photochromic agent is dispersed in a polymerizable monomer, photochromic optical materials of various colors can be prepared. An optical element having a polymer molded body using the photochromic optical material as a constituent member is obtained. Furthermore, the photochromic optical element which uses as a constituent member the optical base material which has the surface at least partially covered with the polymer film formed with the photochromic optical material is obtained. Here, examples of the optical element include a photochromic lens, an optical filter, a display component, a light meter component, and a photochromic ornament.

  Moreover, the benzochromene compound of the present invention can be used in a wide range other than the above optical element. For example, it can be used as various storage materials in place of silver salt photosensitive materials, for example, copying materials, printing photoreceptors, cathode ray tube storage materials, laser photosensitive materials, holographic photosensitive materials, and the like.

  Furthermore, the benzochromene compound of the present invention can be expected to be used in unknown fields such as decoration.

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

<Example 1>
The following naphthalene derivative (4) 254 mg (1.0 mmol),

  The following propargyl alcohol derivative (5) 250 mg (1.2 mmol) is dissolved in 30 mL of toluene,

  10 mg of p-toluenesulfonic acid was added and stirred at room temperature for 6 hours. After the reaction, the solvent was removed and the residue was purified by silica gel column chromatography to obtain 393 mg (0.88 mmol) of a white powder product. The yield was 88%.

The ¹ H-NMR (proton nuclear magnetic resonance) spectrum of this product was measured and found to be ¹ H-NMR (400 MHz, CD ₃ CN), 8.28 (1H, d), 7.98 (1H, d), 7.66 (1H dd), 7.51-7.48 (5H, m), 7.37-7.33 (5H, m), 7.30-7.26 (2H, m), 6.53 (1H, d). From the above results, it was confirmed that the isolated product was a compound represented by the following structural formula (6).

<Example 2>
Further, 100 mg (0.23 mmol) of the above compound (6) and 50 mg (0.30 mmol) of the following carbazole (7),

  Tris (dibenzylideneacetone) dipalladium 4.1 mg (0.0045 mmol), 2- (di-t-butylphosphino) biphenyl 3.0 mg (0.01 mmol), sodium-t-butoxide 35 mg (0.36 mmol) dissolved in toluene 20 mL And refluxed for 12 hours. After the reaction, the reaction mixture was extracted with ethyl acetate, the organic solvent was removed, and the residue was purified by silica gel column chromatography. 85 mg (0.13 mmol) of white powder product was obtained. The yield was 57%.

The ¹ H-NMR spectrum of this synthesized product was measured and found to be ¹ H-NMR (400 MHz, CD ₃ CN), 8.35-8.32 (2H, m), 8.21 (2H, d), 7.79 (1H, dd), 7.58-7.53 (5H, m), 7.50-7.36 (9H, m), 7.33-7.28 (4H, m), 6.60 (1H, d). From the above results, it was confirmed that the isolated product was a benzochromene compound represented by the following structural formula (8).

<Examples 3 to 22>
In the same manner as in Examples 1 and 2, the chromene compounds shown in Tables 1-1 and 1-2 were synthesized, and ¹ H-NMR spectra of the obtained products were measured. It confirmed that it had the structure of.

<Photochromic characteristics test>
The benzochromene compounds of Examples 1 to 22 synthesized above were dissolved in benzene, and the photochromic properties were measured for (a) maximum absorption wavelength and (b) fading rate by the following method.

(a) Maximum absorption wavelength (λ _max ) ...
The ultraviolet-visible absorption spectrum was measured using a spectrophotometer (UV-3150) manufactured by Shimadzu Corporation, and the maximum absorption wavelength (λ _max ) of each of the colorless and colored bodies was determined.

(b) Half-life of fading rate [t 1/2 (sec.)]
The fading speed was measured using a multichannel spectrometer (USB 4000) manufactured by Ocean Optics. As the excitation light, UV-LED 365 nm was used. After the ultraviolet light irradiation is stopped, the time required for the absorbance at the maximum absorption wavelength of the color former of the sample to decrease to half of the absorbance maximum value is defined as the half life of the fading rate. The shorter the time, the faster the fading speed (excellent photochromic properties).

Tables 2 and 3 show R ¹ , R ² , R ³ , R ^4, and R ⁴ ′ in the chromene compounds synthesized in Examples 1 to 22, and the results of the maximum absorption wavelength and fading rate of the colorless and colored bodies. Summarized.

Comparative Examples 1-5
Furthermore, for comparison, as Comparative Examples 1 to 5, benzochromene compounds (commercial products) represented by the following formulas (A), (B), (C), (D) and (E) were used, and the same as above. The photochromic properties were evaluated. The results are shown in Table 4.

  FIG. 1 shows the results of summarizing the fading half-life of the chromene compounds of Examples and Comparative Examples and the absorption wavelength of the color former.

  As shown in Tables 2 and 3, it was confirmed that the present invention can provide a novel benzochromene compound exhibiting various color tones of yellow to blue-violet.

  The absorption wavelength of the color former of each Example shows a longer wavelength than that of the compound (A) of Comparative Example 1 which is an unsubstituted product, and the red color or yellow color to red color (orange, red) and purple / blue color ( It can be confirmed that a variety of colors ranging from blue to purple are exhibited.

  Further, the half-life of fading of all the benzochromene compounds in the examples is within 5 seconds, and compared with the compounds (A), (B), (C), (D) and (E) of Comparative Examples 1 to 5. The color fading speed is twice or more.

  Thus, in the present invention, a high fading speed was realized while maintaining the effect of the substituent appearing in the absorption wavelength. Since compounds having the same kind of substituents can maintain stable performance even in a solvent, it is possible to make optical products such as lenses of arbitrary colors such as gray and brown by mixing a plurality of benzochromene compounds of the present invention. .

In particular, in the example group in which the 3H-bonded phenyl group shown in Table 2 is unsubstituted, the R ¹ is a halogen atom or a nitrogen-containing aromatic heterocyclic group, R ² is H, and R ³ is halogen. In Examples 4, 5, and 15, the fading speed is much faster than in the other examples. Among them, Example 4 in which R ¹ and R ³ are both Br has a particularly fast fading speed.

In addition, when both p-positions of the 3H-bonded phenyl group shown in Table 3 are substituted with alkoxy groups (isopropoxy), the fading rate is much higher than that in Table 2 where the 3H-bonded phenyl group is unsubstituted. Will be faster. Example 16 for Example 2, Example 17 for Example 15, Example 21 for Example 19, and Example 22 for Example 20 are all less than half. Furthermore, when one of the p-positions of the 3H-bonded phenyl group is substituted with a nitrogen-containing saturated heterocyclic group, it varies depending on the substitution position (R ¹ or R ² ) of the halogen atom. When R ¹ is a halogen atom, the fading speed is slow (Example 11 for Example 7), and when R ² is a halogen atom, the fading speed is slightly faster (for Examples 10 and 8 relative to Example 6). Example 12).

Further, when the nitrogen-containing saturated heterocyclic group of R ¹ and R ² is replaced with a nitrogen-containing aromatic heterocyclic group, the fading speed is remarkably increased (Example 17 for Example 13 and Example 18 for Example 14). . It is presumed that the aromatic heterocyclic group is likely to have a resonance structure as compared with the saturated heterocyclic group.

Claims (15)

In the following general formula (I), R ¹ , R ² and R ³ are amino group derivatives (including amino groups; the same shall apply hereinafter), halogen atoms (excluding F; the same shall apply hereinafter) or H (R ¹ , R A benzochromene compound, characterized in that it is a substituent consisting of ² and R ³ except hydrogen.

The benzochromene compound according to claim 1, wherein one of R ¹ and R ² is a halogen atom or amino group derivative and the other is H, and R ³ is a halogen atom or H. The benzochromene compound according to claim 2, wherein R ¹ is a nitrogen-containing aromatic heterocyclic group or a halogen atom, R ² is H, and R ³ is a halogen atom. The benzochromene compound according to claim 3, wherein R ¹ is a carbazolyl group or Br, and R ³ is Br or Cl. In the following general formula (II), R ¹ , R ² and R ³ are amino group derivatives, halogen atoms or H (except when all of R ¹ , R ² and R ³ are hydrogen), and R ⁴ And one or both of R ⁴ ′ are an electron donating group or H (except when both R ⁴ and R ⁴ ′ are H).

6. The benzochromene compound according to claim 5, wherein ^one of R ¹ and R ² is a halogen atom or amino group derivative and the other is H, and R ³ is a halogen atom or H. One of R ¹ and R ² is a halogen atom or a nitrogen-containing heterocyclic group and the other is H, R ³ is a halogen atom or H, and both R ⁴ and R ⁴ ′ have 6 or less carbon atoms. The benzochromene compound according to claim 6, which is an alkoxy group. The benzochromene compound according to claim 7, wherein R ¹ is a halogen atom or a nitrogen-containing aromatic heterocyclic group, R ² is H, and R ³ is H or a halogen atom. The benzochromene compound according to claim 7, wherein R ¹ is Br or a carbazolyl group, R ² is H, and R ³ is H or a halogen atom. One of R ¹ and R ² is a halogen atom or a nitrogen-containing heterocyclic group, R ³ is a halogen atom or H, and one of R ⁴ and R ⁴ ′ is a nitrogen-containing saturated heterocyclic group, and the other The benzochromene compound according to claim 6, wherein is H. One of R ¹ and R ² is a Br or carbazolyl group, R ³ is Cl or H, and one of R ⁴ and R ⁴ 'is a piperidino group and the other is H. Item 10. A benzochromene compound according to Item 10.   A photochromic agent comprising one or a plurality of benzochromene compounds according to any one of claims 1 to 11 and having a fading half-life of 5 seconds or less.   A photochromic optical material comprising one or more benzochromene compounds according to any one of claims 1 to 11 dispersed in a polymerizable monomer.   A photochromic optical element comprising, as a constituent member, a polymer molded body in which one or more of the benzochromene compounds according to any one of claims 1 to 11 are dispersed.   A polymer film in which one or more of the benzochromene compounds according to any one of claims 1 to 11 are dispersed, and an optical substrate having at least a part of the coated surface is provided as a component. A photochromic optical element characterized by

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