JPH0748566A - Photochromic material - Google Patents

Abstract

PURPOSE:To provide an inexpensive chromene-based photochromic material which can be produced from inexpensive raw materials at a low production cost. CONSTITUTION:A photochromic material is represented by general formula A [wherein R<1> is a substituted group represented by one of formulas B to F wherein R<4> is 1-20C alkyl, etc., and R<5> to R<10> are each H, hydroxyl, etc.; R<2> and R<3> are each H, 1-20C alkyl group, etc.; and rings alpha, beta, and gamma are each 5-22C arom. ring].

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photochromic material, which is preferably used as a printing material, an optical device, a recording material, a light control material, clothing, a decorative material and an optical element.

[0002]

2. Description of the Related Art Conventionally, many compounds are known as photochromic materials. For example, JP-A-63-661
No. 78 and U.S. Pat. No. 3,567,605 show the following formulas (1) and (2), respectively.

[Chemical 3] Chromene-based photochromic materials are shown.

[0003]

However, the conventional chromene-based photochromic material is expensive. This is because, for example, in the case of the material of the formula (1), an expensive adamantane derivative is used as the raw material, and in the case of the material of the formula (2), the purification cost is high.

An object of the present invention is to provide an inexpensive chromene-based photochromic material which can be synthesized from low-priced raw materials and has a low other manufacturing cost.

[0005]

In order to solve such a problem, the photochromic material of the present invention has the following constitution.

"The following general formula (A)

[Chemical 4] A photochromic material comprising a compound represented by:

[Wherein R ¹ is the following formulas (B) to (F)

[Chemical 5] Represents any substituent selected from

R ² and R ³ are hydrogen and have 1 to 20 carbon atoms.
Represents an alkyl group having 7 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 19 carbon atoms, and an amino group having 0 to 10 carbon atoms.

The α ring, β ring and γ ring have 5 to 22 carbon atoms.
Represents the aromatic ring.

In the formulas (B) to (F), R ⁴ has 1 to 2 carbon atoms.
It represents a substituent selected from an alkyl group having 0 to 7, an aralkyl group having 7 to 15 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an acyl group having 1 to 20 carbon atoms.

R ^{5 to} R ¹⁰ are hydrogen, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, and 1 to 1 carbon atoms.
20 acyloxy groups, C1-C20 alkyl groups,
Aralkyl group having 7 to 15 carbon atoms, aryl group having 6 to 14 carbon atoms, halo group, carboxyl group, alkoxycarbonyl group having 2 to 20 carbon atoms, aralkoxycarbonyl group having 8 to 20 carbon atoms, and 7 to carbon atoms 20 aryloxycarbonyl group, carbamoyl group having 1 to 20 carbon atoms, 1 to 2 carbon atoms
It represents a substituent selected from a carbamoyloxy group having 0, an acyl group having 1 to 20 carbon atoms, an amino group having 0 to 10 carbon atoms, and a nitro group. ] In the formula (A), R ¹ is the following formulas (B) to (F).

[Chemical 6] Represents any substituent selected from

R ² and R ³ are hydrogen and have 1 to 20 carbon atoms.
Represents a substituent selected from an alkyl group having 7 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 19 carbon atoms, and an amino group having 0 to 10 carbon atoms. Specific examples thereof include a methyl group. , Alkyl group such as ethyl group, propyl group, hexyl group, octadecyl group, icosyl group, isopropyl group, tert-butyl group, 2-ethylhexyl group, cyclohexyl group, norbornyl group, adamantyl group; benzyl group, phenethyl group, naphthylmethyl group And aralkyl groups such as groups; aryl groups such as phenyl groups and naphthyl groups; amino groups such as amino groups, piperidino groups, 1-pyrrolidyl groups, morpholino groups, dimethylamino groups and diethylamino groups.

The α ring, β ring and γ ring have 5 to 22 carbon atoms.
The aromatic ring represented by the formula (1) below is a specific example.

[0014]

[Chemical 7] Of these aromatic rings, the α ring is a benzene ring,
Raw materials corresponding to naphthalene ring and phenanthrene ring are preferable in that they can be obtained at low cost. As the β ring and the γ ring, a raw material corresponding to a benzene ring is preferable because it can be obtained at low cost.

In the formulas (B) to (F), R ⁴ has 1 to 2 carbon atoms.
It represents a substituent selected from an alkyl group having 0 to 7, an aralkyl group having 7 to 15 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an acyl group having 1 to 20 carbon atoms, and specific examples thereof include:
Methyl group, ethyl group, propyl group, hexyl group, octyl group, octadecyl group, isopropyl group, tert-butyl group, 2-ethylhexyl group, vinyl group, allyl group, cyclopentyl group, cyclohexyl group, norbornyl group, adamantyl group, etc. Alkyl group; aralkyl group such as benzyl group, phenethyl group and naphthylmethyl group; aryl group such as phenyl group and naphthyl group; acyl group such as formyl group, acetyl group, propionyl group and (meth) acryloyl group it can.

R ^{5 to} R ¹⁰ are hydrogen, hydroxyl group, alkoxy group having 1 to 20 carbon atoms, aralkoxy group having 7 to 15 carbon atoms, aryloxy group having 6 to 14 carbon atoms, and 1 carbon atom.
˜20 acyloxy group, C 1-20 alkyl group, C 7-15 aralkyl group, C 6-14 aryl group, halo group, carboxyl group, C 2-20
Alkoxycarbonyl group, C8-20 aralkoxycarbonyl group, C7-20 aryloxycarbonyl group, C1-20 carbamoyl group, C1
A substituent selected from a carbamoyloxy group having 20 to 20 carbon atoms, an acyl group having 1 to 20 carbon atoms, an amino group having 0 to 10 carbon atoms and a nitro group, and specific examples thereof include hydrogen; hydroxyl group; Methoxy group, ethoxy group, propoxy group, hexyloxy group, octadecyloxy group, icosyloxy group, isopropoxy group, tert-butoxy group, vinyloxy group, allyloxy group, glycidyloxy group and other alkoxy groups; benzyloxy group, phenethyloxy group,
Aralkoxy group such as naphthylmethyloxy group; aryloxy group such as phenoxy group, naphthyloxy group; formyloxy group, acetoxy group, propionyloxy group, valeryloxy group, hexanoyloxy group, lauroyloxy group, palmitoyloxy group, stearoyloxy group,
Acyloxy groups such as cyclohexanecarbonyloxy group, benzoyloxy group, nicotinoyloxy group, anisoyloxy group, veratroyloxy group, naphthoyloxy group, (meth) acryloyloxy group; methyl group, ethyl group, propyl group, hexyl group Group, octyl group, octadecyl group, isopropyl group, tert-butyl group, 2-ethylhexyl group, vinyl group, allyl group, cyclopentyl group, cyclohexyl group, norbornyl group, adamantyl group and other alkyl groups; benzyl group, phenethyl group, naphthyl group Aralkyl group such as methyl group; aryl group such as phenyl group and naphthyl group; halo group such as fluoro group, chloro group, bromo group, iodo group; carboxyl group; methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, hexyloxy Carbonyl group, isopropoxycarbonyl group, a vinyl oxycarbonyl group, allyloxycarbonyl group, (2,2,6,6-tetramethyl-4
-Piperidyl) oxycarbonyl group, glycidyloxycarbonyl group and other alkoxycarbonyl groups; benzyloxycarbonyl group, phenethyloxycarbonyl group and other aralkoxycarbonyl groups; phenoxycarbonyl group,
Aryloxycarbonyl group such as naphthyloxycarbonyl group; carbamoyl group, N-methylcarbamoyl group, N
Carbamoyl groups such as ethylcarbamoyl group, N-propylcarbamoyl group, N-hexylcarbamoyl group, N-benzylcarbamoyl group and N-phenylcarbamoyl group; carbamoyloxy group, N-methylcarbamoyloxy group, N-ethylcarbamoyloxy group , N-propylcarbamoyloxy group, N-hexylcarbamoyloxy group, N-octadecylcarbamoyloxy group,
Carbamoyloxy groups such as N-isopropylcarbamoyloxy group, N-benzylcarbamoyloxy group, N-phenylcarbamoyloxy group, N-naphthylcarbamoyloxy group, N-methacryloylcarbamoyloxy group and N- (methacryloyloxyethyl) carbamoyloxy group An acyl group such as a formyl group, an acetyl group, a propionyl group, a (meth) acryloyl group; an amino group, a piperidino group, a 1-pyrrolidyl group, a morpholino group,
Amino groups such as dimethylamino group and diethylamino group;
A nitro group etc. can be mentioned.

The α ring, β ring and γ ring may be substituted. If these rings are substituted, the substituent is selected from the same substituents as R ⁵ to R ¹⁰ mentioned above, also include the same specific examples of R ⁵ to R ¹⁰ of the foregoing specific examples To be These rings may be substituted with a plurality of substituents, in which case a plurality of types of substituents may be substituted at the same time.

As the method for producing the compound represented by the general formula (A) of the present invention, many methods can be applied, and one of them is the following general formula (3).

[Chemical 8] And a compound represented by the following general formula (4)

[Chemical 9] [In the formula, R ¹ represents the same substituent as in the general formula (A). ] And a compound represented by the following general formula (5)

[Chemical 10] [In the formula, R ¹ represents the same substituent as in the general formula (A). ] The compound represented by the following formula (6) is obtained by reacting this compound with a reducing agent.

[Chemical 11] [In the formula, R ¹ represents the same substituent as in the general formula (A). ] The compound represented by the following formula is obtained, and dehydration is further performed to obtain the compound of the general formula (A) [wherein, R ² and R ³ represent hydrogen. ] The method of obtaining the compound represented by these is mentioned.

When R ² or R ³ in the general formula (A) represents a substituent other than hydrogen, one example of the method for producing the same is that the compound of the general formula (5) includes a Grignard reagent or an alkyl halide (halogen). Aralkyl) / basic substance and the like, followed by the operation according to the above.

The photochromic material of the present invention is a solution,
It can be used by dispersing it in an inorganic material, a polymer or the like. Specific examples of the polymer in that case include acrylic polymers such as polyacrylic acid, polymethacrylic acid, polyacrylic acid ester, polymethacrylic acid ester, polyacrylonitrile, polymethacrylonitrile, and polyethylene glycol dimethacrylate; polystyrene, polydivinyl. Polystyrene-based polymers such as benzene and poly (α-methylstyrene); polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyethylene,
Polyolefin-based polymers such as polypropylene, polybutadiene, polyvinyl chloride, and polyvinylidene chloride; epoxy polymers such as bisphenol A bisglycidyl ether (co) polymers; (co) polymers of silane-based compounds having organic polymerizable functional groups; Examples thereof include (co) polymers of spirooxazine compounds having an organic polymerizable functional group; and (co) polymers of spiropyran compounds having an organic polymerizable functional group.

When the photochromic material of the present invention is used by being dispersed in a polymer, the content of the photochromic material of the present invention should be determined depending on the purpose and method of use, but from the viewpoint of visual sensitivity, It is preferably 0.01 to 20% by weight based on the polymer.

The photochromic material of the present invention may be used together with other photochromic materials. In that case, as the other photochromic material, all kinds of photochromic materials can be used without particular limitation, and preferred examples thereof include spirooxazine-based photochromic materials, spiropyran-based photochromic materials, diarylethene-based photochromic materials, and fulgide-based materials. Photochromic materials, chromene-based photochromic materials, silver halide-based photochromic materials and the like can be mentioned.

The compound of the general formula (I) may have a polymerizable substituent.

When the photochromic material of the present invention has a polymerizable substituent, it can be used by polymerization alone or by copolymerization with another polymerizable compound. From the point that the solubility of the photochromic polymer to be generated is large, that a polymer having a high degree of polymerization is easily obtained, and that the photochromic material having a polymerizable substituent can be used in a small amount, it is possible to use other polymerizable compounds. It is preferable to use it by copolymerization.

When it is polymerized alone or copolymerized with another polymerizable compound, the solvent resistance and chemical resistance are improved.

When the photochromic material of the present invention has a polymerizable substituent, the other polymerizable compound to be copolymerized with the photochromic material of the present invention may be a compound having a polymerizable substituent, Although it may be functional, as specific examples thereof, acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester,
Acrylic monomers such as acrylonitrile, methacrylonitrile and ethylene glycol dimethacrylate; styrene monomers such as styrene, divinylbenzene and α-methylstyrene; vinyl acetate monomers; olefins such as ethylene, propylene, butadiene, vinyl chloride and vinylidene chloride -Based monomer; Silane-based compound having organic polymerizable functional group; Spirooxazine-based compound having organic polymerizable functional group; Spiropyran-based compound having organic polymerizable functional group; Diarylethene-based photochromic material having organic polymerizable functional group; Organic Examples include fulgide-based photochromic materials having a polymerizable functional group; chromene-based photochromic materials having an organic polymerizable functional group, and the like.

When the photochromic material of the present invention has a polymerizable substituent, the photochromic material of the present invention and other polymerizable compounds may be used by copolymerizing a plurality of kinds together.

When the photochromic material of the present invention has a polymerizable substituent, a plurality of kinds of photochromic polymers obtained by homopolymerizing or copolymerizing the photochromic material of the present invention may be used.

When the photochromic material of the present invention has a polymerizable substituent and is used by being copolymerized with another polymerizable compound, the content of the photochromic material of the present invention should be determined according to the purpose and method of use. However, from the viewpoint of sensitivity to visual sense, it is preferably 0.01 to 20% by weight based on the weight of other resins.

The material in which the photochromic material of the present invention is dispersed in a polymer, or the photochromic polymer obtained by homopolymerizing or copolymerizing the photochromic material of the present invention can be applied to various substrates by applying a coating method or various printing methods. It is possible to form part or all of the above. As the coating method, various methods such as a dip coating method, a spin coating method, a roll coating method and a bar coating method can be adopted.

The material in which the photochromic material of the present invention is dispersed in a polymer, or the photochromic polymer obtained by homopolymerizing or copolymerizing the photochromic material of the present invention can be used as a bulk molding or as a film.

From the viewpoint of improving the repeated durability of the photochromic material of the present invention, it is particularly effective to block oxygen and water during use. Further, known additives for the purpose of improving durability, for example, singlet oxygen quencher typified by nickel salt, nitroxy radical compound, antioxidant represented by hindered amine compound or polymer thereof, ultraviolet absorber, A triplet quencher or the like can be used.

Applications of the photochromic material of the present invention include ink, printed matter, sunglasses lenses, various goggles, protective eyeglass lenses, camera light control filters, helmet shields, recording materials for writing with light, display and erasing repeatedly. Convertable display materials, windshields, automobile windows such as sunroofs, curtains, window blinds, light control films, light control laminated glass, and convert changes in light intensity into changes in refractive index, electrical resistance, absorbance, etc. Suitable examples include optical elements, clothes, toys, cosmetics, and writing instruments.

[0034]

EXAMPLES The present invention will now be described with reference to examples, but the present invention is not limited thereto. Example 1 [1] 1,5-diacetoxynaphthalene (20.0
g), aluminum chloride (30.0 g) and toluene (200 ml) were mixed and stirred under a nitrogen stream while stirring.
The mixture was heated under reflux for 30 minutes. After allowing to cool, water (400 ml)
After adding, toluene was distilled off using a rotary vacuum evaporator. The insoluble matter that had precipitated was collected by filtration and dried under reduced pressure. It was purified by a recrystallization method (ethyl acetate solvent) to obtain 1 ', 5'-dihydroxy-2'-acetonaphthone.

[2] 1 ', 5'-dihydroxy-2'
-Acetonaphthone (7.0 g), xanthone (7.0
g) and pyrrolidine (8 ml) in toluene (150 m
After dissolving in 1), the mixture was heated under reflux for 3 hours while removing water by the Dean-Stark method. After the reaction, the solvent was distilled off using a rotary vacuum evaporator, followed by silica gel column chromatography (developing solvent;
Purified by a mixed solvent of ethyl acetate / hexane) and represented by the following formula (7)

[Chemical 12] Was obtained.

[3] The compound of the formula (7) (1.0 g) was dissolved in 2-propanol (200 ml), sodium borohydride (1.0 g) was further added, and the mixture was heated under reflux for 6 hours. After allowing to cool, water (100 ml) was added, and the mixture was extracted with ethyl acetate. Anhydrous sodium sulfate was added to the extract for dehydration, and then sodium sulfate was removed by filtration. The solvent was distilled off from the filtrate using a rotary vacuum evaporator. Glacial acetic acid (100 ml) was added thereto, and the mixture was heated under reflux for 2.5 hours. After distilling off acetic acid using a rotary vacuum evaporator, silica gel column chromatography (developing solvent; ethyl acetate /
Purified with a mixed solvent of hexane) and represented by the following formula (8)

[Chemical 13] Was obtained.

[4] Compound of formula (8) (500 m
g), triethylamine (150 mg), methylene chloride (70 ml) and acetone (3 ml) were ice-cooled and stirred while a solution of methacryloyl chloride (200 mg) and methylene chloride (20 ml) was added for 10 minutes. It dripped over. After the completion of dropping, stirring was continued for 30 minutes under ice cooling, and further stirring was performed for 30 minutes at room temperature. After distilling off the solvent using a rotary vacuum evaporator, the residue was purified by silica gel column chromatography (developing solvent; ethyl acetate / hexane mixed solvent), and the following formula (9) was used.

[Chemical 14] Was obtained.

[5] Analysis Results The results of elemental analysis of the compound of formula (9) are shown below.

Elemental analysis value: (as C ₂₉ H ₂₀ O ₄ ) Theoretical value: C (80.5), H (4.7) (%) Actual value: C (80.5), H (4. 7) (%) ¹ H-NMR: (measuring instrument; Hitachi 90 MHz, measuring solvent; CDCl ₃ ) around 5.5 ppm to 8.5 ppm (1
7H), around 2.1 ppm (3H) [6] Application Example Compound of formula (9) (3 parts by weight), butyl methacrylate (27 parts by weight), azobisisobutyronitrile (0.5
(Parts by weight) and toluene (70 parts by weight) were placed in a glass ampoule, and oxygen was removed by freeze deaeration. The ampoule was sealed, heated to 80 ° C., and polymerized for 7 hours to obtain a solution of photochromic polymer. After applying this photochromic polymer solution on a slide glass,
The solvent was removed by drying at 100 ° C. for 2 hours. When the obtained film was irradiated with sunlight, it was colored yellow. The film disappeared when left under room light. This change could be repeated any number of times.

Example 2 [1] 1'-Hydroxy-2'-acetonaphthone (7.0 g), thioxanthen-9-one (7.0 g)
And pyrrolidine (8 ml) with toluene (150 ml)
After being dissolved in, the mixture was heated under reflux for 3 hours while removing water by the Dean-Stark method. After the reaction, the solvent was distilled off using a rotary vacuum evaporator, followed by purification by silica gel column chromatography (developing solvent; ethyl acetate / hexane mixed solvent).
0)

[Chemical 15] Was obtained.

[2] Compound of formula (10) (1.0 g)
Was dissolved in 2-propanol (200 ml), sodium borohydride (1.0 g) was further added, and the mixture was heated under reflux for 6 hours. After allowing to cool, water (100 ml) was added, and the mixture was extracted with ethyl acetate. Anhydrous sodium sulfate was added to the extract for dehydration, and then sodium sulfate was removed by filtration. The solvent was distilled off from the filtrate using a rotary vacuum evaporator. Glacial acetic acid (100 ml) was added thereto, and the mixture was heated under reflux for 2.5 hours. After distilling off acetic acid using a rotary vacuum evaporator, silica gel column chromatography (developing solvent; ethyl acetate /
Purified by a mixed solvent of hexane) and represented by the following formula (11).

[Chemical 16] Was obtained.

[3] Analysis Results The elemental analysis results of the compound of formula (11) are shown below.

Elemental analysis value: (as C ₂₅ H ₁₆ OS) Theoretical value: C (82.4), H (4.4), S (8.8)
(%) Measured value: C (82.4), H (4.4), S (8.8)
(%) ¹ H-NMR: (measuring instrument; Hitachi 90 MHz, measuring solvent; CDCl ₃ ) around 6.0 ppm to 8.5 ppm (1
6H) [4] Application Example A solution of the compound of the formula (11) (3 parts by weight), polybutylmethacrylate (27 parts by weight) and toluene (70 parts by weight) was applied on a slide glass, and then 100
Toluene was removed by drying at 2 ° C for 2 hours. When the obtained film was irradiated with sunlight, it was colored yellow. The film disappeared when left under room light. This change could be repeated any number of times.

Example 3 [1] 3 ', 6'-Dimethyl-1', 8'-dihydroxy-2'-acetonaphthone (7.0 g), dibenzosuberone (7.0 g) and pyrrolidine (8 ml) were added to toluene. After dissolving in (150 ml), Dean-Star
The mixture was heated under reflux for 3 hours while removing water by method k. After the reaction, the solvent was distilled off using a rotary vacuum evaporator, followed by purification using silica gel column chromatography (developing solvent; ethyl acetate / hexane mixed solvent), and the following formula (12)

[Chemical 17] Was obtained.

[2] Compound of formula (12) (100 m
A solution consisting of g) and diethyl ether (50 ml) was ice-cooled, and a hexane solution of butyllithium (1.6 mol / l) (0.2 ml) was added while stirring. Then, a solution consisting of acetyl chloride (200 mg) and diethyl ether (30 ml) was added dropwise over 20 minutes. After completion of dropping, continue stirring under ice cooling for 30 minutes,
Further, the mixture was stirred at room temperature for 30 minutes. After the reaction, ethyl acetate (10 ml) was added. Water (100 ml) was further added, and the mixture was extracted with ethyl acetate. Anhydrous sodium sulfate was added to the extract for dehydration, and then sodium sulfate was removed by filtration. After distilling off the solvent using a rotary vacuum evaporator, silica gel column chromatography (developing solvent; ethyl acetate / hexane mixed solvent)
Using the following formula (13)

[Chemical 18] Was obtained.

[3] Application Example A solution consisting of the compound of the formula (13) (3 parts by weight), polymethylmethacrylate (27 parts by weight) and toluene (70 parts by weight) was applied on a slide glass, and then 100
Toluene was removed by drying at 2 ° C for 2 hours. A solution of polyvinyl alcohol (10 parts by weight) and water (90 parts by weight) was further applied onto the film and dried at 100 ° C. for 2 hours. When the multilayer film is irradiated with sunlight,
It was colored yellow. The multilayer film disappeared when left under room light. This change could be repeated any number of times.

Example 4 [1] 2'-Hydroxy-1'-acetonaphthone (7.0 g), 10-methyl-9 (10H) -acridone (7.0 g) and pyrrolidine (8 ml) in toluene (150 ml). After dissolution, the mixture was heated under reflux for 3 hours while removing water by the Dean-Stark method. After the reaction, the solvent was distilled off using a rotary vacuum evaporator, followed by purification by silica gel column chromatography (developing solvent; ethyl acetate / hexane mixed solvent), and the following formula (14)

[Chemical 19] Was obtained.

[2] Compound of formula (14) (1.0 g)
Was dissolved in 2-propanol (200 ml), sodium borohydride (1.0 g) was further added, and the mixture was heated under reflux for 6 hours. After allowing to cool, water (100 ml) was added, and the mixture was extracted with ethyl acetate. Anhydrous sodium sulfate was added to the extract for dehydration, and then sodium sulfate was removed by filtration. The solvent was distilled off from the filtrate using a rotary vacuum evaporator. Glacial acetic acid (100 ml) was added thereto, and the mixture was heated under reflux for 2.5 hours. After distilling off acetic acid using a rotary vacuum evaporator, silica gel column chromatography (developing solvent; ethyl acetate /
Purified by a mixed solvent of hexane) and represented by the following formula (15)

[Chemical 20] Was obtained.

[3] Application Example A solution of the compound of the formula (15) (3 parts by weight), polybutylmethacrylate (27 parts by weight) and toluene (70 parts by weight) was coated on a slide glass, and then 100
Toluene was removed by drying at 0 ° C. for 2 hours to prepare a film. When the film was irradiated with monochromatic light of 360 nm (1.4 mW / cm ² ) at −90 ° C. for 5 minutes, it was colored yellow. The film was decolorized by irradiation with visible light.

Example 5 [1] 2'-hydroxyacetophenone (7.0)
g), dibenzosuberenone (7.0 g) and pyrrolidine (8 ml) were dissolved in toluene (150 ml),
The mixture was heated under reflux for 3 hours while removing water by the Dean-Stark method. After the reaction, toluene was distilled off using a rotary vacuum evaporator, followed by purification by silica gel column chromatography (developing solvent; ethyl acetate / hexane mixed solvent), and the following formula (16)

[Chemical 21] Was obtained.

[2] Compound of formula (16) (1.0 g)
Was dissolved in 2-propanol (200 ml), sodium borohydride (1.0 g) was further added, and the mixture was heated under reflux for 6 hours. After allowing to cool, water (100 ml) was added, and the mixture was extracted with ethyl acetate. Anhydrous sodium sulfate was added to the extract for dehydration, and then sodium sulfate was removed by filtration. The solvent was distilled off from the filtrate using a rotary vacuum evaporator. Glacial acetic acid (100 ml) was added thereto, and the mixture was heated under reflux for 2.5 hours. After distilling off acetic acid using a rotary vacuum evaporator, the product was purified by silica gel column chromatography (developing solvent: chloroform), and the following formula (17) was used.

[Chemical formula 22] Was obtained.

[3] Application Example A solution of the compound of the formula (17) (3 parts by weight), polybutylmethacrylate (27 parts by weight) and toluene (70 parts by weight) was applied on a slide glass, and then 100
Toluene was removed by drying at 0 ° C. for 2 hours to prepare a film. When the film was irradiated with monochromatic light of 360 nm (1.4 mW / cm ² ) at −90 ° C. for 5 minutes, it was colored yellow. The film was decolorized by irradiation with visible light.

Example 6 [1] 1'-Hydroxy-2'-acetonaphthone (7.0 g), 2-chlorothioxanthen-9-one (7.0 g) and pyrrolidine (8 ml) were dissolved in toluene (150 ml). After that, the mixture was heated under reflux for 3 hours while removing water by the Dean-Stark method. After the reaction, the solvent was distilled off using a rotary vacuum evaporator, followed by purification by silica gel column chromatography (developing solvent; ethyl acetate / hexane mixed solvent), and the following formula (18)

[Chemical formula 23] Was obtained.

[2] Compound of formula (18) (1.0 g)
Was dissolved in 2-propanol (200 ml), sodium borohydride (1.0 g) was further added, and the mixture was heated under reflux for 6 hours. After allowing to cool, water (100 ml) was added, and the mixture was extracted with ethyl acetate. Anhydrous sodium sulfate was added to the extract for dehydration, and then sodium sulfate was removed by filtration. The solvent was distilled off from the filtrate using a rotary vacuum evaporator. Glacial acetic acid (100 ml) was added thereto, and the mixture was heated under reflux for 2.5 hours. After distilling off acetic acid using a rotary vacuum evaporator, silica gel column chromatography (developing solvent; ethyl acetate /
Purified by a mixed solvent of hexane) and represented by the following formula (19).

[Chemical formula 24] Was obtained.

[3] Application Example A solution of the compound of the formula (19) (3 parts by weight), polybutylmethacrylate (27 parts by weight) and toluene (70 parts by weight) was applied on a slide glass, and then 100
Toluene was removed by drying at 2 ° C for 2 hours. When the obtained film was irradiated with sunlight, it was colored yellow. The film disappeared when left under room light. This change could be repeated any number of times.

Example 7 [1] 1 ′, 5′-dihydroxy-2′-acetonaphthone (7.0 g) synthesized in Example 1- [1], the following formula (20)

[Chemical 25] The compound (7.0 g) of Example 1 and pyrrolidine (8 ml) were dissolved in toluene (150 ml), and then Dean-Sta was used.
The mixture was heated under reflux for 3 hours while removing water by the rk method.
After the reaction, the solvent was distilled off using a rotary vacuum evaporator, followed by purification using silica gel column chromatography (developing solvent; ethyl acetate / hexane mixed solvent) to obtain the following formula (21).

[Chemical formula 26] Was obtained.

[2] Compound of formula (21) (1.0 g)
Was dissolved in 2-propanol (200 ml), sodium borohydride (1.0 g) was further added, and the mixture was heated under reflux for 6 hours. After allowing to cool, water (100 ml) was added, and the mixture was extracted with ethyl acetate. Anhydrous sodium sulfate was added to the extract for dehydration, and then sodium sulfate was removed by filtration. The solvent was distilled off from the filtrate using a rotary vacuum evaporator. Glacial acetic acid (100 ml) was added thereto, and the mixture was heated under reflux for 2.5 hours. After distilling off acetic acid using a rotary vacuum evaporator, silica gel column chromatography (developing solvent; ethyl acetate /
Purified by a mixed solvent of hexane) and represented by the following formula (22)

[Chemical 27] Was obtained.

[3] Compound of formula (22) (50 m
g), a solution of di-n-butyltin dilaurate (5 mg) and diethyl ether (50 ml) was ice-cooled and stirred to the following formula (23).

[Chemical 28] Compound (20 mg) and diethyl ether (10 m
The solution consisting of l) was added dropwise over 20 minutes. After completion of the dropping, stirring was continued for 30 minutes under ice cooling, then at room temperature for 30 minutes, and further at reflux temperature for 1 hour. After distilling off the solvent using a rotary vacuum evaporator, the product was purified using silica gel column chromatography (developing solvent; ethyl acetate / hexane mixed solvent),
The following formula (24)

[Chemical 29] Was obtained.

[4] Application Example The compound of the formula (24) (3 parts by weight), butyl methacrylate (27 parts by weight), azobisisobutyronitrile (0.
5 parts by weight) and toluene (70 parts by weight) were placed in a glass ampoule, and dissolved oxygen was removed by freeze deaeration. The ampoule was sealed, heated to 80 ° C., and polymerized for 7 hours to obtain a solution of photochromic polymer. The photochromic polymer solution was applied on a slide glass and dried at 100 ° C. for 2 hours to remove toluene.
A solution of polyvinyl alcohol (10 parts by weight) and water (90 parts by weight) was applied onto the film, and 1
It was dried at 00 ° C. for 2 hours. The multilayer film turned yellow when exposed to sunlight. The multilayer film disappeared when left under room light. This change could be repeated any number of times.

[0060]

EFFECTS OF THE INVENTION Since it can be synthesized from low-priced raw materials and the other manufacturing costs are low, an inexpensive chromene-based photochromic material could be provided.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location C07D 493/10 C 495/10

Claims (2)

[Claims] 1. The following general formula (A): A photochromic material comprising a compound represented by: [Wherein R ¹ is the following formulas (B) to (F): Represents any substituent selected from R ² and R
³ is hydrogen, an alkyl group having 1 to 20 carbon atoms, and 7 to carbon atoms
It represents a substituent selected from an aralkyl group having 20 carbon atoms, an aryl group having 6 to 19 carbon atoms and an amino group having 0 to 10 carbon atoms. The α ring, β ring and γ ring represent an aromatic ring having 5 to 22 carbon atoms. In formulas (B) to (F), R ⁴ has 1 to 2 carbon atoms.
It represents a substituent selected from an alkyl group having 0 to 7, an aralkyl group having 7 to 15 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an acyl group having 1 to 20 carbon atoms. R ^{5 to} R ¹⁰ are hydrogen, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, and 7 to 1 carbon atoms.
5 aralkoxy groups, C 6-14 aryloxy groups, C 1-20 acyloxy groups, C 1-20
Alkyl group, C 7-15 aralkyl group, C 6-14 aryl group, halo group, carboxyl group, C 2-20 alkoxycarbonyl group, C 8-20
Aralkoxycarbonyl group, C7-20 aryloxycarbonyl group, C1-20 carbamoyl group, C1-20 carbamoyloxy group, C1
It represents a substituent selected from an acyl group having ˜20, an amino group having 0 to 10 carbon atoms and a nitro group. ] 2. The photochromic material according to claim 1, wherein the α ring is selected from a benzene ring, a naphthalene ring and a phenanthrene ring, and the β ring and the γ ring are benzene rings.