JPH0748567A - Photochromic material - Google Patents

Abstract

PURPOSE:To obtain an inexpensive chromene-based photochromic material produced from inexpensive raw materials at a low production cost by selecting a specific compd. having an arom. ring condensed with a pyran ring as a photochromic material. CONSTITUTION:A photochromic material is represented by formula I [wherein R<2> and R<3> are H, 1-20C alkyl, 7-20C aralkyl, etc.; ring alpha is a 5-22C arom. ring condensed with a pyran ring; and R<1> is a group substituted group represented by one of formulas II to IV (wherein R<4> to R<13> are H, hydroxyl, 1-20C alkoxy, 7-15C aralkoxy, 6-14C aryloxy, etc.; X is 0 or S; and rings beta, gamma, and delta are each 5-22C arom. ring)]. The compd. of formula I is produced, e.g. by subjecting a compd. of formula V and a compd. of formula VI to condensation by dehydration in the presence of a basic substance, reacting the resultant compd. of formula VII with a reducing agent, and dehydrating the resultant compd. of formula VIII to provide the compd. of formula I (wherein R<2> and R<3> are each H).

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 a raw material, and in the case of the material of the formula (2), for example, 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.

"[1] The following general formula (A)

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

[In the formula (A), R ² and R ³ are hydrogen,
Alkyl group having 1 to 20 carbon atoms, aralkyl group having 7 to 20 carbon atoms, aryl group having 6 to 19 carbon atoms and 0 to carbon atoms
It represents a substituent selected from 10 amino groups.

The α ring has 5 to 2 carbon atoms condensed to the pyran ring.
Represents an aromatic ring of 2.

R ¹ is represented by the following formulas (B) to (G)

[Chemical 5] Represents any substituent selected from

{In the formulas (B) to (G), R ^{4 to} R ²⁹ are hydrogen, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms,
Aralkoxy group having 7 to 15 carbon atoms, aryloxy group having 6 to 14 carbon atoms, acyloxy group having 1 to 20 carbon atoms, alkyl group having 1 to 20 carbon atoms, aralkyl group having 7 to 15 carbon atoms, and 6 to 14 carbon atoms Aryl group, halo group, carboxyl group, C2-C20 alkoxycarbonyl group, C8-C20 aralkoxycarbonyl group, C7-C2
An aryloxycarbonyl group having 0, a carbamoyl group having 1 to 20 carbon atoms, a carbamoyloxy group having 1 to 20 carbon atoms,
It represents a substituent selected from an acyl group having 1 to 20 carbon atoms, an amino group having 0 to 10 carbon atoms and a nitro group.

X and Y represent a substituent selected from O and S.

The β ring, γ ring, δ ring, ε ring, ζ ring and η ring represent aromatic rings having 5 to 22 carbon atoms. }] ”In the formula (A), R ² and R ³ are hydrogen, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and 6 carbon atoms.
~ 19 represents a substituent selected from an aryl group and an amino group having 0 to 10 carbon atoms, and specific examples thereof include:
Alkyl groups such as methyl group, 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, Aralkyl groups such as naphthylmethyl group; aryl groups such as phenyl group and naphthyl group; amino group, piperidino group, 1-pyrrolidyl group, morpholino group,
Examples thereof include amino groups such as dimethylamino group and diethylamino group.

The α ring has 5 to 2 carbon atoms condensed with a pyran ring.
2 represents an aromatic ring, and specific examples thereof include an aromatic ring represented by the following formula.

[0014]

[Chemical 6] These aromatic rings may share any of the sides of each ring with the pyran ring. Of these, the benzene ring, naphthalene ring and phenanthrene ring are preferable because the corresponding raw materials can be obtained at low cost.

R ¹ is represented by the following formulas (B) to (G)

[Chemical 7] Represents any substituent represented by.

In the formulas (B) to (G), R ^{4 to} R ²⁹ are hydrogen, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms,
Aralkoxy group having 7 to 15 carbon atoms, aryloxy group having 6 to 14 carbon atoms, acyloxy group having 1 to 20 carbon atoms, alkyl group having 1 to 20 carbon atoms, aralkyl group having 7 to 15 carbon atoms, and 6 to 14 carbon atoms Aryl group, halo group, carboxyl group, C2-C20 alkoxycarbonyl group, C8-C20 aralkoxycarbonyl group, C7-C2
An aryloxycarbonyl group having 0, a carbamoyl group having 1 to 20 carbon atoms, a carbamoyloxy group having 1 to 20 carbon atoms,
It represents a substituent selected from 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; a hydroxyl group; a methoxy group,
Ethoxy group, propoxy group, hexyloxy group, octadecyloxy group, icosyloxy group, isopropoxy group, tert
An alkoxy group such as a butoxy group, a vinyloxy group, an allyloxy group, a glycidyloxy group; a benzyloxy group,
Aralkoxy groups such as phenethyloxy group and naphthylmethyloxy group; aryloxy groups such as phenoxy group and naphthyloxy group; formyloxy group, acetoxy group, propionyloxy group, valeryloxy group, hexanoyloxy group, lauroyloxy group, palmitoyloxy group, stearoyl Acyloxy groups such as oxy group, cyclohexanecarbonyloxy group, benzoyloxy group, nicotinoyloxy group, anisoyloxy group, veratroyloxy group, naphthoyloxy group, (meth) acryloyloxy group; methyl group, ethyl group, propyl group Group, hexyl group,
Octyl group, octadecyl group, isopropyl group, tert-
Alkyl groups such as butyl group, 2-ethylhexyl group, vinyl group, allyl group, cyclopentyl group, cyclohexyl group, norbornyl group, adamantyl group; benzyl group,
Aralkyl groups such as phenethyl group and naphthylmethyl 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, hexyloxycarbonyl group, isopropoxycarbonyl group , Vinyloxycarbonyl 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, naphthyloxycarbonyl group, etc. An aryloxycarbonyl group of: carbamoyl group, N-methylcarbamoyl group, N-ethylcarbamoyl group, N-propylcarbamoyl group, N-hexylcarbamoyl group,
Carbamoyl groups such as N-benzylcarbamoyl group and N-phenylcarbamoyl group; carbamoyloxy groups, N
-Methylcarbamoyloxy group, N-ethylcarbamoyloxy group, N-propylcarbamoyloxy group, N-
Hexylcarbamoyloxy group, N-octadecylcarbamoyloxy group, N-isopropylcarbamoyloxy group, N-benzylcarbamoyloxy group, N-phenylcarbamoyloxy group, N-naphthylcarbamoyloxy group, N-methacryloylcarbamoyloxy group, N
A carbamoyloxy group such as-(methacryloyloxyethyl) carbamoyloxy group; an acyl group such as formyl group, acetyl group, propionyl group, (meth) acryloyl group; amino group, piperidino group, 1-pyrrolidyl group,
Examples thereof include amino groups such as morpholino group, dimethylamino group and diethylamino group; and nitro group.

X and Y represent a substituent selected from O and S.

The β-ring, γ-ring, δ-ring, ε-ring, ζ-ring and η-ring represent aromatic rings having 5 to 22 carbon atoms, and specific examples thereof include aromatic compounds represented by the following formulas. A group ring can be mentioned.

[0019]

[Chemical 8] Among them, the benzene ring is preferable because the corresponding raw material can be obtained at low cost.

The α ring, β ring, γ ring, δ ring, ε ring, ζ ring and η ring may be substituted. If these rings are substituted, the substituent is selected from the same substituents as R ⁴ to R ²⁹ mentioned above, also include the same specific examples of the above R ⁴ to R ²⁹ and 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. One of them is the following general formula (3).

[Chemical 9] And a compound represented by the following general formula (4)

[Chemical 10] [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 11] [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 12] [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 a 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 the method of use, but from the viewpoint of sensitivity to vision, 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 other polymerizable compounds. 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 used by polymerization alone or by copolymerization with other polymerizable compounds, solvent resistance, chemical resistance and the like 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 any 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 another polymerizable compound 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 by 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.

[0037]

EXAMPLES The present invention will now be described with reference to examples, but the present invention is not limited thereto. Example 1 [1] 1'-Hydroxy-2'-acetonaphthone (7.0 g), 1-tetralone (7.0 g) and pyrrolidine (8 ml) were dissolved in toluene (150 ml), and then water was prepared by the Dean-Stark method. While removing
The mixture was heated under reflux for 3 hours. 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 (7)

[Chemical 13] Was obtained.

[2] The compound of 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 14] Was obtained.

[3] Analysis Results The elemental analysis results of the compound of formula (8) are shown below.

Elemental analysis value: (as C ₂₂ H ₁₈ O) Theoretical value: C (88.6), H (6.1) (%) Actual value: C (88.6), H (6.1) ) (%) ¹ H-NMR: (measuring instrument; Hitachi 90 MHz, measuring solvent; CDCl ₃ ) around 6.0 ppm to 8.5 ppm (1
2H), around 2.9 ppm (2H), around 1.8 ppm (4H) [4] Application Example The compound of formula (8) (3 parts by weight), polybutyl methacrylate (27 parts by weight) and toluene (70 parts by weight). After applying the solution consisting of
Toluene was removed by drying 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] 1,5-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), 2-tetralone (7.
0 g) and pyrrolidine (8 ml) were added to toluene (150
(ml) and then 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 (9)

[Chemical 15] Was obtained.

[3] The compound of formula (9) (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 (10).

[Chemical 16] Was obtained.

[4] Compound of formula (10) (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 (11) was used.

[Chemical 17] Was obtained.

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

Elemental analysis value: (as C ₃₀ H ₂₂ O ₃ ) Theoretical value: C (83.7), H (5.2) (%) Actual value: C (83.7), H (5. 2) (%) ¹ H-NMR: (measuring instrument; Hitachi 90 MHz, measuring solvent; CDCl ₃ ) around 5.5 ppm to 8.5 ppm (1
3H), around 2.8 ppm (4H), around 2.1 ppm (3H), around 1.8 ppm (2H) [6] Application Example Compound of formula (11) (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. The solution of this photochromic polymer was applied on a slide glass and then dried at 100 ° C. for 2 hours to remove the solvent. 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), 2-indanone (5.0 g) and pyrrolidine (8 ml) were added to toluene. After dissolving in (150 ml), Dean-Stark
The mixture was heated under reflux for 3 hours while removing water by the 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), and the following formula (12)

[Chemical 18] 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 19] Was obtained.

[3] Application Example A solution 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), 1-indanone (7.0 g) and pyrrolidine (8 ml) were dissolved in toluene (150 ml) and then Dean-Stark. While removing water by the method,
The mixture was heated under reflux for 3 hours. 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 20] 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 21] 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 applied on a slide glass, and then 100
Toluene was removed by drying at 0 ° C. for 2 hours to prepare a film. The film was colored by irradiating it with monochromatic light of 360 nm (1.4 mW / cm ² ) at −90 ° C. for 5 minutes. The film was decolorized by irradiation with visible light.

Example 5 [1] 2'-hydroxyacetophenone (7.0)
g), 3-coumaranone (7.0 g) and pyrrolidine (8 ml) were dissolved in toluene (150 ml) and then D
The mixture was heated under reflux for 3 hours while removing water by the ean-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 formula 22] 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 23] Was obtained.

[3] Application Example A solution consisting 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), 4-chromanone (7.0 g) and pyrrolidine (8 ml) were dissolved in toluene (150 ml) and then Dean-Stark. While removing water by the method,
The mixture was heated under reflux for 3 hours. 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 24] 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 25] 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 coated 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 2- [1], 5-methoxy-1-tetralone (7.0 g) and Pyrrolidine (8 ml) was dissolved in toluene (150 ml) and then D
The mixture was heated under reflux for 3 hours while removing water by the ean-Stark 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 (20).

[Chemical formula 26] Was obtained.

[2] Compound of formula (20) (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 (21).

[Chemical 27] Was obtained.

[3] Compound of formula (21) (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 (22).

[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 (23)

[Chemical 29] Was obtained.

[4] Application Example The compound of the formula (23) (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 colored when exposed to sunlight. The multilayer film disappeared when left under room light. This change could be repeated any number of times.

Example 8 [1] 1'-Hydroxy-2'-acetonaphthone (7.0 g), thiochroman-4-one (7.0 g) and pyrrolidine (8 ml) were dissolved in toluene (150 ml) and then Dean. -The mixture was heated under reflux for 3 hours while removing water by the 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 (24)

[Chemical 30] Was obtained.

[2] Compound of formula (24) (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 (25)

[Chemical 31] Was obtained.

[3] Analysis Results The elemental analysis results of the compound of formula (25) are shown below.

Elemental analysis value: (as C ₂₅ H ₁₆ O) Theoretical value: C (90.3), H (4.9) (%) Actual value: C (90.3), H (4.9) ) (%) ¹ H-NMR: (measuring instrument; Hitachi 90 MHz, measuring solvent; CDCl ₃ ) around 6.0 ppm to 8.5 ppm (1
2H), around 2.7 ppm (2H), around 1.8 ppm (2H) [4] Application Example Compound of formula (25) (3 parts by weight), polybutylmethacrylate (27 parts by weight) and toluene (70 parts by weight). After applying the solution consisting of
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.

[0067]

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: [In the formula (A), R ² and R ³ are hydrogen,
Alkyl group having 1 to 20 carbon atoms, aralkyl group having 7 to 20 carbon atoms, aryl group having 6 to 19 carbon atoms and 0 to carbon atoms
It represents a substituent selected from 10 amino groups. The α ring represents an aromatic ring having 5 to 22 carbon atoms which is condensed to a pyran ring.
R ¹ is represented by the following formulas (B) to (G): Represents any substituent selected from {Formula (B) ~
In (G), R ^{4 to} R ²⁹ 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 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. X and Y represent a substituent selected from O and S. The β ring, γ ring, δ ring, ε ring, ζ ring and η ring represent an aromatic ring having 5 to 22 carbon atoms. }] 2. The α ring is selected from a benzene ring, a naphthalene ring and a phenanthrene ring, and a β ring, a γ ring and a δ ring.
The photochromic material according to claim 1, wherein the ring, the ε ring, the ζ ring, and the η ring are benzene rings.