JP2758936B2 - Photochromic compounds - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel photochromic compound, and more particularly to a photochromic compound useful as various recording materials or light control materials.

[Conventional technology]

Conventionally, various photochromic organic compounds have been known, and spirooxazine compounds have been known as compounds having relatively good repetition durability of a coloring action, for example, Japanese Patent Publication Nos. 45-28892 and 49-49. 48631, JP-A-55-36284, JP-A-60-53586,
JP-A-61-53288 and JP-A-61-263982 disclose 1,3,3-trimethylspiro [indoline-2,3 '-(3H) -naphtho (2,1-b) (1,4) oxazine]. And derivatives thereof.

Also, as a request for coloring other than blue,
For example, JP-A-62-145089 and JP-A-63-179879 disclose photochromic compounds that emit red light.

[Problems to be solved by the invention]

However, such a conventional photochromic compound composed of a spirooxazine compound has a problem in that the color developability at room temperature or higher temperatures is not always good.

An object of the present invention is to solve the above problems and to provide a novel photochromic compound having good coloring properties even at a high temperature of room temperature or higher.

[Means to solve the problem]

The photochromic compound of the present invention is characterized by comprising a spirooxazine compound represented by the following general formula (I) or (II).

(In the formula, A ¹ represents an alkyl group having 1 to 24 carbon atoms, an allyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryloxyalkyl group or an alkoxyalkyl group, and R ^{1 to} R ⁸ represent A hydrogen atom, a linear or branched alkyl group, R ⁹ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group or an alkoxyalkyl group, one of X and Y represents a nitrogen atom, and the other represents It represents a methine group.) (Wherein A ² is an alkylene group, alkylene (polyoxy)
Represents an alkylene group or an alkylenearylalkylene group, R ^{1 to} R ⁸ represent a hydrogen atom, a linear or branched alkyl group, and R ⁹ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group or an alkoxyalkyl And one of X and Y represents a nitrogen atom, and the other represents a methine group. Hereinafter, the present invention will be described specifically.

In the present invention, a spirooxazine compound represented by the general formula (I) or (II) is used as a photochromic compound.

Among the spirooxazine compounds represented by the general formula (I), those represented by the following general formula (IA) are particularly preferable.

(In the formula, A ¹ represents an alkyl group having 1 to 24 carbon atoms, an allyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryloxyalkyl group or an alkoxyalkyl group, and R ¹ and R ² represent Specific examples of the compound represented by formula (IA) include (1) 1,3,3-trimethylspiro [piperidine-2,3 '.
(3H) -pyrido (3,4-f) (1,4) benzoxazine] (2) 1-isopropyl-3,3-dimethylspiro [piperidine-2,3 '-(3H) -pyrido (3,4 -F) (1,4) benzoxazine] (3) 1- (2-phenoxyethyl) -3,3-dimethylspiro [piperidine-2,3 '-(3H) -pyrido (3,4-
f) (1,4) benzoxazine] (4) 1- (p-methoxybenzyl) -3,3-dimethylspiro [piperidine-2,3 '-(3H) -pyrido (3,4-
f) (1,4) benzoxazine] (5) 1-isopropyl-3-methyl-3-ethylspiro [piperidine-2,3 '-(3H) -pyrido (3,4-f)
(1,4) benzoxazine] (6) 1-methoxyethyl-3-methyl-3-ethylspiro [piperidine-2,3 '-(3H) -pyrido (3,4-f)
(1,4) benzoxazine] (7) 1-hexyl-3,3-dimethylspiro [piperidine-2,3 '-(3H) -pyrido (3,4-f) (1,4) benzoxazine] ( 8) 1-octadecyl-3,3-dimethylspiro [piperidine-2,3 '-(3H) -pyrido (3,4-f) (1,4) benzoxazine] (9) 1-heptyl-3-methyl -3-Ethylspiro [piperidine-2,3 '-(3H) -pyrido (3,4-f) (1,
4) Benzoxazine] (10) 1-cyclohexylmethyl-3,3-dimethylspiro [piperidine-2,3 '-(3H) -pyrido (3,4-f)
(1,4) benzoxazine] Others can be mentioned, but of course the present invention is not limited to these. Further, a compound in which a bulky group such as an octadecyl group or a cyclohexylmethyl group is introduced at the 1-position is preferable because a large coloration can be obtained.

In addition to the above, specific examples of the spirooxazine compound represented by the general formula (I) include (11) 1,3,3-trimethylspiro [piperidine-2,3'-
(3H) -pyrido (3,2-f) (1,4) benzoxazine] (12) 1-isopropyl-3,3-dimethylspiro [piperidine-2,3 '-(3H) -pyrido (3,2 -F) (1,4) benzoxazine] (13) 1-benzyl-3,3-dimethylspiro [piperidine-2,3 '-(3H) -pyrido (3,2-f) (1,4) benzo Oxazine] (14) 1- (2-phenoxyethyl) -3,3-dimethylspiro [piperidine-2,3 '-(3H) -pyrido (3,2-
f) (1,4) benzoxazine] (15) 1- (p-methoxybenzyl) -3,3-dimethylspiro [piperidine-2,3 '-(3H) -pyrido (3,2-
f) (1,4) benzoxazine] (16) 1- (2-methoxyethyl) -3,3-dimethylspiro [piperidine-2,3 '-(3H) -pyrido (3,2-f)
(1,4) benzoxazine] (17) 1,3-dimethyl-3-ethylspiro [piperidine-2,3 '-(3H) -pyrido (3,2-f) (1,4) benzoxazine] (18 ) 1,3,3,4,5-pentamethylspiro [piperidine-
2,3 '-(3H) -pyrido (3,2-f) (1,4) benzoxazine] (19) 1-isopropyl-3-methyl-3-ethylspiro [piperidine-2,3'-(3H) -Pyrido (3,2-f)
(1,4) benzoxazine] (20) 1,3,3,4,5-pentamethylspiro [piperidine-
2,3 '-(3H) -pyrido (3,4-f) (1,4) benzoxazine] (21) 1,3,3,5-tetramethylspiro [piperidine-2,
3 '-(3H) -pyrido (3,4-f) (1,4) benzoxazine] (22) 1-hexyl-3,3-dimethylspiro [piperidine-2,3'-(3H) -pyrido ( 3,23-f) (1,4) benzoxazine] (23) 1-hexadecyl-3,3-dimethylspiro [piperidine-2,3 ′-(3H) -pyrido (3,2-f) (1, 4) Benzoxazine] (24) 1-octyl-3,5,6-trimethyl-3-ethylspiro [piperidine-2,3 '-(3H) -pyrido (3,4-
f) (1,4) Benzoxazine] and others, but of course, the present invention is not limited thereto.

Among the above compounds, the spirooxazine compound represented by the general formula (IA) is particularly preferable because of its high degree of color development and good color development at room temperature or higher temperatures.

The spirooxazine compound represented by the general formula (II) also has a good degree of color development.

Among the spirooxazine compounds represented by the general formula (II), those represented by the following general formula (II-A) are particularly preferable.

(Wherein A ² is an alkylene group, alkylene (polyoxy)
It represents an alkylene group or an alkylenearylalkylene group, and R ¹ and R ² represent an alkyl group having 5 or less carbon atoms. Specific examples of the compound represented by the general formula (II-A) include: (1) 1,1 ″-(1,5-pentanediyl) bis [3,3-dimethylspiro [piperidine-2,3 ′-( 3H) -pyrido (3,4-f) (1,4) benzoxazine]] (2) 1,1 ″-[1,4-phenylenebis (methylene)] bis [3,3-dimethylspiro [piperidine- 2,3 '-(3H)
-Pyrido (3,4-f) (1,4) benzoxazine]] and the like, but are not limited thereto.

In addition to the above, specific examples of the spirooxazine compound represented by the general formula (II) include (3) 1,1 ″-(1,5-pentanediyl) bis [3,3-dimethylspiro [piperidine-2,3 '-(3H) -pyrido (3,2-f) (1,4) benzoxazine]] (4) 1,1 "-(1,6-hexanediyl) bis [5-methyl-3,3-dimethyl Spiro [piperidine-2,3 '-(3H)
-Pyrido (3,2-f) (1,4) benzoxazine]] (5) 1,1 ″-(1,10-decanediyl) bis [5-methoxy-3,3-dimethylspiro [piperidine-2, 3 '-(3
H) -pyrido (3,4-f) (1,4) benzoxazine]] (6) 1,1 ″-[1,4-phenylenebis (methylene)] bis [3-ethyl-3-methylspiro [piperidine −2,
3 ′-(3H) -pyrido (3,2-f) (1,4) benzoxazine]] (7) 1,1 ″-(1,6-hexanediyl) bis [3,3-dimethylspiro [piperidine -2,3 '-(3H) -pyrido (3,2-f) (1,4) benzoxazine]] and the like, but are not limited thereto.

Among the above compounds, the spirooxazine compound represented by the general formula (II-A) is particularly preferable because of its high degree of color development and good color development at room temperature or higher temperatures.

The above spirooxazine compound can be synthesized, for example, by reacting a 5-nitroso-6-quinolinol or 8-nitroso-7-isoquinolinol derivative with a piperidine compound having a desired substituent. Specifically, both of them may be dissolved in an appropriate solvent such as ethyl alcohol or toluene, and the resulting mixture may be refluxed under a nitrogen gas atmosphere to cause a reaction. Instead of the piperidine compound, a piperidinium salt compound having a desired substituent may be used. In these reactions, a base such as triethylamine can be added as a catalyst. Further, the synthesized spirooxazine compound can be purified by a method such as a recrystallization method, a column separation method, or an activated carbon treatment method, if necessary.

The photochromic compound of the present invention can be embodied as an object having a photochromic action by dispersing or dissolving it in a solid medium.

Here, the solid medium is not particularly limited as long as the photochromic compound can be contained alone or together with other necessary additives. Therefore, it may be a simple binder, or a resin constituting an article having a unique function by itself, for example, a resin constituting an optical material.

Specific examples of the resin used as the solid medium include polyol (allyl carbonate), acrylic resin, cellulose resin, polyvinyl alcohol, polyvinyl acetate,
Examples include urethane resins, epoxy resins, silicone resins, polyesters such as polystyrene and polyethylene terephthalate, polyvinyl butyral, polyamide, polyvinyl chloride, polyvinylidene chloride, and other resins.

The proportion of the spirooxazine compound in the solid medium composed of such a resin is not particularly limited,
It is used in an amount of 0.001 to 100 parts by weight, preferably 0.01 to 50 parts by weight, based on 100 parts by weight of the solid medium.

The photochromic compound of the present invention can be used in the same manner as a normal photochromic substance. Therefore, it can be put to practical use using, for example, the following method.

A method in which a mixture obtained by mixing the photochromic compound with a binder is used as a material, and the mixture is formed into a film, plate, or other desired form by a method such as a casting method or a melting method.

According to this method, a solid article having a photochromic action itself can be manufactured.

Dissolve the photochromic compound in a suitable common solvent together with a binder, the resulting solution as a coating solution,
For example, a method in which a photochromic layer is formed on the substrate by applying to a substrate made of various optical materials and then removing the solvent.

According to this method, an optical material such as a lens having a photochromic layer can be manufactured.

A method of casting the solution in the above method.

According to this method, a photochromic film can be suitably formed.

In the above method or the above method, a suitable dispersion medium is used in place of the solvent, and the photochromic compound is dispersed in the dispersion medium together with a binder to obtain a dispersion, which is then used.

In the method from the above, in place of part or all of the binder, using a polymerizable monomer that becomes a binder by polymerization, a photochromic article formed,
A method of further polymerizing a layer or a film.

According to this method, an article, layer, film, or the like made of a polymer having a photochromic action can be obtained. Therefore, for example, by adding the above-mentioned photochromic compound to a monomer composition that gives an optical material by polymerization, filling this into a casting polymerization container and performing a polymerization treatment, a lens having a direct photochromic action, etc. Can be manufactured.

In carrying out the above method, it is possible to further add an antioxidant, an ultraviolet absorber for blocking unnecessary short-wavelength light, a light stabilizer, and other additives.

By using a hindered amine-based light stabilizer as the light stabilizer, it is possible to improve the weather resistance of the obtained photochromic optical material.

Such light stabilizers include bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, di ( 1,2,2,6,6-pentamethyl-4-piperidyl) -butyl (3'-5'-ditert-butyl-4-hydroxybenzyl) malonate, 1- {2- [3- (3,5- Di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl} -4-
[3- (3,5-ditert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, poly {[6-((1,1,3,3-tetra Methylbutyl) amino) -1,3,5-triazine-2,4-diyl] [1,6- (2,
2,6,6-tetramethyl-4-piperidinyl) aminohexamethylene], poly {[6- (morpholino) -S-triazine-2,4
-Diyl] [1,6- (2,2,6,6-tetramethyl-4-piperidyl) amino] hexamethylene}, 4-hydroxy-
A dimethyl succinate polymer with 2,2,6,6-tetramethyl-1-piperidinethanol and other commercially available products can be usefully used.

The light stabilizer is used in an amount of 0.01 to 50 parts by weight, preferably 0.01 to 30 parts by weight, based on 100 parts by weight of the solid medium.

Further, the addition of the singlet oxygen quencher is effective in improving the repetition durability of the spirooxazine compound in the coloring state since the singlet oxygen quencher suppresses the adverse effect of oxygen on the coloring mechanism of the spirooxazine compound. It is.

Specific examples of such a singlet oxygen quencher include β-
Examples include carotene, various Schiff base Ni (II) complexes, amine compounds such as 1,4-diazabicyclo [2,2,2] octane, triethylamine, and phenol compounds. Of these, amine compounds and phenol compounds can be preferably used because the singlet oxygen quenching coefficient is slightly reduced but does not have absorption in the visible region. The addition amount of the singlet oxygen quencher is desirably as large as possible, and is used in the range of 0.1 to 100 parts by weight, preferably 0.5 to 50 parts by weight, based on 100 parts by weight of the solid medium.

〔The invention's effect〕

Since the photochromic compound of the present invention is composed of a spirooxazine compound having a specific chemical structure, the specificity of the photochromic compound stabilizes the color development and, as is clear from the description of the examples described later, increases the color development. It has a good concentration of color and has a good color repetition durability even at a high temperature of room temperature or higher.

Therefore, the photochromic compound of the present invention is suitably used for various displays, memories, light control lenses, light control filters, optical materials for optical devices such as light meters, and the like, utilizing the above-described properties. be able to.

Hereinafter, examples of the present invention will be described, but the present invention is not limited thereto. The measurement of the light transmittance in each of the examples and the comparative examples was performed using light having a wavelength at which the change in the light transmittance was maximized.

Example 1 [Synthesis Example] 1,3,3-trimethylspiro [piperidine-2,3 '-(3H)
-Pyrido (3,4-f) (1,4) benzoxazine] 5.61 g of 1,3,3-trimethyl-2-methylenepiperidine
And 6.97 g of 8-nitroso-7-isoquinolinol were dissolved in 200 ml of toluene.
The reaction was carried out by refluxing at the boiling point for an hour.

After completion of the reaction, the solvent was concentrated, and separation was performed by column chromatography using silica gel as a carrier and a mixed solvent of ethyl acetate and hexane as a developing solvent. After the developing solvent was distilled off, the obtained solid was purified by a recrystallization method using a mixed solvent of acetone and hexane to obtain 1.26 g of a white powder.

This compound has a nuclear magnetic resonance spectroscopy (NMR) spectrum,
By infrared absorption spectrum and CHN elemental analysis, 1,3,3
-Trimethylspiro [piperidine-2,3 '-(3H) -pyrido (3,4-f) (1,4) benzoxazine].

The result of elemental analysis was as follows: 73.17% by weight of carbon, 7.25% of hydrogen
% By weight, 14.11% by weight of nitrogen, which is almost the same as the calculated value of 73.19% by weight of carbon, 7.17% by weight of hydrogen and 14.23% by weight of nitrogen, and the NMR spectrum is 0.9-3.
0 ppm (15H) and 7.0 to 10.0 ppm (6H).

[Application example]

1,3,3-trimethylspiro [piperidine-2,3 '-(3
H) -pyrido (3,4-f) (1,4) benzoxazine] 4.0
The weight part was dissolved in 100 parts by weight of methyl ethyl ketone together with 60 parts by weight of an epoxy resin precursor "Eponix # 1100 Clear" (manufactured by Dainippon Paint Co., Ltd.) to obtain a coating solution.

This coating solution is applied to the surface of the slide glass by a dipping method, and methyl ethyl ketone is evaporated at 40 ° C. until the tackiness of the coated surface is lost, and then cured at 80 ° C. for 16 hours to obtain a slightly red color of 10 μm. A tinged photochromic film was produced.

When this film is irradiated with ultraviolet light, it develops a color, and the change in the transmittance of light having a wavelength of 578 nm is caused at room temperature by
It was 92% before ultraviolet irradiation, and dropped to 51% after 5 minutes of ultraviolet irradiation.

Thereafter, when the film was placed in a dark place, the light transmittance returned to the original state.

Example 2 [Synthesis Example] 1,3,3-trimethylspiro [piperidine-2,3 '-(3H)
-Pyrido (3,2-f) (1,4) benzoxazine] 5.61 g of 1,3,3-trimethyl-2-methylenepiperidine
And 6.97 g of 5-nitroso-6-quinolinol were dissolved in 200 ml of toluene, and the mixture was reacted at a boiling point of reflux for 8 hours in a nitrogen gas atmosphere.

After completion of the reaction, the solvent was concentrated, and separation was performed by column chromatography using silica gel as a carrier and a mixed solvent of ethyl acetate and hexane as a developing solvent. After the developing solvent was distilled off, the obtained solid was purified by a recrystallization method using a mixed solvent of acetone and hexane to obtain 0.88 g of a white powder.

This compound was analyzed for its 1,3,3-trimethylspiro [piperidine-2,3 '-(3H) -pyrido (3,2-f) (1,2-f) by NMR spectrum, infrared absorption spectrum and CHN elemental analysis.
4) Benzoxazine].

The result of elemental analysis was as follows: 73.11% by weight of carbon, 7.33% of hydrogen
% Of nitrogen and 14.35% by weight of nitrogen, which are almost the same as the calculated values of 73.19% by weight of carbon, 7.17% by weight of hydrogen and 14.23% by weight of nitrogen, and the NMR spectrum is 0.9-3.
It was 0 ppm (15H) and 7.0 to 9.0 ppm (6H).

[Application example]

1,3,3-trimethylspiro [piperidine-2,3 '-(3
H) -pyrido (3,4-f) (1,4) benzoxazine] 4.0
Except that 4.0 parts by weight of 1,3,3-trimethylspiro [piperidine-2,3 '-(3H) -pyrido (3,2-f) (1,4) benzoxazine] was used instead of parts by weight. Example 1
A slightly reddish photochromic film having a thickness of 10 μm was prepared in exactly the same manner as described above.

When this film is irradiated with ultraviolet light, it develops a color, and the change in the transmittance of light having a wavelength of 578 nm is caused at room temperature by
It was 92% before ultraviolet irradiation, and dropped to 60% after 5 minutes of ultraviolet irradiation time.

Thereafter, when the film was placed in a dark place, the light transmittance returned to the original state.

Comparative Example 1 1,3,3-trimethylspiro [piperidine-2,3 '-(3
H) -pyrido (3,4-f) (1,4) benzoxazine] 4.0
Except that 4.0 parts by weight of 1,3,3-trimethylspiro [piperidine-2,3 '-(3H) -naphtho (2,1-b) (1,4) oxazine] was used instead of parts by weight. A colorless photochromic film having a thickness of 10 μm was produced in exactly the same manner as in Example 1.

When this film was irradiated with ultraviolet light, it developed color.
At room temperature, the change in the transmittance of the 578 nm light beam was 92% before the UV irradiation, and only dropped to 84% after 5 minutes of the UV irradiation time.

Example 3 [Synthesis Example] 1-benzyl-3,3-dimethylspiro [piperidine-2,
Synthesis of 3 '-(3H) -pyrido (3,4-f) (1,4) benzoxazine] 5.92 g of 1-benzyl-2,3,3-trimethylpiperidinium bromide and 8-nitroso-7- Isoquinolinol
3.48 g of triethylamine and 4.0 g of triethylamine were dissolved in 150 ml of toluene, and the mixture was reacted at a boiling point of reflux for 6 hours in a nitrogen gas atmosphere.

After the completion of the reaction, the solvent was concentrated, and the precipitated yellow-brown crystals were separated and washed with a small amount of ethyl alcohol. The obtained powder was purified by a recrystallization method using ethyl alcohol to obtain 1.1 g of a pale yellow powder.

This compound was analyzed by NMR spectrum, infrared absorption spectrum and CHN elemental analysis to obtain 1-benzyl-3,3-dimethylspiro [piperidine-2,3 ′-(3H) -pyrido (3,4
-F) (1,4) benzoxazine].

The result of elemental analysis was as follows: 77.58% by weight of carbon, 6.97% of hydrogen
% Of nitrogen and 11.20% by weight of nitrogen, which are almost the same as the calculated values of 77.60% by weight of carbon, 6.78% by weight of hydrogen and 11.31% by weight of nitrogen, and the NMR spectrum is 0.9 to 3.
They were 0 ppm (12H), 4.4 ppm (2H), and 7.0 to 10.0 ppm (11H).

[Application example]

26.97 parts by weight of 2-hydroxyethyl methacrylate, 23.03 parts by weight of isophorone diisocyanate,
To 50 parts by weight of ethylhexyl methacrylate, 5 parts by weight of 2,6-ditert-butyl-p-cresol as an antioxidant, and 0.05 part by weight of di-n-butyltin dilaurate, which is a urethanation catalyst, were added. The urethanization reaction was performed at 60 ° C. for 3 hours.

To the urethane monomer composition thus obtained, 1
-Benzyl-3,3-dimethylspiro [piperidine-2,3 '
-3H) -pyrido (3,4-f) (1,4) benzoxazine]
0.1 parts by weight and 1- which is a hindered amine light stabilizer
{2- [3- (3,5-ditert-butyl-4-hydroxyphenyl) propionyloxy] ethyl} -4- [3-
(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine "Sanol LS-2626" (manufactured by Sankyo Co., Ltd.) in an amount of 0.5 part by weight. After mixing, 1 part by weight of tert-butyl peroxypiparate was added as a polymerization initiator to obtain a monomer composition solution containing a photochromic compound.

This monomer composition solution was poured into a glass mold for producing a lens, and was heated at 50 ° C. for 10 hours, at 60 ° C. for 5 hours, and at 80 ° C. for 2 hours.
The polymerization was carried out by gradually raising the polymerization temperature to 100 ° C. for 1 hour, producing a slightly reddish lens having a center thickness of 1.3 mm.

When this lens is irradiated with ultraviolet light, it develops color, and the change in transmittance of light with a wavelength of 575 nm caused by this is 89% at room temperature before UV irradiation and decreases to 55% after 5 minutes of UV irradiation time. did.

Thereafter, when the lens was placed in a dark place, the transmittance of the light beam returned to the original state.

Example 4 1-Cyclohexylmethyl-3,3-, dimethylspiro [piperidine-2,3 '-(3H) -pyrido (3,4-f) (1,4
4) Synthesis of benzoxazine] 4.43 g of 1-cyclohexylmethyl-3,3-dimethyl-2-methylenepiperidine and 3.48 g of 8-nitroso-7-isoquinolinol were dissolved in 100 ml of toluene, and this was dissolved in a nitrogen gas atmosphere. At reflux for 6 hours.

After the completion of the reaction, the solution was allowed to cool, filtered to remove insolubles, and then concentrated to obtain a black-brown viscous liquid.Next, a hexane-soluble component was extracted from this liquid, and further concentrated, and then acetone and Purification by a recrystallization method using a mixed solvent with hexane gave 1.3 g of a white powder.

This compound was analyzed by NMR spectrum, infrared absorption spectrum and CHN elemental analysis to find 1-cyclohexylmethyl-3,3-dimethylspiro [piperidine-2,3 '-(3H)
-Pyrido (3,4-f) (1,4) benzoxazine].

The result of elemental analysis was as follows: 76.29% by weight of carbon, 8.51% of hydrogen
% Of nitrogen, 11.02% by weight of nitrogen, which are almost the same as the calculated values of 76.35% by weight of carbon, 8.28% by weight of hydrogen and 11.13% by weight of nitrogen, and the NMR spectrum is 0.8 to 3.
0 ppm (25H) and 7.0 to 10.0 ppm (6H).

[Application example]

1-benzyl-3,3-dimethylspiro [piperidine-
2,3 '-(3H) -pyrido (3,4-f) (1,4) benzoxazine] and 0.1 part by weight of a hindered amine light stabilizer instead of 1 part by weight of 1-cyclohexylmethyl-3,3- Dimethylspiro [piperidine-2,3 ′-(3H) -pyrido (3,4-f) (1,4) benzoxazine] Saga
A 1.3mm slightly reddish lens was produced.

When this lens is irradiated with ultraviolet light, it develops color, and the change in transmittance of light with a wavelength of 575 nm is 85% at room temperature before ultraviolet light irradiation, and decreases to 31% after 5 minutes of ultraviolet light irradiation time at room temperature. did.

Thereafter, when the lens was placed in a dark place, the transmittance of the light beam returned to the original state.

Example 5 [Synthesis Example] 1,1 ″-(1,6-hexanediyl) bis [3,3-dimethylspiro [piperidine-2,3 ′-(3H) -pyrido (3,4-
f) Synthesis of (1,4) benzoxazine]] 3.31 g of 1,1 ″-(1,6-hexanediyl) bis [3,3-dimethyl-2-methylenepiperidine] and 8-nitroso-7-iso 3.48 g of quinolinol was dissolved in 100 ml of toluene, and the mixture was reacted at a boiling point of reflux for 8 hours in a nitrogen gas atmosphere.

After completion of the reaction, the solvent was concentrated, and separation was performed by column chromatography using silica gel as a carrier and a mixed solvent of ethyl acetate and hexane as a developing solvent. After the developing solvent was distilled off, the obtained solid was purified by a recrystallization method using a mixed solvent of acetone and hexane to obtain 0.55 g of a pale yellow powder.

This compound was analyzed by NMR spectrum, infrared absorption spectrum and CHN elemental analysis to find 1,1 ″-(1,6-hexanediyl) bis [3,3-dimethylspiro [piperidine-2,
3 '-(3H) -pyrido (3,4-f) (1,4) benzoxazine]].

The results of elemental analysis were as follows: 74.45% by weight of carbon, 7.68% of hydrogen
% Of nitrogen and 12.95% by weight of nitrogen, which are almost the same as the calculated values of 74.50% by weight of carbon, 7.50% by weight of hydrogen and 13.03% by weight of nitrogen, and the NMR spectrum is 0.9-3.
They were 0 ppm (32H), 3.2 ppm (4H), and 7.0 to 10.0 ppm (12H).

[Application example]

1,3,3-trimethylspiro [piperidine-2,3 '-(3
H) -pyrido (3,4-f) (1,4) benzoxazine] 4.0
Instead of parts by weight, 1,1 ″-(1,6-hexanediyl) bis [3,3-dimethylspiro [piperidine-2,3 ′-(3H)-
Pyrido (3,4-f) (1,4) benzoxazine]] except that 4.0 parts by weight were used.
A 10 μm slightly reddish photochromic film was produced.

When this film is irradiated with ultraviolet light, it develops a color, and the change in the transmittance of light having a wavelength of 578 nm is caused at room temperature by
It was 89% before UV irradiation, and dropped to 44% after 5 minutes of UV irradiation time.

Thereafter, when the film was placed in a dark place, the light transmittance returned to the original state.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ identification code FI C07D 265: 00) (C07D 519/00 498: 20) (58) Fields investigated (Int.Cl. ⁶ , DB name) C07D 498 / 20 C07D 519/00 C09K 9/02 CA (STN) REGISTRY (STN)

Claims (4)

(57) [Claims] 1. A photochromic compound comprising a spirooxazine compound represented by the following general formula (I). (In the formula, A ¹ represents an alkyl group having 1 to 24 carbon atoms, an allyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryloxyalkyl group or an alkoxyalkyl group, and R ^{1 to} R ⁸ represent A hydrogen atom, a linear or branched alkyl group, R ⁹ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group or an alkoxyalkyl group, one of X and Y represents a nitrogen atom, and the other represents It represents a methine group.) 2. The photochromic compound according to claim 1, comprising a spirooxazine compound represented by the following general formula (IA). (In the formula, A ¹ represents an alkyl group having 1 to 24 carbon atoms, an allyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryloxyalkyl group or an alkoxyalkyl group, and R ¹ and R ² represent An alkyl group having 5 or less carbon atoms is shown.) 3. A photochromic compound comprising a spirooxazine compound represented by the following general formula (II). (Wherein A ² is an alkylene group, alkylene (polyoxy)
Represents an alkylene group or an alkylenearylalkylene group, R ^{1 to} R ⁸ represent a hydrogen atom, a linear or branched alkyl group, and R ⁹ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group or an alkoxyalkyl And one of X and Y represents a nitrogen atom, and the other represents a methine group. ) 4. The photochromic compound according to claim 3, comprising a spirooxazine compound represented by the following general formula (II-A). (Wherein A ² is an alkylene group, alkylene (polyoxy)
It represents an alkylene group or an alkylenearylalkylene group, and R ¹ and R ² represent an alkyl group having 5 or less carbon atoms. )