JPH07165762A - Photochromic substance and material therefor - Google Patents

Abstract

PURPOSE:To obtain a photochromic substance good in compatibility with and solubility to resins and the weatherability for color development and fading when exposed to light, high in photosensitivity, good in contrast, presenting great developed color deepness, thus useful for printing, optical instruments, etc. CONSTITUTION:A compound of formula I [R<1>-R<6> are each H, Cl, Br, nitro, methoxy or an 1-4C alkyl; R<7> is an 1-8C alkyl or a (substituted)benzyl; R<8> is a 2-12C heterocyclic compound (except piperidine) whose linkage part is a tertiary amine, and at a part where is other than the linkage part, one or two N atom(s) or one O or S atom may exist, and alkyl group(s) may be substituted at the heterocycle], e.g. a compound of formula II. The compound of formula I is obtained, for example, by the following processes: a halogen compound is reacted with a starting material of formula III, and the reactional product is reacted with a basic substance such as a tertiary amine to produce a compound of formula IV; in a separate procedure, 1-nitroso-2-naphthol and a heterocyclic compound are dissolved in a solvent to form a solution, and the compound of the formula IV is reacted with this solution under reflux.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to novel photochromic materials and materials. In particular, it relates to novel spirooxazine-based photochromic substances and materials.

[0002]

2. Description of the Related Art Photochromic materials obtained by blending a photochromic substance with a resin are used for printing, optical devices, recording materials, clothing, ornaments and the like.

Typical compounds of photochromic substances include spiropyran compounds, and many compounds (GH Brown “photochromism”, Wiley Innterscien).
ce, New York (1971)) is known. However,
Photochromic materials using spiropyran compounds are
There is a problem in light resistance in repeated use of coloring and erasing by light (ultraviolet rays) (hereinafter, referred to as light erasing and erasing).

As photochromic substances having improved light resistance of photo-bleaching and decoloring, JP-B-45-28892, JP-B-49-48631, JP-A-48-23787, JP-A-55-36284 and JP-A-55-36284 are disclosed. 61-501145,
JP-A-62-145089 and JP-B-2-14284 describe 1,3,3-trimethylspiro [indoline-2,3 ′].
Disclosed are-[3H] -naphtho [2,1-b] (1,4) oxazines] and their substituted isomers, spirooxazine compounds.

Although the photochromic material using a spirooxazine compound has improved light fastness in light emission and decoloration compared to the spiropyran compound, it is still insufficient. Further, since the spirooxazine compound has insufficient compatibility and solubility with the resin and the concentration at the time of blending cannot be increased, the photochromic material obtained has insufficient photosensitivity.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to solve such problems and to provide a novel photochromic substance having good compatibility and solubility with a resin, and at the same time, exhibiting photobleaching and erasing properties. To provide a photochromic material having good light resistance, high photosensitivity, good contrast, and high color density.

[0007]

As a result of intensive studies, the present inventors have found a novel spirooxazine-based photochromic substance that solves the above-mentioned problems, and have prepared a photochromic material containing the same in a transparent resin. Thus, the present invention has been completed.

That is, the present invention is a spirooxazine-based photochromic substance represented by the general formula <A>,
Further, it is a photochromic material containing a spirooxazine-based photochromic substance represented by the general formula <A> and a transparent resin. Furthermore, the spirooxazine-based photochromic substance having the thermochromic property represented by the general formula <A>, or the photochromic substance having the thermochromic property containing the spirooxazine-based photochromic substance represented by the general formula <A> and a transparent resin is also included. It is a material.

[0009]

[Chemical 2]

In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are
It represents a hydrogen atom, a chlorine atom, a bromine atom, a nitro group, a methoxy group or an alkyl group having 1 to 4 carbon atoms.

Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n
-Butyl group, isobutyl group, sec-butyl group, tert-butyl group and the like.

R ⁷ is an alkyl group having 1 to 8 carbon atoms, or an unsubstituted benzyl group, a chlorine atom, a bromine atom,
It represents a benzyl group having one substituent such as a nitro group and a methoxy group.

Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group and n-
Butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tret-pentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, Examples thereof include a cyclohexyl group.

R ⁸ is a heterocyclic compound having 2 to 12 carbon atoms (excluding piperidine) whose connecting portion is a tertiary amine,
There may be one or two nitrogen atoms, or one oxygen atom or sulfur atom other than the linking portion, and the heterocycle may be substituted with an alkyl group.

Examples of the heterocyclic compound of R ⁸ are shown below.

[0016]

[Chemical 3]

[0017]

[Chemical 4]

Representative examples of the spirooxazine-based photochromic substance of the present invention are shown below. The present invention is not limited to these examples.

[0019]

[Chemical 5]

[0020]

[Chemical 6]

[0021]

[Chemical 7]

The spirooxazine-based photochromic substance of the present invention can be obtained, for example, by the following steps.

[0023]

[Chemical 8]

In the first step, the compound represented by the general formula <B> is reacted with a halide to obtain the compound represented by the general formula <C>. The compound represented by the general formula <C> goes to the second step without isolation.

In the second step, the compound represented by the general formula <C> is reacted with a basic substance such as a tertiary amine to give a compound represented by the general formula <
D> to obtain a compound, which is concentrated, extracted, washed, dehydrated,
After performing operations such as concentration, isolation is performed and the process proceeds to the third step.

In the third step, 1-nitroso-2-naphthol and the heterocyclic compound are dissolved, and the compound of the general formula <D> is refluxed.
The compound represented by is added and reacted to obtain a spirooxazine-based photochromic substance represented by the general formula <A>.

The above reaction is usually carried out in an alcohol solvent such as methanol, ethanol, propanol or butanol,
It is carried out at a temperature of 0 to 120 ° C. in the presence of a polar or nonpolar solvent such as an aromatic hydrocarbon solvent such as toluene or xylene or a halogenated hydrocarbon solvent such as dichloromethane, trichloroethane or trichloroethylene.

As a method for purifying the spirooxazine-based photochromic substance of the present invention, separation by column chromatography using a column packed with alumina, silica gel or the like, activated carbon treatment and the like are preferable.

Further, the spirooxazine-based photochromic material of the present invention has the general formula <
Instead of the compound represented by D>, 2-methyleneindolenine compound was used as a starting material, and 1-nitroso-2-
It can also be obtained by reacting with naphthol and a heterocyclic compound.

The spirooxazine-based photochromic substance of the present invention is mixed with an optically transparent resin and used as a photochromic material.

The transparent resin used in the present invention includes polyurethane; nylon; urethane-modified diacrylate polymer of bisphenol A, urethane-modified diacrylate polymer of halogenated bisphenol A, urethane-modified dimethacrylate polymer of bisphenol A, halogenated bisphenol A. Urethane-modified dimethacrylate polymer and copolymer thereof; bisphenol A diacrylate polymer, halogenated bisphenol A diacrylate polymer, bisphenol A dimethacrylate polymer, halogenated bisphenol A dimethacrylate polymer and copolymer thereof; epoxy, Polystyrene and its copolymers; Polycarbonate; Polyester; Polyvinyl butyral; Polyvinyl alcohol; Polyvinyl acetate; Loin like; polyacrylates, polymethacrylates and copolymers thereof; diethylene glycol bis acrylic carbonate polymer and the like.

The amount of the spirooxazine-based photochromic substance of the present invention to be incorporated in the transparent resin varies depending on the purpose and application, but from the viewpoint of visual sensitivity, 0.01 to 50 parts by weight, preferably 100 parts by weight of the transparent resin is preferable. Is 0.5 ~
40 parts by weight.

The photochromic material of the present invention can be obtained by the following method, as in the case of obtaining a normal photochromic material.

Method 1 The spirooxazine-based photochromic substance of the present invention is mixed with a transparent resin, and the mixture is prepared by a method such as melting or casting.
It is formed into a film, a plate, or any other desired form to produce a photochromic material which itself has a photochromic effect.

Method 2 A solution of the spirooxazine-based photochromic substance of the present invention and a transparent resin dissolved in a suitable solvent is applied as a coating solution to a substrate made of various optical materials, the solvent is removed, and then the photochromic on the substrate. The layers are formed to produce a photochromic material such as a lens having a photochromic layer.

Method 3 The solution obtained by the above Method 2 is cast to prepare a film-shaped photochromic material.

Method 4 In Methods 2 and 3, the spirooxazine-based photochromic substance and the transparent resin of the present invention are dispersed in a dispersion medium used instead of a solvent, and a photochromic material is prepared by using the dispersion medium.

Method 5 In Methods 1 to 4, a transparent monomer is used in place of a part or all of the transparent resin to form a photochromic material, and then a polymerization treatment is further performed.

In addition, microcapsules can be obtained using the spirooxazine-based photochromic substance of the present invention as a core substance and used as an ink having photochromic properties.

Further, in the above method, a light stabilizer,
It is also possible to add a quencher, an antioxidant, an ultraviolet absorber for blocking unnecessary light in the short wavelength region, and the like.

By using a hindered amine-based light stabilizer as the light stabilizer, the light resistance of the obtained photochromic material can be improved. The amount of the light stabilizer used in the present invention is 0.0 with respect to 100 parts by weight of the transparent resin.
1 to 30 parts by weight.

Further, the addition of the singlet oxygen quencher suppresses the adverse effect of oxygen on the coloring mechanism of the spirooxazine-based photochromic substance of the present invention, and is effective in improving the durability of light coloring and quenching. Such singlet oxygen quenchers include various Schiff bases Ni (II), β-carotene, 1,
Examples include 4-diazabicyclo [2,2,2] octane, tertiary amines such as triethylamine, and phenol compounds. The amount of the singlet oxygen quencher used in the present invention is 0.5 to 50 parts by weight based on 100 parts by weight of the transparent resin.

The material in which the spirooxazine-based photochromic substance of the present invention is mixed with a transparent resin is used as a photochromic material having photobleaching / decoloring properties in sunglasses lenses, ski goggles, lenses for protective glasses, curtains, clothes, toys and the like. Used.

[0044]

EXAMPLES The present invention will now be described with reference to examples. "Parts" in the examples represent "parts by weight". The present invention is not limited to the examples.

Example 1 5.0 g of 1-nitroso-2-naphthol under a nitrogen stream, 1,
7.6 g of 2,3,4-tetrahydroquinoline was dissolved in 40 ml of trichloroethylene under reflux at a temperature of 86 ° C., and then 1,3,
30 ml of a trichloroethylene solution of 3-trimethyl-2-methyleneindolenin was added dropwise under reflux at a temperature of 86 ° C. over 1 hour. Then, after reacting at a temperature of 86 ° C for 2 hours,
Trichloroethylene was distilled off, and methanol was added to precipitate crystals. This crystal was passed through a silica gel column with chloroform, separated and purified, and then recrystallized with methanol to obtain a pale green crystal having a melting point of 134 to 136 ° C.

From the NMR spectrum, elemental analysis and infrared absorption spectrum, the obtained crystals were 1,3,3-trimethylspiro [indoline-2 '-[1- (1,2,3,4-
Tetrahydroquinolyl)]-2,3 '-[3H] -naphtho [2,1-b] (1,4) oxazine], compound <1>.

Example 2 A coating solution prepared by dissolving 2 parts of the compound <1> obtained in Example 1 and 16 parts of polymethacrylate in 100 parts of 2-butanone was prepared.
After coating on a glass plate with a bar coater, it was dried at a temperature of 50 ° C. to obtain a transparent film having a thickness of 20 μm. It was confirmed that the obtained transparent film rapidly developed color when exposed to sunlight, and immediately returned to colorless when placed in a dark place, and had excellent photochromic properties. Wavelength of the obtained film is 400 ~ 7
The initial transmittance at 00 nm (hereinafter abbreviated as initial transmittance) is
The average was 50%. Further, as a light resistance test, after continuously irradiating with a carbon arc lamp for 50 hours using a fade meter, the color was developed and the transmittance was measured. The transmittance ratio expressed by the ratio between the transmittance at the time of color development after irradiation and the initial transmittance is 80
% Or more. The results are shown in Table 1.

Example 3 In Example 2, the compound <1> 2 obtained in Example 1 was used.
A 20 μm-thick transparent film was obtained in the same manner as in Example 2 except that 6.5 parts were used instead of the parts. The obtained film had an average initial transmittance of 49% and a transmittance ratio of 80% or more. The results are shown in Table 1.

Example 4 In Example 2, the compound <1> 2 obtained in Example 1 was used.
A transparent film having a thickness of 20 μm was obtained in the same manner as in Example 2 except that 0.08 part was used instead of the part. The obtained film had an average initial transmittance of 60% and a transmittance ratio of 70% or more. The results are shown in Table 1.

Example 5 2 parts of the compound <1> obtained in Example 1 and 16 parts of polymethacrylate were dissolved in 100 parts of 2-butanone, and then the hindered amine light stabilizer Sanol LS-770 (Sankyo Co., Ltd.) was used.
0.5 parts (registered trademark) was added to prepare a coating solution. After coating this coating solution on a glass plate with a bar coater, the temperature is 50 ° C.
After drying, a transparent film having a thickness of 20 μm was obtained. The film obtained is
The initial transmittance was 50% on average and the transmittance ratio was 90% or more.
The results are shown in Table 1.

Example 6 Under a nitrogen stream, 5.0 g of 1-nitroso-2-naphthol and 5.0 g of morpholine were dissolved in 40 ml of trichlorethylene at a temperature of 86 ° C. under reflux and then 1,3,3-trimethyl-2-methylene. 30 ml of a solution of indolenine in trichlorethylene,
Under reflux, the mixture was added dropwise at a temperature of 86 ° C. over 1 hour. Then, after reacting at a temperature of 86 ° C. for 2 hours, trichloroethylene was distilled off and methanol was added to precipitate crystals. This crystal was passed through a silica gel column with chloroform, separated and purified, and then recrystallized with methanol to obtain a pale yellow crystal having a melting point of 119 to 121 ° C.

According to NMR spectrum, elemental analysis and infrared absorption spectrum, the obtained crystal was 1,3,3-trimethylspiro [indoline-2 '-(1-morpholino)-
It was 2,3 ′-[3H] -naphtho [2,1-b] (1,4) oxazine], compound <2>.

Example 7 The same as Example 2 except that 2 parts of the compound <2> obtained in Example 6 was used in place of the compound <1> obtained in Example 1 in Example 2. A transparent film having a thickness of 20 μm was obtained. The obtained film had an average initial transmittance of 52% and a transmittance ratio of 90% or more. The results are shown in Table 1.

Example 8 0.2 part of the compound <2> obtained in Example 6 was mixed with 50 parts of toluene.
Part and 50 parts of isopropanol, and then 20 parts of polyvinyl butyral was added to prepare a coating solution. After coating this coating solution on a glass plate with a bar coater,
It was dried at 80 ° C. to obtain a transparent film having a thickness of 20 μm. The obtained film had an average initial transmittance of 61% and a transmittance ratio of 90% or more. The results are shown in Table 1.

Further, the obtained film was colorless and transparent at room temperature, but rapidly developed color when heated to a temperature of 100 ° C., rapidly discolored when returned to room temperature and became colorless and transparent, showing thermochromic properties.

Example 9 0.2 part of the compound <2> obtained in Example 6 was mixed with 50 parts of toluene.
After dissolving in a solution of 1 part and 50 parts of isopropanol, 20 parts of polyvinyl butyral was added, and 0.5 part of N, N-dimethylaniline as a singlet oxygen quencher was added to prepare a coating solution. This coating solution was applied on a glass plate with a bar coater and then dried at a temperature of 80 ° C. to obtain a transparent film having a thickness of 20 μm. The obtained film had an average initial transmittance of 61% and a transmittance ratio of 90% or more. The results are shown in Table 1.

The obtained film was colorless and transparent at room temperature, but it rapidly developed color when heated to a temperature of 100 ° C., rapidly disappeared when returned to room temperature and became colorless and transparent, showing thermochromic properties.

Example 10 Under a nitrogen stream, 5.0 g of 1-nitroso-2-naphthol and 7.0 g of pyrrole were refluxed at a temperature of 110 ° C. and dried with 50 ml of toluene.
1-benzyl-3,3-dimethyl-2-
30 ml of a toluene solution of methylene indolenine is refluxed,
The mixture was added dropwise at a temperature of 110 ° C over 1 hour. After that, the temperature is 110 ℃
After reacting for 2 hours with toluene, toluene was distilled off, and methanol was added to precipitate crystals. The crystals were passed through a silica gel column with chloroform and separated and purified to obtain almost colorless crystals.

From the NMR spectrum, elemental analysis and infrared absorption spectrum, the obtained crystal was 1-benzyl-
3,3-Dimethylspiro [indoline-2 '-(1-pyrrolyl) -2,3'-[3H] -naphtho [2,1-b] (1,
4) Oxazine] and compound <5>.

Example 11 The same as Example 2 except that 2 parts of the compound <5> obtained in Example 10 was used in place of the compound <1> obtained in Example 1 in Example 2. A transparent film having a thickness of 20 μm was obtained. The obtained film had an average initial transmittance of 51% and a transmittance ratio of 80% or more. The results are shown in Table 2.

Example 12 6 parts of the compound <5> obtained in Example 10 and epoxy resin precursor Eponix # 1100 clear (Dainippon Paint Co., Ltd.)
A coating solution prepared by dissolving 60 parts (registered trademark) in 100 parts of methyl ethyl ketone was applied on a glass plate with a bar coater, dried at a temperature of 40 ° C, and then cured at a temperature of 80 ° C for 16 hours to give a thick film. A transparent film having a size of 10 μm was obtained. The obtained film had an average initial transmittance of 68% and a transmittance ratio of 80% or more. The results are shown in Table 2.

Example 13 In Example 12, the compound <5 obtained in Example 10 was used.
A transparent film having a thickness of 20 μm was obtained in the same manner as in Example 12 except that 2 parts were used instead of> 6 parts. The obtained film had an average initial transmittance of 72% and a transmittance ratio of 75% or more. The results are shown in Table 2.

Example 14 Under a stream of nitrogen, 7.3 g of 7-bromo-1-nitroso-2-naphthol and 6.0 g of N-methyl-piperazine were dissolved in 50 ml of dry toluene at a temperature of 110 ° C. under reflux, and then 1. 3, 3, 5,
30 ml of a toluene solution of 6-pentamethyl-2-methyleneindolenin was added dropwise under reflux at a temperature of 110 ° C. over 1 hour. Then, after reacting at a temperature of 110 ° C. for 2 hours, toluene was distilled off and methanol was added to precipitate crystals.
Pass this crystal through a silica gel column with chloroform,
Separation and purification gave almost colorless crystals.

The crystal obtained from the NMR spectrum, elemental analysis and infrared absorption spectrum was the compound <11>.

Example 15 The same as Example 2 except that 6.5 parts of the compound <11> obtained in Example 14 was used in place of the compound <1> obtained in Example 1 in Example 2. A transparent film having a thickness of 20 μm was obtained. The obtained film had an average initial transmittance of 52% and a transmittance ratio of 85% or more. The results are shown in Table 2.

Example 16 The same as Example 2 except that 2 parts of the compound <11> obtained in Example 14 was used in place of the compound <1> obtained in Example 1 in Example 2. A transparent film having a thickness of 20 μm was obtained. The obtained film had an average initial transmittance of 51% and a transmittance ratio of 85% or more. The results are shown in Table 2.

Comparative Example 1 In Example 2, instead of the compound <1> obtained in Example 1, 1,3,3-trimethylspiro [indoline-
A membrane was prepared in the same manner as in Example 2 except that 6.5 parts of 2,3 ′-[3H] -naphtho [2,1-b] (1,4) oxazine] was used. Crystals precipitated and became cloudy, and a transparent film could not be obtained. The results are shown in Table 3.

Comparative Example 2 In Example 2, instead of the compound <1> obtained in Example 1, 1,3,3-trimethylspiro [indoline-
Example 2 was repeated except that 2 parts of 2,3 ′-[3H] -naphtho [2,1-b] (1,4) oxazine] was used.
A transparent film having a thickness of 20 μm was obtained. The obtained film had an average initial transmittance of 75% and a transmittance ratio of about 45%. The results are shown in Table 3.

Comparative Example 3 In Example 10, the compound <5> obtained in Example 9 was used.
Instead of 1,3,3-trimethylspiro [5-chloroindoline-2,3 '-[3H] -naphtho [2,1-b]
Example 1 except that 6 parts of (1,4) oxazine] were used.
A film was prepared in the same manner as in Example 0, but after removing the solvent, crystals were precipitated and a transparent film could not be obtained. The results are shown in Table 3.

Comparative Example 4 In Example 10, the compound <5> obtained in Example 9 was used.
Instead of 1,3,3-trimethylspiro [5-chloroindoline-2,3 '-[3H] -naphtho [2,1-b]
Example 1, except that 2 parts of (1,4) oxazine] were used.
In the same manner as in 0, a transparent film having a thickness of 20 μm was obtained. The obtained film had a transmittance ratio of 40% or less. The results are shown in Table 3.

[0071]

[Table 1]

[0072]

[Table 2]

[0073]

[Table 3]

[0074]

The photochromic material obtained by blending the spirooxazine-based photochromic substance of the present invention in a transparent resin is usually almost colorless (transparent), but it is light (ultraviolet).
It rapidly develops color upon irradiation with, and when the irradiation with light (ultraviolet light) is stopped, it immediately disappears and returns to the original colorless (transparent) color, which has a high speed of color development and decolorization, high color density, and excellent light resistance. It has photo-bleaching properties. Further, it also has a thermochromic property that it develops color by heating and disappears when cooled and returns to the original colorless (transparent).

Claims (15)

[Claims] 1. A spirooxazine-based photochromic substance represented by the general formula <A>. [Chemical 1] (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are hydrogen atoms,
Chlorine atom, bromine atom, nitro group, methoxy group, carbon number 1
To R 4 and R ⁷ represents an alkyl group having 1 to 8 carbon atoms, an unsubstituted benzyl group or a benzyl group having one substituent. R ⁸ is a heterocyclic compound having 2 to 12 carbon atoms (excluding piperidine) in which the connecting portion is a tertiary amine, and has 1 or 2 nitrogen atoms in addition to the connecting portion.
Or one oxygen atom or one sulfur atom may be present, and the heterocycle may be substituted with an alkyl group. ) 2. The spirooxazine-based photochromic substance according to claim 1, wherein R ⁷ is a linear or branched alkyl group having 1 to 8 carbon atoms. 3. The spirooxazine system according to claim 1, wherein R ⁷ is an unsubstituted benzyl group or a benzyl group having one substituent selected from the group consisting of chlorine atom, bromine atom, nitro group and methoxy group. Photochromic substance. 4. A heterocyclic compound having 4 to 12 carbon atoms in which R ⁸ is a tertiary amine in the connecting portion (excluding piperidine)
The spirooxazine-based photochromic substance according to claim 1, which is (one oxygen atom or sulfur atom may be present in addition to the connecting portion). 5. A hetero 5-membered ring compound having 2 to 4 carbon atoms (excluding piperidine) in which R ⁸ is a tertiary amine in the connecting part (one or two nitrogen atoms are present in the connecting part). The spirooxazine-based photochromic substance according to claim 1. 6. The spirooxazine-based photochromic material according to claim 1, which also has thermochromic properties. 7. A photochromic material containing the spirooxazine-based photochromic substance according to claim 1 and a transparent resin. 8. A photochromic material containing a spirooxazine-based photochromic material according to claim 1, which also has thermochromic properties, and a transparent resin. 9. A photochromic material containing the spirooxazine-based photochromic substance according to claim 1, a light stabilizer, and a transparent resin. 10. The spirooxazine-based photochromic substance according to claim 1, which also has thermochromic properties.
A photochromic material containing a light stabilizer and a transparent resin. 11. A photochromic material containing the spirooxazine-based photochromic substance according to claim 1, a singlet oxygen quencher and a transparent resin. 12. The spirooxazine-based photochromic substance according to claim 1, which also has thermochromic properties.
A photochromic material containing a singlet oxygen quencher and a transparent resin. 13. A photochromic material containing the spirooxazine-based photochromic substance according to claim 1, a light stabilizer, a singlet oxygen quencher and a transparent resin. 14. The spirooxazine-based photochromic material according to claim 1, which also has thermochromic properties.
A photochromic material containing a light stabilizer, a singlet oxygen quencher and a transparent resin. 15. The spirooxazine-based photochromic substance according to claim 1 is 0.0 per 100 parts by weight of the transparent resin.
1 to 50 parts by weight, any one of claims 7 to 14.
The photochromic material according to the item.