JPH0765035B2 - Photochromic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application] The present invention relates to a photochromic material,
More specifically, it relates to a photochromic material having a high elution resistance of the photochromic substance in a matrix made of a resin.

[Conventional technology]

In recent years, the use of photochromic substances that reversibly exhibit a change in color tone depending on the presence or absence of light irradiation has attracted attention in the fields of light control materials, recording materials, and the like. In particular, organic photochromic substances have a degree of change in color tone. It is considered to be useful because it is considerably large and has good dispersibility in organic materials such as various resins, but on the other hand, it has a fatal drawback that it has low repeatability of photochromic action. Therefore, it has not been put to practical use yet.

Among the conventionally known organic photochromic substances, those having relatively good repetition resistance of photochromic action include spironaphthoxazine compounds, for example, JP-B-45-28892 and JP-B-49.
-48631, JP-A-48-23783, JP-A-55-36
284, JP 60-53586, JP 60-112880
JP-A No. 61-138686 and 1,3,3-trimethylspiro [indoline-2,3 '-(3H) -naphtho [2,1-b] (1,4) oxazine] and Derivatives thereof have been disclosed, and attempts have been made to further improve the resistance to repeated photochromic action.

[Problems to be solved by the invention]

In order to obtain a practically useful photochromic material using such an organic photochromic substance, it is necessary to include the photochromic substance in a dispersed state in a matrix usually composed of a high molecular weight substance. Therefore, the actually obtained photochromic action is affected by the state of dispersion of the photochromic substance in the matrix. For this reason, a dispersion means capable of realizing an optimum dispersion state in order to obtain a good photochromic action has been sought, but an established one has not been known yet.

Specific means for dispersing the photochromic substance include A) means for incorporating an organic photochromic substance in the matrix by a kneading method or casting method, and B) a matrix having a high-density three-dimensional crosslinked structure,
Means for permeating an organic photochromic substance by diffusion and containing it. C) An organic photochromic substance is dispersed in a crosslinkable composition forming a high-density three-dimensional crosslinked structure, and the crosslinkable composition is crosslinked to form a tertiary structure. Means for fixing the organic photochromic substance in the matrix of the original network structure, D) The organic photochromic substance having a double bond is polymerized alone or in combination with other polymerizable monomers to form an organic compound in the polymer chain formed. A means for fixing the photochromic substance is considered to be general.

On the other hand, a photochromic substance has good resistance to repeated photochromic action, has high stability, easily undergoes reversible color tone change depending on the presence or absence of light irradiation, and when it is irradiated with light. It is basically required that the substance itself has excellent properties, such as that the colored species that occur in the matrix are sufficiently stable. In addition, in reality, the color tone changes due to light irradiation even when dispersed in the matrix. Is required, and the elution resistance is high, that is, the photochromic substance is not eluted from the matrix by a solvent or the like.

Considering the above-mentioned means A to D in consideration of such a request,
The means A and B have a problem in the elution resistance of the organic photochromic substance, and the means C also needs to have a considerably high crosslink density in order to prevent the elution of the photochromic substance. However, in such a matrix, the transformation function is well restricted by the light of the photochromic substance, the good photochromic action is not exhibited, and the degree of change in the obtained color tone is likely to be low. Further, in the means of C and D, since the photochromic substance is already contained in the crosslinkable composition or the polymerizable composition, the photochromic substance is deteriorated in the crosslinking or polymerization treatment, and the excellent photochromic property is lost. There is a possibility that For example, when a photochromic substance having a hydroxy group is present during the polymerization of allyl isocyanate or glycidyl methacrylate to perform a polymerization treatment, the photochromic substance reacts and bonds with the polymer, and it is possible to obtain excellent elution resistance. However, the photochromic compound may be deteriorated by radicals during the progress of polymerization, and a photochromic material having good characteristics cannot be obtained in this respect.

[Object of the Invention]

An object of the present invention is to provide a photochromic material in which a photochromic substance excellent in repeated photochromic action resistance is contained in a matrix made of a resin and which has high elution resistance of the photochromic substance.

[Means for solving problems]

The photochromic material of the present invention has the following general formula (I):
It is characterized by being obtained by reacting and curing the photochromic substance represented by (3) with an epoxy resin precursor or a urethane resin precursor.

[Wherein, a and b are each 0 or 1 and a + b
= 1 and R ₁ is a hydrogen atom, a halogen atom, a cyano group,
A lower alkyl group and a lower alkoxy group are shown, and R ₂ is a lower alkyl group, a lower alkoxyalkyl group, various substituted arylalkyl groups, and CH _{2 n} COOR. However, R shows a lower alkyl group and n shows the integer of 1-6. The photochromic substance used in the present invention is a spironaphthoxazine compound containing a nuclear-substituted hydroxy group. Since it has a group, by reacting with the epoxy group of the epoxy resin precursor or the isocyanuric group of the urethane resin precursor, it is contained in a state of being bonded to the epoxy resin or the urethane resin, respectively. As a result, the elution resistance of the photochromic substance becomes extremely high, and it is possible to obtain a photochromic material in which the photochromic substance does not elute with a solvent or the like. Moreover, in the reaction curing with the precursor of the epoxy resin or the precursor of the urethane resin, there are practically few factors that deteriorate the photochromic performance of the spironaphthoxazine compound used.

The photochromic material of the present invention can of course be obtained as a simple substance, but is particularly applicable and advantageous in a mode in which it is formed as a thin layer on the surface of various types of substrates that require a photochromic action. Here, the substrate can be selected from a wide range such as a decorative material, a recording material, an optical material, and the like.

The present invention will be specifically described below.

In the present invention, a spironaphthoxazine compound having a nucleus-substituted hydroxy group represented by the above general formula (I) is used as a photochromic substance.

A typical example of such a spironaphthooxysazine compound is 9'-hydroxy-1,3,3-trimethylspiro [indoline-2,3 '-(3H) -naphtho [2,1-b] (1 , 4) Oxazine], 9′-hydroxy-1-benzyl-3,3-dimethylspiro [indoline-2,3 ′-(3H) naphtho [2,1-b] (1,
4) Oxazine, 8'-hydroxyne-1,3,3-trimethylspiro [indoline-2,3 '(3H) -naphtho [2,1-b] (1,4) oxazine], 8'-hydroxy- 5-chloro-1,3,3-trimethylspiro [indoline-2,3 '-(3H) -naphtho [2,1-b]
(1,4) oxazine], 8'-hydroxy-1-benzyl-1,3,3-trimethylspiro [indoline-2,3 '-(3H) -naphtho [2,1-]
b] (1,4) oxazine], 7'-hydroxy-5-methoxy-1,3,3-trimethylspiro [indoline-2,3 '-(3H) naphtho [2,1-b]
(1,4) oxazine], 6′-hydroxy-1,3,3-trimethylspiro [indoline-2,3 ′-(3H) naphtho [2,1-b] (1,4) oxazine], and others Can be mentioned.

The spironaphthoxazine compound as described above has at least one hydroxy group at the β-position and α
It can be synthesized by using dihydroxynaphthalene capable of nitrosating the position, nitrosating this, and reacting the corresponding indoline compound with boiling point reflux in the presence of a suitable solvent such as ethanol or toluene. It can also be synthesized by using a corresponding indium salt compound instead of the indoline compound. Further, a base such as triethylamine can be added as a catalyst. This spironaphthoxazine compound is
If necessary, a pure product can be obtained by refining using a technique such as a recrystallization method, a column separation method, and an activated carbon treatment method.

The epoxy resin or urethane resin forming the matrix in the photochromic material of the present invention is not particularly limited, and any kind can be used.

As the epoxy resin, a high molecular weight compound containing two or more epoxy groups in one molecule and a resin formed by a ring-opening reaction of the epoxy group are used, and preferably a reaction between a compound containing an epoxy group and an active hydrogen compound. The product is used.

Examples of active hydrogen compounds include phenolic compounds such as bisphenol A and bisphenol F, polypropylene glycol, hydroxy group-containing compounds such as alcoholic compounds such as hydrogenated bisphenol A, carboxylic acid-containing compounds such as dimer acid, and isocyanuric acid. The amine-containing compound and the like can be mentioned. Aliphatic polyamines, amidoamines, polyamides, aromatic polyamines, acid anhydrides, catalytic curing agents and the like can be used as a curing agent for accelerating the reaction.

As the urethane resin, a resin having repeating urethane bonds, preferably a reaction product of diisocyanate and polyol is used. Examples of the diisocyanate include aliphatic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane-
Alicyclic diisocyanates such as 1,4-diisocyanate,
Xylylene diisocyanate, aliphatic isocyanate having an aromatic ring such as 1,3-diphenylpropane-1,3-diisocyanate, 1-methyl-2,4-phenylene diisocyanate, diphenylmethane-4,4'- Aromatic isocyanates such as diisocyanate and the like can be preferably used, and as the polyol, for example, polyester polyol, polyether polyol, acrylpolyol, etc. can be preferably used. In order to obtain a urethane resin having more preferable characteristics, ethylene glycol, 1,4-butanediol, trimethylolpropane or the like can be added in the urethane reaction. In order to accelerate the urethanization reaction, dibutyltin dilaurate, 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, etc. are added as a catalyst to the mixture of diisocyanate and polyol to lower the curing temperature. It is also possible.

The final product of these epoxy resins or urethane resins is preferably colorless.

In the present invention, the photochromic substance is mixed with the above-mentioned epoxy resin precursor or urethane resin precursor, and the hydroxy group in the molecule of the photochromic substance is
By reacting with the epoxy group in the precursor of the epoxy resin or the isocyanate group in the precursor of the urethane resin, the photochromic substance is contained in the resin in a chemically bonded state. Therefore, the photochromic material of the present invention has a very high elution resistance of the photochromic substance. The term "precursor of epoxy resin" or "precursor of urethane resin" as used herein means a mixture of the raw materials of those resins, an oligomer or the like, which gives the epoxy resin or urethane resin by heat or other means.

The ratio of the epoxy resin or urethane resin and the photochromic substance in the photochromic material of the present invention is
0.01 to 50 parts by weight per 100 parts by weight of resin, preferably 0.05 to 4
It is 0 parts by weight. Outside this range, it is difficult to obtain a photochromic material having a good photochromic action.

The present invention can be carried out in various modes. For example, a glass plate, a lens body, a surface of a substrate made of a transparent resin film, or the like, and the photochromic substance described above and a precursor of an epoxy resin or a urethane resin are used. By applying a coating solution obtained by mixing the precursor and subjecting it to a curing reaction by heat treatment or the like, it is possible to manufacture an optical member or the like in which a thin layer is well formed on the photochromic material of the present invention. By using the precursor of the resin in this manner, the photochromic substance is chemically bonded and integrated with the resin during the curing, so that the production is easy, and since the precursor has a low molecular weight, the viscosity is low. There is an advantage that a coating solution can be obtained and therefore coating is easy.

It is preferable to use a solvent for the preparation of the coating liquid, which can easily reduce the viscosity of the coating liquid. As this solvent, for example, methyl ethyl ketone, ethyl acetate, butyl acetate, isobutyl ketone, xylene and a mixture thereof, and the like are used. When an epoxy resin is used as the resin, it is also possible to use a reactive diluent. If necessary, various additives such as a curing catalyst, an antioxidant and an ultraviolet absorber can be added to the coating liquid. After applying the coating liquid to the substrate, the photochromic material of the present invention is formed by reacting and curing by heating or the like. This reaction and curing may be carried out under the conditions sufficient to cause the reaction of the hydroxy group of the photochromic substance and the high molecular weight (resinization) of the precursor, but usually 10 minutes in the temperature range of 20 ° C to 100 ° C. Heat for ~ 20 minutes. The thickness of the coating curtain of the coating liquid is preferably 1 to 100 μm.

The photochromic material of the present invention thus formed has an extremely excellent elution resistance in which the photochromic substance contained in the matrix does not elute even when contacted with a solvent or the like. Therefore, it is possible to freely use various solvents when applying other coatings on the surface of the photochromic material,
Various coatings can be applied without being restricted by the solvent aspect. For example, even when forming a so-called hard coat layer for surface protection of the photochromic material of the present invention, the characteristics of the photochromic substance are not deteriorated by the solvent of the hard coding agent.

〔Example〕

Examples of the present invention will be described below, but the present invention is not limited thereto.

Example 1 [I] Nitrosation of 2,7-naphthodiol 8 g of 2,7-naphthodiol was dissolved in a mixed solvent of 100 ml of acetic acid and 50 ml of acetone and cooled to 0 ° C. or lower in an ice bath. Then, add 13.8 g of sodium nitrite to 50 m of this solution.
What was melt | dissolved in 1 l of water was dripped over 2 hours, and nitrosation was performed. After the reaction, the solution was stirred overnight, and the formed precipitate was filtered off, washed with acetone and water, and dried sufficiently with a vacuum drier to obtain 7.6 g of a product.

As a result of TLC and elemental analysis, this product was 2,7-
It was found to be a mixture of 37% by weight of naphthodiol and 63% by weight of its mononitros compound. This product was subjected to the following synthesis without purification.

[II] 9'-hydroxy-1,3,3-trimethylspiro [indoline-2,3 '-(3H) -naphtho [2,1-b] (1,
4) Synthesis of Oxazine] 4.36 g of the nitrosation product of 2,7-naphthodiol obtained in [I] and 10.35 g of 1,3,3-trimethyl-2-methyleneindoline were dissolved in 50 ml of absolute ethanol. And nitrogen
After bubbling for 30 minutes, the temperature was raised, and the reaction was carried out by refluxing the boiling point for 3 hours.

After completion of the reaction, the solvent was distilled off, and the column was separated by a silica gel column using chloroform as a developing solvent. After the solvent was distilled off, the obtained solid was recrystallized from a chloroform-hexane mixed solvent to obtain 1.8 g of a pale yellow powder.

This product was analyzed by nuclear magnetic resonance and infrared spectroscopy to give 9'-hydroxy-1,3,3-trimethylspiro [indoline-2,3 '-(3H) -naphtho [2,1-b] (1 , 4) Oxazine] was identified.

[III] Application Spironaphthoxazine compound 4 obtained as described above
Parts by weight and precursor of epoxy resin "Eponics # 1100
48 parts by weight of "Clear" (manufactured by Dainippon Paint Co., Ltd.) and 1 part by weight of "Irganox 245" (manufactured by Ciba Geigy) were dissolved in 100 parts by weight of methyl ethyl ketone to obtain a coating solution.

Apply this coating solution on a slide glass by the dipping method,
By heat-curing at 80 ° C. for 16 hours, a light control layer made of the photochromic material of the present invention was formed. The thickness of the light control layer was 35 μm, and it was transparent with a slight green tinge.

When this glass member was irradiated with ultraviolet rays having a wavelength of 365 nm, it became dark blue, and when it was left in a dark place except for the ultraviolet rays, it returned to its original colorless state.

In addition, in order to investigate the elution resistance of the photochromic substance in the light control layer, the slide glass was immersed in methyl ethyl ketone for 5 minutes at room temperature, then taken out, the methyl ethyl ketone was cut off well, and dried at 80 ° C for 10 minutes, and similarly at a wavelength of 365 nm. When the sample was irradiated with ultraviolet rays, a slight color fading was observed, but almost the same color development was observed, and the absorbance at the absorption peak (340 nm) of the non-colored species was about 60% of that before the immersion treatment with methyl ethyl ketone. From this, it is clear that the photochromic substance is stably present in the light control layer and is difficult to be eluted in the solvent.

Comparative Example 1 9'-Hydroxy-1,3,3-trimethylspiro [indoline-2,3 '(3H) -naphtho [2,1-b] (1,4) oxazine] was substituted with a hydroxy group. No 1,3,3-trimethylspiro [indoline-2,3 '-(3H) naphtho [2,1-b] (1,4) oxazine] was used, except that [III] of Example 1 was used. Prepare a coating solution in the same manner,
This coating solution was applied on a slide glass and heat-cured at 80 ° C. for 16 hours to form a light control layer.

When the glass member thus obtained was irradiated with ultraviolet light having a wavelength of 365 nm, it exhibited the same color as the glass member of Example 1 and almost the same density, and returned to the original colorless state upon removal of light irradiation.

A part of this slide glass was immersed in methyl ethyl ketone for 5 minutes at room temperature to take it out, the methyl ethyl ketone was cut off well, dried at 80 ° C for 10 minutes, and then at a wavelength of 365 nm in the same manner.
When it was irradiated with the ultraviolet rays of No. 3, no color was developed in the immersed portion, and the color was completely lost. The portion not immersed in methyl ethyl ketone developed a blue color like the original one.

Example 2 [I] Nitrosation of 2,6-naphthodiol 8 g of 2,6-naphthodiol was dissolved in a mixed solvent of 100 ml of acetic acid and 100 ml of ethanol, and cooled to 0 ° C. or lower by ice and ice. Then, a solution prepared by dissolving 13.8 g of sodium nitrite in 50 ml of water was added dropwise to this solution over 2 hours, followed by stirring for 4 hours to complete the reaction. This was allowed to stand overnight, the deposited precipitate was separated by filtration, washed with water and ethanol, and vacuum dried at 50 ° C. to obtain 5.7 g of a product.

As a result of thin-layer chromatography and CHN elemental analysis, this product was confirmed to be a mixture of starting 2,6-naphthodiol, a mononitrosated product, and a dinitrosated product. This product was subjected to the following synthesis without purification.

[II] 8'-hydroxy-1,3,3-trimethylspiro [indoline-2,3 '-(3H) -naphtho [2,1-b] (1,
4) Synthesis of Oxazine] 4.36 g of the nitrosation product of 2,6-naphthodiol obtained in [I] and 6.9 g of 1,33-trimethyl-2-methyleneindoline were dissolved in 70 ml of absolute ethanol, The reaction was carried out by refluxing under nitrogen gas for 2 hours.

After completion of the reaction, the solvent was concentrated, and column separation was performed using a silica gel column with chloroform as a developing solvent. After the solvent was distilled off, the obtained solid was recrystallized from a chloroform-hexane mixed solvent to obtain 0.7 g of a pale yellow powder.

This product was analyzed by nuclear magnetic resonance and infrared spectroscopy to give 8'-hydroxy-1,3,3-trimethylspiro [indoline-2,3 '-(3H) -naphtho [2,1-b] (1 , 4) Oxazine] was identified.

[III] Application A coating liquid was obtained in the same manner as in Example 1 except that the spironaphthoxazine compound obtained as described above was used, and this coating liquid was used to form a light control layer on a slide glass. This light control layer was transparent with a slight green tinge.

When this glass member was irradiated with ultraviolet rays having a wavelength of 365 nm, it became dark blue, and when it was left in a dark place except for the ultraviolet rays, it returned to its original colorless state.

Further, in order to examine the elution resistance of the photochromic substance in the light control layer, the same dipping treatment and drying as in Example 1 were performed, and similarly, irradiation with ultraviolet light having a wavelength of 365 nm was performed.
It showed almost the same color development as that before the dipping treatment with methyl ethyl ketone, and the absorbance at the absorption peak (340 nm) of the uncolored species was about 60% of that before the dipping treatment with methyl ethyl ketone. From this, it is clear that the photochromic substance in the light control layer is stably present and is hardly eluted in the solvent.

Example 3 [I] 9'-Hydroxy-1-benzyl-3,3-dimethylspiro [indoline-2,3 '-(3H) naphtho [2,1-
b] Synthesis of (1,4) oxazine 5.3 g of 2,3,3-trimethylindolenine was dissolved in 40 ml of ethanol, and a nitrogen bubble was added.
After 30 minutes, 5.7 g of benzyl bromide was added, and the mixture was refluxed at boiling point for 2 hours. After cooling to room temperature, 3.4 g of triethylamene and 50 ml of ethanol were added, and after stirring, 6.8 g of the nitrone product of 2,7-naphthodiol synthesized in [I] of Example 1 was added and dissolved. After stirring for 30 minutes with a nitrogen bubble, boiling point reflux was carried out for 2 hours.

After completion of the reaction, the solvent was distilled off, and the column was separated by a silica gel column using chloroform as a developing solvent. After the solvent was distilled off, the obtained solid was recrystallized from a chloroform-hexane mixed solvent to obtain 2.1 g of a pale yellow powder.

This product was analyzed by nuclear magnetic resonance and infrared spectroscopy to give 9'-hydroxy-1-benzyl-3,3-dimethylspiro [indoline-2,3 '-(3H) -naphtho [2,1-b].
The (1,4) oxazint was fixed.

[II] Application Spironaphthoxazine compound 8 obtained as described above
Parts by weight and urethane resin precursor "Olestar NP2000"
22 parts by weight (manufactured by Mitsui Toatsu Chemicals, Inc.) and "Orestar Q
-602 "(manufactured by Mitsui Toatsu Chemicals, Inc.) 11 parts by weight was dissolved in a mixed solvent of 40 parts by weight of ethyl acetate, 30 parts by weight of methyl isobutyl ketone and 30 parts by weight of toluene to obtain a coating solution.

Apply this coating solution to a lens body made of diethylene glycol bisallyl carbonate "CR-39" (power -2.00, diameter
78mm) surface by dipping method, and then at 40 ℃ for 24 hours,
Further, it was heated and cured at 60 ° C. for 24 hours to form a light control layer.

This light control layer had a thickness of 16 μm and was transparent with a slight green tinge. When this lens was placed under sunlight, the light control layer became colored and became dark blue, and when left in the dark except for sunlight, the original colorless state was restored.

Then, a silicone-based hard coat liquid "X-12-1100" (manufactured by Shin-Etsu Chemical Co., Ltd.) was applied on the light control layer of this lens by a dipping method, left at room temperature for 30 minutes, and then at 80 ° C for 2 minutes. It was heat-cured for an hour to form a hard coat layer.

The lens thus obtained was clear and colorless and had no adverse effect even during immersion for the step of forming the hard coat layer. When this lens was left in the sunlight, it became dark blue and returned to the original colorless and transparent state left in the dark.

Claims (1)

[Claims] 1. A photochromic material obtained by reacting and curing a photochromic substance represented by the following general formula (I) with an epoxy resin precursor or a urethane resin precursor. General formula (I) [Wherein, a and b are each 0 or 1 and a + b
= 1 and R ₁ is a hydrogen atom, a halogen atom, a cyano group,
A lower alkyl group and a lower alkoxy group are shown, and R ₂ is a lower alkyl group, a lower alkoxyalkyl group, various substituted arylalkyl groups, and CH _{2 n} COOR. However, R shows a lower alkyl group and n shows the integer of 1-6. ]