JPH0241388A - Photochromic substance - Google Patents

Abstract

PURPOSE:To obtain the title substance having excellent coloring properties, effective only by dispersion or dissolution of a small amount in a high polymer binder, having excellent transparency and repeating performance comprising a specific vinyl group-substituted spironaphthoxazine derivative. CONSTITUTION:A photochromic substance shown by the formula (one of X1 and X2 is unsaturated bond-containing hydrocarbon, organic substituent group containing C-C unsaturated bond and the other is H; X3 and X4 are 1-30C straight-chain alkyl, straight-chain alkoxy, H, halogen, nitro or cyano; R1-R3 are 1-30C straight-chain alkyl) prepared by introducing an unsaturated bond- containing hydrocarbon or a C-C unsaturated bond-containing organic substituent group to the 8'- or 9'-position of a 1-alkyl-3,3-dimethylspiro[indoline-2,3-(3H)- naphth(2,1-b)-1,4-oxazine] derivative.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a photochromic substance that undergoes a reversible color change when exposed to light.

(Prior art) It is known that spironaphthoxazine derivatives exhibit photochromism, and focusing on the reversible coloring ability, sunglasses, optical filter,
Practical application in fields such as curtains is progressing.

For example, in Japanese Patent Publication No. 45-28892.

1.3.3-trimethylspiro[indoline-2,3'
-[3H]-naphtho(2,1-b)-1,4-oxazine], and in JP-A-61-138686, a hydroxyl group is introduced at the 8' or 9' position of the oxazine. It is proposed that these spironaphthoxazine derivatives dissolved in a suitable polymeric binder be coated on a transparent support and dried. These spironaphthoxazine derivatives have superior repeatability compared to other organic photochromic substances 1, such as spirobenzopyrans and dithizones, and are being actively researched for practical use.

(Problem to be Solved by the Invention) However, these spironaphthoxazine derivatives, as photochromic substances, do not have good change in optical density at the maximum absorption wavelength (hereinafter referred to as 1 color development performance) when activated by light irradiation. Ta. Therefore, a considerable amount of the spironaphthoxazine derivative must be dissolved and dispersed in the polymeric binder, and as a result, in the system of the spironaphthoxazine derivative and the polymeric binder, aggregation of the spironaphthoxazine derivative occurs, resulting in a loss of transparency. The problem was that it was easily damaged.

The present invention is intended to solve the problems of the prior art, and its purpose is to provide a transparent photochromic material that has excellent repeatability, excellent coloring performance, exhibits sufficient photochromism with a small amount, and The object of the present invention is to provide a photochromic substance from which a material can be obtained.

(Means for Solving the Problems) In order to solve the above problems, the present inventors have conducted intensive research and found that 1-alkyl-3,3-dimethylspiro[indoline-2,3'-(3H)- Naphtho [2゜1-b)-1
, 4-oxazine] derivative has been found to be able to achieve the above object by introducing a hydrocarbon containing an unsaturated bond or an organic substituent containing a carbon-carbon unsaturated bond to the 8' or 9' position of the derivative.

We have arrived at the present invention.

That is, the present invention provides - maximum (N (wherein, one of X+ and Xz is a hydrocarbon containing an unsaturated bond or an organic substituent containing a carbon-carbon unsaturated bond.

The other is a hydrogen atom, and X11X4 is a linear alkyl group or a linear alkoxy group having 1 to 30 carbon atoms, a hydrogen atom, a halogen atom, a nitro group, or a cyano group, R
1, R2 and R3 each represent a straight chain alkyl group having 1 to 30 carbon atoms. ) is a photochromic substance.

The present invention will be explained in detail below. Photochromism refers to the tendency of photochromism to develop color under the influence of light of a certain wavelength when irradiated with light, and to return to its original state when brought to a dark place. In addition, photochromic substance refers to a compound that exhibits photochromism.

First, in the definition of equation (1) above, X, ,X.

One of them is a hydrocarbon containing an unsaturated bond or an organic substituent containing a carbon-carbon unsaturated bond, such as a vinyl group, allyl M, 3-7'tenyl group, 4-pentenyl group, acryloxy group, vinylamide group, etc. and the other is a hydrogen atom. X3. Examples of the straight chain alkyl group having 1 to 30 carbon atoms for X4 include methyl and propyl, and examples of the straight chain alkoxy group having 1 to 30 carbon atoms include methoxy and ethoxy.

Examples include propoxy, and halogen atoms include fluorine, chlorine, bromine, and iodine atoms. However, Rz and R1 are straight chain alkyl groups having 1 to 30 carbon atoms.

The photochromic substance of the present invention can be obtained, for example, by the following method.

First, a triflate of a spironaphthoxazine derivative is synthesized by reacting a spironaphthoxazine derivative having a hydroxyl group at the 8' or 9' position with trifluorosulfonic acid (Synthesis P85-126
(1982)). By coupling this with an organic stannane in the presence of a palladium catalyst (e.g. Pd(P P h 3) #), the
m.

Soc,, 109. 5478 (1987) )
, spironaphthoxazine derivatives with vinyl substitution can be synthesized.

The vinyl group-substituted spironaphthoxazine derivative of the present invention, like other spironaphthoxazine derivatives,
If it is dissolved or dispersed in an organic solvent or a suitable polymer binder and irradiated with ultraviolet rays, it will immediately develop a color, and if it is left in a dark place or irradiated with visible light, it will return to its original colorless state. . Furthermore, the photochromic substance of the present invention has the property of reversibly repeating these changes, that is, has good photochromic properties.

Examples of organic solvents that can be used for the photochromic substance of the present invention include various solvents such as methyl alcohol, ethyl alcohol, acetone, methyl ethyl ketone, chloroform, methylene chloride, ethyl acetate, tetrahydrofuran, dioxane, methyl cellosolve, and dimethyl sulfoxide. Can be mentioned.

9. Polymer binders that can be used for the substance of the present invention include 1. For example, acrylic polymers such as polymethyl methacrylate, styrene polymers such as polystyrene, polyester polymers such as polycarbonate, and polyethylene oxide. Polyether-based polymers Polyamide-based polymers such as nylon 6,
Olefin polymers such as polyethylene, cellulose polymers such as ethyl cellulose, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyglycidyl methacrylate poly-N-vinyl carbazole and copolymers thereof. etc. can be mentioned.

Furthermore, a photochromic polymer can be obtained by coaddition polymerizing the vinyl group-substituted spironaphthoxazine derivative of the present invention with another vinyl monomer. As its vinyl monomer.

Olefins such as ethylene, propylene and butadiene, styrene derivatives such as styrene, p-methylstyrene and p-chlorostyrene, and methylnucleic acid. Examples include acrylic ester derivatives and acrylic acids such as ethyl methacrylate, propyl methacrylate, butyl meccrylate, and benzyl methacrylate, as well as vinyl acetate, acrylonitrile, and vinyl chloride. The copolymerization ratio of the vinyl group-substituted spironaphthoxazine derivative in such a copolymer is suitably from 0.1 to 80 mol%, preferably from 1 to 30 mol%.

Furthermore, by hydrosilating with silicone rubber, silicone rubber having a photochromic substance in the side chain can be obtained. Silicone rubber is non-toxic and has good transparency, making it suitable for photochromic substances.

In this case as well, the copolymerization ratio of the spironaphthoxazine derivative is suitably 0.1 to 80 mol%, preferably 1 to 3 mol%.
It is 0 mol%.

(Example) Next, one embodiment of the present invention will be specifically explained using examples.

Example 1 As described in JP-A-61-138686, 27 g of 1-nitroso-2,7-hydroxynaphthalene was dissolved in 200 ml of ethanol and heated to about 80°C.
heated to. To this solution, 100 ml of an ethanol solution containing 17 g of triethylamine and 47 g of 1.2.3.3-tetramethylindole iodide was added dropwise over 30 minutes, and the mixture was refluxed for 2 hours. Next, the excess ethanol is distilled off to about a quarter, and when cooled, 1,3.3-
) Crude crystals of limethyl-9''-hydroxy-spiroindoline-naphthoxazine were precipitated. The crude crystals were purified by recrystallization with ethyl alcohol to obtain 20 g of crystals.

20 g of this crystal was dissolved in pyridine at -20°C.

To this was added 16.5 g of trifluoromethanesulfonic anhydride. Then, it was heated to 0°C and left at 0°C for 2 days. This was dispersed in ether, and the mixed solution was washed three times with water and then dried by adding magnesium sulfate.

As a result, powder crystals of 1,3,3-trimethyl-9°-triflate-spiroindoline-naphthoxazine were obtained.

This triflate and 15.5 g of vinyltri-n-butylstannane were combined in dioxane with 0.1 g of tetrakistriphenylphosphine palladium as a catalyst.
By refluxing for 4 hours and cooling, 12 g of 1.3.
3-) Limethyl-9”-vinyl-spiroindoline-
Naphthoxazine crystals were obtained.

100 Mllz, H-NMR analysis results show double peaks at 5.2PPM and 5.7PPM, and four peaks around 6.7PPM, similar to styrene monomers, and IR analysis results also show that, like styrene monomers, carbon A peak from the unsaturated bond appeared near 1645 am −', and a vinyl group was confirmed. This melting point is 170-178
℃, and the results of two-element analysis are.

Theoretical value (%) of C: 81.4. H:6.2. N
Near, 9, the actual value (%) is C: 81.0.
H: 6.5°N near, 8.

The above substance was dissolved in polymethyl methacrylate in toluene so that the molar ratio to the monomer was 3 mol%, and the film was cast on a glass plate to a thickness of 100 μm. After drying, the film was exposed to light. Irradiation was performed. Light irradiation was performed using an ultra-high pressure mercury lamp (manufactured by Ushiyo Denki Co., Ltd.) 50
The measurement was carried out using 0W as a light source and a cut filter UV-31 (manufactured by Toshiba Glass Co., Ltd.).

The film was colorless and transparent before being exposed to light.

It developed a deep blue color upon irradiation with light for 30 seconds. When the colored film was left in a dark place, it returned to its original colorless state in about 10 seconds. Maximum absorption wavelength in activated state by light irradiation (
λ, @X) was 618 nm. λ1. The change in absorbance (ΔOD) of X was 0.88.

Example 2 The same steps as in Example 1 were carried out except that 5-chloro-1,2,3,3-tetramethylindole iodide was used instead of 1.2,3,3-tetramethylindole iodide. Crystals of 5-chloro-1,3,3-)dimethyl-9'-vinyl-spiroindoline-naphthoxazine were obtained.

The H-NMR and IR analysis results were almost the same as those of Example 1, and the melting point was 205 to 210°C.

The results of elemental analysis are the theoretical value (%) of C near 4.1°H:
5.4. The actual value (%) is C near 3. compared to N near 2.
9. H:5.6. N near, it was 0.

A film was prepared from this substance in the same manner as in Example 1, and when it was irradiated with light for 30 seconds, it developed a deep blue color. λ
□8 is 615 nm, and the change in absorbance of λ, 1X (Δ
00) was 0.79.

Example 3 1.3.3-1- was prepared in the same manner as in Example 1 except that 1-nitroso-2,6-cyhydroxynaphthalene was used instead of 1-nitroso-2,7-cyhydroxynaphthalene.
methyl-3'-vinyl-spiroindoline-naphthoxazine was synthesized.

The H-NMR and IR analysis results were almost the same as in Example 1, and the melting point was 175-183°C.

The result of elemental analysis is the theoretical value (%) of C: 81.0°H:
6.5. N: 1.8, actual value (%) is C: 8
1.3. H:6.7. Nia, it was 5.

A film was prepared from this substance in the same manner as in Example 1, and when it was irradiated with light for 30 seconds, it developed a deep blue color. λ
□8 is 620 nm, and the change in absorbance of λ1IaX (
ΔOD) was 0.85.

Example 4 5-
Methoxy-1,3,3-trimethyl-8'' vinyl-spiroindoline-naphthoxazine was synthesized.

The H-NMR and IR analysis results were almost the same as in Example 1, and the melting point was 198-205°C.

The results of elemental analysis are the theoretical value (%) of C near 3.3°H:
6.0. The actual value (%) is C near 3. compared to N near 3.
6. H:6.2. It was Nia, O.

A film was prepared from this substance in the same manner as in Example 1, and when it was irradiated with light for 30 seconds, it developed a deep blue color. λ
wax is 620 nm, and the change in absorbance of λ□8 (Δ
OD) was 0.83.

Example 5 A 1° 3.
3,4.5-pentamethyl-8'-vinyl-oxazine was synthesized.

) (-NMR and IH analysis results are almost the same as in Example 1, and the melting point is 220 to 228°C.

The result of elemental analysis is the theoretical value (%) of C: 81.9°H:
6.6. The actual value (%) is C: 82.
3. H:6.9. N: 6.9.

A film was prepared from this substance in the same manner as in Example 1, and when it was irradiated with light for 30 seconds, it developed a deep blue color. λ
lI□ was 625 nm, and the change in absorbance (Δ00) of λ1111+1 was 0.80.

Comparative Example 1 1,3.3-trimethyl-spiroindoline naphthoxazine was mixed in chloroform at a concentration of 35% by weight (15 mol%) based on polystyrene, and the mixture was cast onto a glass plate. After drying, the film was colorless and transparent, and had good photochromic properties when irradiated with light. However, after being left in the dark for 15 hours, the dyes aggregated in the film, and although it exhibited photochromism, the color development performance was considerably reduced. was.

Comparative Example 2 In methylene chloride, 1,3,3-1-dimethyl-9'-hydroxy-spiroindoline-naphthoxazine was 55% by weight (26 mol%) based on polymethyl methacrylate.
) and cast on a glass plate. After drying, the film is colorless and transparent.

Although it had good photochromic properties when exposed to light, the dye aggregated in the film after being left in the dark for 20 hours.
It did not show photochromic properties.

Reference Example 1 The 1,3.3-)dimethyl-9'-vinyl-spiroindoline-naphthoxazine crystals synthesized in Example 1 were added to purified styrene monomer at a ratio of 10 mol %, and the mixture was subjected to radical polymerization.

Addition polymerization was performed in degassed toluene using AIBN as an initiator to obtain a copolymer. This copolymer was soluble in chloroform and was purified by precipitation of the chloroform solution with methanol.

As a result of HNMR analysis, it was found that 8.5 mol% of the photochromic monomer was copolymerized with respect to the styrene unit.

This copolymer was dissolved in chloroform and cast onto a glass plate to obtain a film with a thickness of 30 μm. The film after drying was colorless and transparent, and no aggregation of the two dye parts was observed. Furthermore, this film was irradiated with light. Light irradiation was performed using an ultra-high pressure mercury lamp (manufactured by Ushiyo Denki Co., Ltd.) 5QQW as a light source and a cut filter UV-31 (manufactured by Toshiba Glass Co., Ltd.). The film before light irradiation was colorless and transparent, but it developed a deep blue color after 30 seconds of light irradiation.

When the colored film was left in a dark place, it returned to its original colorless state in about 30 seconds. The maximum absorption wavelength (λ□8) in the activated state by light irradiation was 628 nm.

Reference Example 2 The 1,3,3-)dimethyl-9'vinyl-spiroindoline-naphthoxazine crystals synthesized in Example 1 were added in an amount of 30 mol% to the styrene monomer, and addition polymerization was carried out in the manner described above.

As a result of purification, H-NMR analysis revealed that 17 mol% of the photochromic monomer was copolymerized. The dry film obtained by casting from chloroform is colorless and transparent.

No aggregation of the dye part was observed. The film developed a deep blue color after being exposed to light for 30 seconds.

When left in a dark place, it returned to its original colorless state in about 30 seconds.

The maximum absorption wavelength (λ□X) in the activated state by light irradiation was 628 nm.

Reference Example 3 5-chloro-1,3゜3- synthesized in Example 2
Trimethyl-9'-vinyl-spiroindoline naphthoxazine crystals were charged at a ratio of 30 mol% to the purified methyl methacrylate monomer, and A was prepared using a well-known method.
Addition polymerization was carried out in degassed toluene using IBN as an initiator to obtain a copolymer.

This copolymer is soluble in chloroform and was purified by precipitating a chloroform solution with methanol.

As a result of H-NMR analysis, it was found that 12 mol% of the photochromic monomer was copolymerized with respect to the methyl methacrylate unit.

The dry film obtained by the casting method from methylene chloride was colorless and transparent, and no aggregation of the two dye parts was observed. Ficilem, which developed a deep blue color after irradiation with light for 30 seconds, returned to its original colorless state in about 30 seconds when left in a dark place. Maximum absorption wavelength in activated state by light irradiation (
λ11,) was 617 nm.

(Effects of the Invention) Since the photochromic substance of the present invention has excellent coloring performance, a small amount thereof can be dispersed or dissolved in a polymer binder and exhibit sufficient photochromism. Therefore, unlike the conventional spironaphthoxazine derivatives mentioned above, it is not necessary to dissolve and disperse a large amount in a polymer binder, so that aggregation is less likely to occur in the polymer binder system, and a photochromic material exhibiting excellent transparency can be obtained. Can be done. Furthermore, it has excellent repeatability and is comparable to the conventional photochromic materials mentioned above.

Furthermore, the photochromic substance of the present invention can be introduced into the side chain of a polymer, which could not be done with conventional spironaphthoxazine derivatives, and it can be copolymerized with other general-purpose vinyl monomers or copolymerized with unsaturated side groups of the photochromic substance. By reacting with a reactive main chain polymer, a photochromic group can be introduced into the polymer, and a wide range of photochromic materials can be expected to be expanded into commercial products.

Examples of products using the substance of the present invention include 9.

Light control materials such as light control plastic lenses and window light control materials, holographic photosensitive materials, display materials,
Examples include photometers, decorative materials, and various electronic device materials using the LB film method.

Patent applicant: Uni-Tei Riki Co., Ltd.

Claims (1)

[Claims] (1) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, one of X_1 and X_2 is a hydrocarbon containing an unsaturated bond or an organic substituent containing a carbon-carbon unsaturated bond. , the other is a hydrogen atom, and X_3 and X_4 each have 1 carbon number.
~30 straight chain alkyl group or straight chain alkoxy group, hydrogen atom, halogen atom, nitro group or cyano group, R_1
, R_2, and R_3 each represent a straight-chain alkyl group having 1 to 30 carbon atoms. ) photochromic substance.