JPH0439383A - Photochromic composition - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [R1 is trifluoromethyl; m >=2; these rings A and B are (substituted)hydrocarbon aromatic ring or heterocyclic aromatic ring; R<1> to R<4> are H, 1-25C hydrocarbon, alkoxy, halogen, etc.]. EXAMPLE:1,3,3-Trimethyl-6',8'-bistrifluoromethyl-spiro[indoline--2,3'- (3H)-naphtho(2,1-b)(1,4)-oxazine]. USE:A photochromic material. PREPARATION:A hydroxy derivative expressed by formula II is reacted with trifluoromethyliodide in the presence of copper powder to give a fluorine- containing hydroxy derivative, which is converted into a nitroso-hydroxy derivative by NaNO2. Then an indonylene derivative expressed by formula III is reacted with a compound expressed by the formula R<1>X (X is SO3C6H4CH2 and then reacted with the above-mentioned nitroso-hydroxy derivative to synthesize the compound expressed by formula I.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to light control materials for windows, curtains, sunglasses, ski goggles, etc., photosensitive materials for printing such as recyclable copy paper, Copying materials, various recording/storage materials, display materials, photosensitive materials for lasers, photosensitive materials for holography, optical filters, masking materials, photometers, display materials, or paints, clothing, toys, sports The present invention relates to a novel photochromic material useful as a material for supplies, cosmetics, and ornaments.

[Prior Art] Many photochromic compounds are known, and a typical example is a spiropyran compound.

(G,H,Brown,” Photochromis
m, Wiley Inter-science
, New York (1971) It is also known that spirooxazine compounds have photochromic properties, such as coloring when exposed to ultraviolet light and decolorizing when exposed to heat or visible light.
No. 48631, JP-A-55-36284, JP-A-61
Substituted conductors of spironaphthoxazine compounds and photochromic materials containing the compounds have been proposed in Japanese Patent Application Laid-open Nos. 53288-53288, JP-A-61-263982, JP-A-62-33184, and IJSP4342568.

Also, Japanese Patent Publication No. 60-53586, Special Publication No. 2-5008
No. 39 discloses a photochromic material using a spirooxazine compound having a trifluoromethyl group on a benzene ring. Further, JP-A-62-288682 describes that spironaphthoxanedine compounds having a trifluoromethyl group in the naphthalene ring have excellent high-temperature coloring performance.

Also, JP-A-60-112880, JP-A-62-15
No. 3292 proposes a spiropyridobenzoxazine compound and a photochromic material using the compound.

Also, JP-A-62-3.64685, JP-A-63-3
No. 0489 proposes a subirofuenanthrooxazine compound and a photosensitive material using the compound.

[Problems to be Solved by the Invention] Spiropyran compounds have a problem in durability over repeated photo-emission and decolorization. Further, although the known spirooxazine compounds have improved repeat durability compared to the above-mentioned compounds, they are still insufficient for practical use.

[Means for Solving the Problems] The present invention relates to a novel photochromic material for solving the above problems. The photochromic material of the present invention solves the above problems by containing a novel spirooxazine compound represented by the following general formula (b) in which two or more trifluoromethyl groups are introduced into R2.

(In the formula, R2 represents a trifluoromethyl group, and m=2.
[A, B represents a hydrocarbon aromatic ring or a heterocyclic aromatic ring which may be substituted in addition to R1, R1, R2, R
", R" is a hydrogen atom, a hydrocarbon group having 1 to 25 carbon atoms, or an alkoxy group, F, or C1, Br,
■Halogen atoms such as ester groups, cyano groups, nitro groups, ether groups, thioether groups, carbonyl groups, sulfonyl groups, amino groups, substituted amino groups, imino groups, amide groups, thioamide groups, urethane groups, urea groups, in Indicates a hydrocarbon group having a cyanate group, an azo group, or a hydroxy group, a thiol group, a carboxyl group, a sulfonic acid group, and its metal base. R1, R2, R1, and R4 are each the same or different substituents, and R2 and R1' may be bonded to each other and cyclized. ) In the above formula (b), the number of substitutions for R2 is represented by m=2, but preferably m
=2.

Further, in the compound represented by the above formula (b), examples of the hydrocarbon aromatic ring or heterocyclic aromatic ring which may be substituted other than R1 of rings A and B include a benzene ring, a naphthalene ring, and a quinoline ring. , a phenanthrene ring, an anthracene ring, a pyridine ring, and the like. Preferably, the ring is a benzene ring or a pyridine ring, and the ring B is a naphthalene ring, a quinoline ring, or a phenanthrene ring. These substituents other than R7 include polyfluoroalkyl groups, fluoroalkyl groups, halogen atoms such as F or C1, Br, ■, ester groups, cyan groups, nitro groups, ether groups, thioether groups, carbonyl groups, and sulfonyl groups. , amino group, substituted amino group, imino group, amide group, thioamide group, urethane group,
Urea group, incyanate group, azo group, or hydroxy group, thiol group, carboxyl group, sulfonic acid group and its metal base, hydrocarbon group having 1 to 25 carbon atoms, or alkoxy group, F, or C1, Br, ■ Halogen atoms, ester groups, cyano groups, nitro groups, ether groups, thioether groups, carbonyl groups, sulfonyl groups, amino groups, substituted amino groups, imino groups, amide groups, thioamide groups, urethane groups, urea groups, isocyanate groups, etc. Azo group, or hydroxy group, thiol group, carboxyl group,
Examples include hydrocarbon groups having a sulfonic acid group and its metal base.

Further, R1, R1, and R8 are bonded to another spirooxazine ring via an alkyl group, an alkylene group, etc. to form a dimer compound as a whole. Introducing reactive groups such as double bonds and silane coupling groups into the mata R', R2, R'', Af!J, and B rings,
It can also be combined with a matrix material.

The novel photochromic material of the present invention has excellent durability over repeated photo-emission and decolorization by introducing two or more trifluoromethyl groups into R in general formula (b), and can be used at a practical level. Has characteristics.

The compound of the present invention can be produced, for example, as follows. A hydroxy derivative represented by the following general formula (c) (where m and yJB are the same as defined above) is reacted with trifluoromethyl iodide in the presence of copper powder to form the following general formula (d) (wherein m and yJB are the same as defined above). , m, and ring B are the same as defined above.) A fluorine-containing hydroxy derivative was obtained. Subsequently, by nitrosation with NaN0□, the same formula as the following general formula (e) is obtained. ) and then reacted with the nitroso-hydroxy derivative (e).

A nitroso-hydroxy derivative represented by the formula (where m and ff1B are the same as defined above) was obtained.

Here, the indolenine derivative represented by the following general formula (f) (wherein R1, R2, R3, R4, and IA are the same as the above definitions) is converted to the following general formula (g) R'X (g )
(In the formula, .Preferably DMSO1DNAc, D
50°C to 150°C in an aprotic polar medium such as MF
It can be carried out smoothly.

In addition, the coupling reaction between an indolenine derivative and a nitroso-hydroxy derivative is carried out by reacting the indolenine derivative and R'X without a solvent or in a solvent at a reaction temperature of 0°C to 150°C for 1 to 8 hours. Rust conductor, as well as triethylamine, piperidine, piperazine,
The reaction is carried out by adding a base such as morpholine and reacting at a reaction temperature of 0° C. to 150° C. for 1 hour to 8 hours. Preferably, it can be carried out smoothly at 40°C to 120°C in toluene or ethanol in the presence of triethylamine.

Matrix materials for the photochromic material of the present invention include glass, optically transparent resin 1 such as polyvinyl butyral, polyvinyl alcohol, polyester, polystyrene, polycarbonate, polyvinylidene chloride,
Polyvinyl chloride, polymethyl methacrylate, polyvinyl acetate, cellulose acetate, epoxy resin, phenol resin, nylon resin, polyurethane, (urethane-modified) acrylate polymer of (halogenated) bisphenol A,
Amorphous polyolefins and mixtures or copolymers of the above resins can be used.

Methods for blending the photochromic compound of the present invention into the matrix material include dyeing, casting, coating of a blended polymer solution, or attachment after microencapsulating the photochromic compound of the present invention; Various methods can be applied, such as a method of bonding by reacting a reactive group such as a double bond or a silane coupling group with a matrix material.

Further, in the photochromic material of the present invention, ultraviolet absorbers, antioxidants, hindered amine stabilizers, etc. can be added to improve light resistance.

Furthermore, the thermal stability of the coloring state can be increased by adding an organic metal salt such as a zinc salt of 1-hydroxy-2-naphthoic acid.

[Example] Synthesis Example 1 Synthesis of 4.6-pisdo-2-naphthol
Dissolve in 50 ml of trifluoromethylioguide 2
0g and 10g of copper powder were added, and the mixture was stirred at 120°C for 3 hours. After the extraction process, the organic solvent was distilled off under reduced pressure, and the resulting residue was separated and purified using silica gel column chromatography to obtain 5 g of the title compound.

HNMR (CD, C1) 65.8 ppm (BS, L H), 7.
0-8.0 ppm (m, 5H) 'FNMR (CD, CI, CFCl, standard) δ -61
ppm (3F), -62ppm (3F).

Synthesis Example 2 1.33-trimethyl-6',8°-bistrifluoromethyl-spiro[indoline-23'-(38)
-Synthesis of (2,1-b)(1゜4)oxazine] 4.6-Pisdofluoromethyl-2-naphthol 5 g
was dissolved in 50 ml of dioxane, and 18 ml of IN aqueous sodium hydroxide solution was added. Under water-cooled stirring, sodium nitrite 3
After dropping 10 ml of an aqueous solution of 25 g of IN sulfuric acid aqueous solution,
ml was added dropwise, and the mixture was stirred at room temperature for 3 hours. After the extraction process, the organic solvent was distilled off under reduced pressure, and the resulting residue was dissolved in 50 ml of ethanol, and 2.6 g of 1.3.3-trimethyl-2-methyleneindoline and 1.5 g of triethylamine were added.
g was added.

After heating under reflux for 3 hours, the solvent was distilled off under reduced pressure, and the resulting residue was separated and purified using silica gel column chromatography to obtain the title compound.

Emax=605nm HNMR: (CD, C1) δ 1.3ppm (s, 6t(), 2.7
ppm (s.

3H), 6.4-8.0 ppm (m, 8H
)8.6 ppm (m, IH) 'FNMR (CD, CI, CFCl3 standards) δ -6
1 ppm (3F), -62 ppm (3F) Comparative Synthesis Example 1 1.3.3-Trimethyl-8-trifluoromethyl-spiro[indoline-2,3°-(3H)-naphtho(2,
1-b) Synthesis of (1,4)oxazine] 4. In the same manner as in Synthesis Example 1.2, using 6-iodo-2-naphthol instead of 6-diiodo-2-naphthol, The indicated compound was synthesized.

Emax=605r+n+ Comparative Example 2 λma,, x = 605 nm Example 1
Comparative Examples 1 to 2 The following tests were conducted using the above spirooxazine compounds obtained in Synthesis Example 2 as Example 1, Comparative Example 1 as Comparative Synthesis Example 1, and Comparative Example 2 as Comparative Example 2.

Add toluene solution of spirooxazine compound to 30% toluene of polyvinyl butyral and isopropyl alcohol (42 + 58) solution (spirooxazine compound/polyvinyl butyral = 0.15 mmol/g
) Stirred. A film having a thickness of about 50 μm was obtained by casting from this solution. It was air-dried at room temperature for 2 hours and at 40°C for 1 hour.

A xenon lamp was used as the excitation light source for measurement, and a HOYA glass filter U3 was used as the ultraviolet light transmission filter.
It was 60. Absorption wavelength and absorbance were measured using Tenba Denshi's instantaneous multi-photometering system MCPD-1000 at 20°C.
I went there.

Further, FIG. 1 shows the change in absorbance after long-term irradiation with ultraviolet light using a UV lamp.

[Effects of the Invention] The novel photochromic material of the present invention is characterized by extremely excellent durability against repeated light-emitting and decoloring, and has sufficient light resistance at a practical level.

Such photochromic materials are used for window dimming glass,
Light control materials for curtains, sunglasses, ski goggles, etc., photosensitive materials for printing such as recyclable copy paper, copying materials, various recording/memory materials, display materials, photosensitive materials for lasers, photosensitive materials for holography It is used as a material for optical filters, masking materials, photometers, display materials, or clothing and decorative items.

[Brief explanation of drawings]

FIG. 1 is a graph showing changes in absorbance after long-term irradiation with ultraviolet light using an LJV lamp. Figure 1

Claims (1)

[Claims] General formula (a) ▲Mathematical formulas, chemical formulas, tables, etc.▼(a) (In the formula, R_f represents a trifluoromethyl group, m≧2
. Rings A and B represent a hydrocarbon aromatic ring or a heterocyclic aromatic ring which may be substituted in addition to R_f. R^1, R^
2, R^3, R^4 are hydrogen atoms or have 1 to 2 carbon atoms
5 hydrocarbon group, or alkoxy group, F, or C
Halogen atoms such as L, Br, I, ester groups, cyano groups, nitro groups, ether groups, thioether groups, carbonyl groups, sulfonyl groups, amino groups, substituted amino groups, imino groups, amide groups, thioamide groups, urethane groups, It represents a urea group, an isocyanate group, an azo group, or a hydrocarbon group having a hydroxy group, a thiol group, a carboxyl group, a sulfonic acid group, and its metal base. R^1, R^2, R^3
, R^4 are the same or different substituents,
R^2 and R^3 may be bonded to each other and may be cyclized. )
A spirooxazine-based photochromic material represented by