JPH03234786A - Photochromic material - Google Patents

Abstract

PURPOSE:To obtain a photochromic material with excellent resistance to repeated development and disappearance of color with light and being useful for a light intensity adjusting material of a window panel or sunglasses, a photo-sensitive material for printing and photographing, etc. CONSTITUTION:A spiro-oxazine compd. of the formula (wherein Rf is polyfluoroalkyl or fluoroalkyl; R<1>, R<2> and R<3> are the same or different each other and each a 1-25C hydrocarbon group, a hydrocarbon group with alkoxy, halogen, ester, cyano, nitro, ether, thioether, carbonyl, sulfonyl, amino, imino, amide, thioamide, urethane, urea, isocyanate, azo, hydroxyl, thiol, carboxyl, sulfonic acid and metal salt groups; rings A and B are each a substd. or unsubstd. hydrocarbon arom. ring or heterocyclic arom. ring), e.g. 1,3,3-trimethyl- spiro [indolino-2'-trifluoromethyl-2,3'-(3H)-naphtho[2,1-b) (1,4-oxazine] is used as a photochromic material.

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/memory materials, display materials, photosensitive materials for lasers, photosensitive materials for holography, optical filters, masking materials, photometers, display materials, or paints, clothing, toys, sporting goods. This invention relates to a novel photochromic material useful as a material for cosmetics and ornaments.

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

(G. H. Brown, “Photochromi
sm”, Interscience, NewYo
rk (1971)) It is also known that spirooxazine compounds have photochromic properties in which they develop color when exposed to ultraviolet light and disappear when exposed to heat or visible light.

For example, Special Publication No. 45-28892, Special Publication No. 49-86
No. 31, JP-A-55-36284, JP-A-61-53
No. 288, JP-A-61-263982, JP-A-62-
No. 33184, USP 4342668 proposes substituted derivatives of spironaphthoxazine compounds and photochromic materials containing the compounds.

Also, JP-A No. 60-53586, JP-A No. 62-288
No. 682 discloses a rhotochromic material using a spironaphthoxazine compound having a trifluoromethyl group on a benzene ring or a naphthalene ring.

In addition, Japanese Patent Application Publication No. 61-501145 proposes a photochromic material using a spironaphthoxazine compound having an alkyl group or an alkylamino group in R2 of the general formula (a) for the purpose of improving high-temperature color development stability. ing.

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-62-164685, JP-A-63-30
No. 489 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. In addition, spirooxazine compounds have improved durability over repeated use compared to the above-mentioned compounds, and various substituted derivatives are known, but they lack diversity in color tone.

[Means for Solving the Problems] The present invention relates to a novel photochromic material for solving the above-mentioned problems. The above problems are solved by containing a novel spirooxazine compound into which an alkyl group or a fluoroalkyl group is introduced.

(In the formula, Rt represents a polyfluoroalkyl group or a fluoroalkyl group, R', R", and R' have 1 to 25 carbon atoms.
hydrocarbon group, or alkoxy group, F, or 01
%Br, halogen atoms such as engineering, ester groups, cyano groups,
Nitro group, ether group, thioether group, carbonyl group, sulfonyl group, amino group, substituted amino group, imino group,
It represents an amide group, a thioamide group, a urethane group, a urea group, an incyanate 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'R2 and R3 are the same or different substituents, and R2 and R' may be bonded to each other and cyclized. Rings A and B represent an optionally substituted hydrocarbon aromatic ring or a heterocyclic aromatic ring.

) In the above formula (a), the polyfluoroalkyl group represented by R is a linear, branched, or cyclic perfluoroalkyl group that may have an ether bond,
Or the following general formula (b)XCF! R,' (
b) (wherein, X represents F(, CI, Br, I, etc., R2
゛ is a linear, branched, or cyclic perfluoroalkylene group which may have an ether bond. A linear perfluoroalkyl group having 1 to 10 carbon atoms is preferred, and a trifluoromethyl group is particularly preferred.

In addition, in the compound represented by the above formula (a), the optionally substituted hydrocarbon aromatic ring or heterocyclic aromatic ring of rings A and H include a benzene ring, a naphthalene ring, a quinoline ring, a phenanthrene ring, and an anthracene ring. , pyridine ring, etc. These substituents include trifluoromethyl group, polyfluoroalkyl group, fluoroalkyl group,
F or C1%Br, a halogen atom such as an ester group, a cyano group, a nitro group, an ether group, a thioether group,
carbonyl group, sulfonyl group, 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 their A metal base, a hydrocarbon group having 1 to 25 carbon atoms, or an alkoxy group, a halogen atom such as F or C1, Br, etc., an ester group, a cyano group, a nitro group, an ether group,
Thioether group, carbonyl group, sulfonyl group, amino group, substituted amino group, imino group, amide group, thioamide group, urethane group, urea group, isocyanate group, azo group,
Alternatively, hydrocarbon groups having a hydroxy group, a thiol group, a carboxyl group, a sulfonic acid group, and their metal bases may be mentioned. Examples of R I RI R3 include compounds that are bonded to another spirooxazine ring via an alkyl group, an alkylene group, etc. to form a dimeric compound as a whole. Also RI RlR”, A ring,
It is also possible to introduce a reactive group such as a double bond or a silane coupling group into the B ring and bond it to the matrix material.

The novel photochromic material of the present invention has excellent durability for repeated photochromic and decoloring, and by introducing a polyfluoroalkyl group or a fluoroalkyl group to R2 in general formula (a), the maximum absorption during coloring is 60°nl11 to 700nm. It has the characteristic that

The compound of the present invention can be produced, for example, as follows. An indoline derivative represented by the following general formula (C) (wherein, R'R"R" and the ring are the same as defined above) and the following general formula (d
) R, I (d) (R is the same as defined above) is reacted with polyfluoro or fluoroalkyl iodosite by irradiation with light, and then the following general formula (e) 0 (in the formula , Ring B is the same as defined above, by reacting it with a nitroso-hydroxy derivative represented by ) in the presence of a base.

The polyfluoro or fluoroalkylation reaction of indoline derivatives is carried out without a solvent or in a solvent at -80°C to 200°C.
It is carried out by light irradiation at a reaction temperature of °C. The reaction with the nitroso-hydroxy derivative, which can be carried out smoothly at 0° C. to 50° C., preferably in a fluorinated solvent such as trichlorotrifluoroethane, is performed using triethylamine,
In the presence of a base such as piperidine, piperazine, morpholine, etc.
The reaction is carried out without a solvent or in a solvent at a reaction temperature of 0°C to 200°C. 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 resins 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.

[Example 1] 1,3.3-) Limethylosubilo [indolino-2°
-trifluoromethyl-2,3°-(3H)-naphtho(
2,1-b) Synthesis of (1゜4)oxazine] 1.3.3-Trimethyl-2-methyleneindoline is
F and I were dissolved in a 10% 1.12-trichloro-1,2,2-trifluoroethane solution and irradiated with light at 0°C for 1 hour. After evaporation of the solvent, the residue was dissolved in ethanol and 1
-Nitroso-2-naphthol and triethylamine were added and heated under reflux for 2 hours. After evaporation of the solvent, the residue was separated and purified by silica gel column chromatography to obtain the title compound.

Introduction of trifluoromethyl group was confirmed by F NMR spectrum.

[Example 2] 1.3.3-trimethyl-spiro[indolino-2°-
Pentafluoroethyl-2,3°-(3H)-naphtho(
2,1-b) Synthesis of (l,4)oxazine] The target compound was obtained in the same manner as in Example 1, using C, F, and I in place of CF3I.

[Example 3] 1,3.3-trimethyl-spiro[indolino-2°
-Synthesis of nonafluorobutyl-2,3'-(:Hl)-naphtho(2,1-b) (14oxazine) In the same manner as in Example 1, using C4F, ■ instead of CF, I. The target compound was obtained.

[Test Example] A toluene solution of a spirooxazine compound was added to a 30% toluene:isopropyl alcohol (42:5 g) mixed solution of polyvinyl butyral and stirred.

A film having a thickness of about 50 μm was obtained by casting from this solution. After air drying at room temperature for 2 hours and drying at 40° C. for 1 hour, the spectrum was measured.

[Effects of the Invention] The novel photochromic material of the present invention has excellent durability over repeated light-emitting and decoloring, and has an absorption maximum of 600 nm to 70 nm during color development.
It has the characteristic of 0na+.

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.

Claims (1)

[Claims] General formula (a) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (a) (In the formula, R_f represents a polyfluoroalkyl group or a fluoroalkyl group. R^1, R^2, R ^3 is a hydrocarbon group having 1 to 25 carbon atoms, an alkoxy group, F, or a halogen atom such as Cl, Br, or I, an ester group, a cyano group, a nitro group, an ether group, a thioether group, a carbonyl group, or a sulfonyl group. , amino group, substituted amino group, imino group, amide group, thioamide group, urethane group, urea group, isocyanate group, azo group, or hydrocarbon group having a hydroxy group, thiol group, carboxyl group, sulfonic acid group and its metal base. Indicates.R^1, R^2, R
^3 are the same or different substituents, and R^
2. R^3 may be bonded to each other and cyclized. Ring A,
B represents an optionally substituted hydrocarbon aromatic ring or heterocyclic aromatic ring. ) is a spirooxazine-based photochromic material.