JPH04209692A - photochromic materials - Google Patents

Abstract

PURPOSE:To improve the durability in repeated photochrominism by coupling a specific indolenine derivative with a specific nitroso-hydroxy derivative. CONSTITUTION:An indolenine derivative of formula IV is obtained by reacting an amine derivative of formula I (wherein Rf is F or a polyfluoroalkyl; m>=2, ring A is an aromatic hydrocarbon ring that may be substituted by Rf and other groups or an aromatic heterocyclic ring), a hydrazine derivative of formula II obtained by diazotizing and reducing the amino derivative and a ketone of formula III (wherein R<2> to R<4> are each H, a 1-25C hydrocarbon group, alkoxy, halogen, ester, cyano, nitro, ((thio)ether, etc.), followed by the Fischer indole reaction. Then, a nitroso-hydroxy derivative of formula VI is obtained by nitrosating a hydroxy compound of formula V (wherein ring B is identical to ring A). Subsequently, the indolenine derivative is made to react with a compound of formula VII (wherein X is SO3C6H4CH3; R<1> is identical to R<2>) and then with the nitroso-hydroxy derivative to obtain a photochromic material.

Description

[Detailed description of the invention]

[00011

[Industrial Field of Application] The present invention is applicable to light control materials for windows, curtains, sunglasses, ski goggles, photosensitive materials for printing such as recyclable copy paper, copying materials,
or 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, cosmetics,
The present invention relates to a novel photochromic material useful as a material for decorative articles. [0002] [0002] Many photochromic compounds are known, and spiropyran compounds are a typical example. (G.H.Brown, “Photochromi
sm''', Wiley Intersctence,
New York (1971)) [0003] 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,
No. 28892, Japanese Patent Publication No. 49-48631, Japanese Patent Publication No. 1983
-36284, JP-A-61-53288, JP-A-6
No. 1-263982, Japanese Patent Publication No. 62-33184, US
P4342668 proposes a substituted derivative of a spironaphthoxazine compound and a photochromic material containing the compound. [0004] Furthermore, JP-A-60-53586 and JP-A-62-288682 disclose photochromic materials using spironaphthoxazine compounds having trifluoromethyl groups in benzene rings and naphthalene rings. [0005] Furthermore, JP-A-60-112880 and JP-A-62-153292 propose spiropyridobenzoxazine compounds and photochromic materials using the compounds. [0006] Furthermore, JP-A-62-164685 and JP-A-63-30489 propose subirophenanthrooxazine compounds and photosensitive materials using the compounds. [0007]

[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. [0008]

SUMMARY OF THE INVENTION 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 chemical formula 2 in which a polyfluoroalkyl group or a fluorine atom is introduced into Rf. [0009]

[00101] [In Chemical Formula 2, Rf represents a polyfluoroalkyl group or a fluorine atom, m≧2゜Rings A and B are a hydrocarbon aromatic ring or a heterocyclic ring system which may be substituted in addition to Rf] Represents an aromatic ring. R1, R2, R3, and R4 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 25 carbon atoms,
or an alkoxy group, halogen atom, ester group, cyan group, nitro group, ether group, thioether group, carbonyl group, sulfonyl group, amine group, substituted amino group, imino group, amide group, thioamide group, urethane group, urea group, A hydrocarbon group having at least one group selected from an isocyanate group, an azo group, a hydroxy group, a thiol group, a carboxyl group, a sulfonic acid group, and a metal base thereof. R1, R2, R3, and R4 are each the same or different substituents, and R2 and R3 may be bonded to each other and cyclized. ) [0011] In Formula 2, Rf represents a polyfluoroalkyl group or a fluorine atom, and may be the same or different. [0012] Ring A in the compound represented by formula 2. Examples of the hydrocarbon aromatic ring or heterocyclic aromatic ring which may be substituted in addition to Rf of B include a benzene ring, a naphthalene ring, a quinoline ring, a phenanthrene ring, an anthracene ring, a pyridine ring, and the like. Preferably, ring A is a benzene ring or pyridine ring, and ring B is preferably a naphthalene ring, quinoline ring, or phenanthrene ring. These substituents other than Rf include a fluoromethyl group, a halogen atom such as CI, Br, and I, an ester group, a cyano group, a nitro group, an ether group, a thioether group, a carbonyl group, a sulfonyl group,
Amino group, substituted amino group, imino group, amide group, thioamide group, urethane group, urea group, isocyanate group, azo group, or hydroxy group, thiol group, carboxyl group, sulfonic acid group and its metal base, carbon number 1 - 25
hydrocarbon group, or alkoxy group, CI, Br,
Halogen atoms such as I, ester groups, cyano groups, nitro groups, ether groups, thioether groups, carbonyl groups, sulfonyl groups, amino groups, substituted amine groups, imino groups, amide groups, thioamide groups, urethane groups, urea groups, isocyanates Examples include a hydrocarbon group having a group selected from a group, an azo group, a hydroxy group, a thiol group, a carboxyl group, a sulfonic acid group, or a metal base thereof. [0013] R1, R2, and R3 may also be bonded to another spirooxazine ring via an alkyl group, an alkylene group, etc. to form a dimeric compound as a whole. It is also possible to introduce a reactive group such as a double bond or a silane coupling group into R1, R2, R3, the A ring, and the B ring, and bond them to the Matri-Zix material. [00141 The novel photochromic material of the present invention has the characteristics that it has extremely excellent durability over repeated photo-coloring and decoloring by introducing a polyfluoroalkyl group or a fluorine atom into Rf of chemical formula 2, and can be used at a practical level. have [00151 The compound of the present invention can be produced, for example, as follows. [0016] The following chemical formula 3

[Chemical Formula 3] (In Chemical Formula 3, m, Rf, and ring A are the same as the definitions of the above Chemical Formula 2.) The amine derivative represented by the formula 3 is diazotized with NaNO2 and reduced with Na2SO:l to form the following Formula 4.
[0017]

A hydrazine derivative represented by the formula (in formula 4, m, Rf and term A are the same as defined in formula 2 above) was obtained. [0018] This is expressed as below 5

[0019
]

[Chemical formula 6] (m, Rf, R2, R3, R' in Chemical formula 6,
and Ring A is the same as defined in Chemical Formula 2 above. ) was obtained. [00201 Also, the following formula 7

[Chemical Formula 7] (In Chemical Formula 7, ring B is the same as defined in Chemical Formula 2 above.) By nitrosating with NaNO2, the following Chemical Formula 8 [0021] [Chemical Formula 8] (In Chemical Formula 8) , and ring B are the same as defined in chemical formula 2 above.)
A nitroso-hydroxy derivative represented by was obtained. [0022] Herein, the previously obtained indolenine derivative (
Formula 6) is converted to the following formula 9

[Chemical Formula 9] (In Chemical Formula 9, X is ■ or S03 Cs H4CH
3. R1 is the same as defined in Chemical Formula 2 above. ) and then a nitroso-hydroxy derivative (chemical formula 8) (see chemical formula 10 below). [0023]

[0024] The coupling reaction between an indolenine derivative and a nitroso-hydroxy derivative is a reaction between an indolenine derivative and R
After reacting X without a solvent or in a solvent at a reaction temperature of 0°C to 150°C for 1 to 8 hours, a nitroso-hydroxy derivative and a base such as triethylamine, piperidine, piperazine, or morpholine are added, and the reaction temperature is 0°C to 150°C. It is carried out by reacting for 1 to 8 hours at a reaction temperature of . Preferably, it can be carried out smoothly in toluene or ethanol in the presence of triethylamine at 0°C to 80°C. [00251 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, and polyacetic acid. Vinyl, cellulose acetate, epoxy resins, phenolic resins, nylon resins, polyurethanes, (urethane-modified) acrylate polymers of (halogenated) bisphenol A, amorphous polyolefins, and mixtures or copolymers of the above resins can be used. [0026] Methods for blending the photochromic compound of the present invention into the matrix material include a dyeing method, a casting method, a coating method with a blended polymer solution, a method of attaching the photochromic compound of the present invention after microencapsulating it, or a method of attaching the photochromic compound of the present invention to the matrix material. 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 in a compound with a matrix material. [0027] Further, in the photochromic material of the present invention, ultraviolet absorbers, antioxidants, hindered amine stabilizers, etc. can be added to improve light resistance. [0028]

[Examples] The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples in any way. [0029] [Synthesis Example 1] Synthesis of isopropylmethylketone-(3,5-bistrifluoromethyl)phenylhydrazone [003033, After dissolving 25 g of 5-bistrifluoromethylaniline in 100 ml of dioxane, 100 ml of water
ml and 40 ml of concentrated hydrochloric acid were added. While cooling with water and stirring, 100 ml of an aqueous solution containing 8.0 g of sodium nitrite was added dropwise, and then 200 ml of an aqueous solution containing 40 g of sodium sulfite was added. After being left at room temperature overnight, it was heated to 80°C. After the extraction process, the organic solvent was distilled off under reduced pressure. 15 g of isopropyl methyl ketone was added to the resulting residue, heated under reflux for 2 hours, and then distilled under reduced pressure to obtain 20 g of the title compound. [00311 [Synthesis Example 2] 4.6-Pisdofluoromethyl-2. 3. Synthesis of 3-trimethylindolenine [0032] 20g of isopropylmethylketone-(3,5-bistrifluoromethyl)phenylhydrazone was dissolved in 120ml of acetic acid and stirred at 90°C overnight. After the extraction process, the organic solvent was distilled off under reduced pressure, and the resulting residue was distilled under reduced pressure to obtain 12 g of the title compound. [0033] 'HNMR (CD3 C1): δ1.
3ppm (s, 6H), 2. 3ppm
(s, 3H), 7. 4-7°7ppm
(m, 2H) 19FNMR (CD3 C1, CFC13 standard): δ-
61ppm (3F), -62ppm (3
F) [0034] [Synthesis Example 3] 4.6-Pisdorifluoromethyl-1. 2. 3.
Synthesis of 3-tetramethylindoleninium iododide [
0035] 4,6-pisdofluoromethyl-2゜3
, 12 g of 3-trimethylindolenine was dissolved in 50 ml of chloroform, and 12 g of methyl iodosite was added. After stirring at 60° C. for one day, the reaction solution was filtered to obtain 17 g of the title compound. [oo36] [Synthesis Example 41 4.6-Pisdofluoromethyl-1. 3. 3-trimethyl-spiroindoline-2,3'-(3H)
-naphtho(2,1-b) (1,4)oxazine] Synthesis [0037] 4,6-pisdorifluoromethyl-1°2, 3. Dissolve 10.0 g of 3-tetramethylindoleninium iododide in 50 ml of ethanol,
5.0 g of -nitroso-2-naphthol and 4.6 g of triethylamine were 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 5.1 g of the title compound. This compound was used in the examples below. [0038] λmax=575nm HNMR (CD3Cl): δ1. 4ppm (
s, 6H), 2. 7ppm (s,
3H), 6. 3-7. 9ppm (m, 8
H), 8. 6ppm (m, LH)19
F NMR (CD3Cl, CF C13 standard):
δ-61ppm (3F), -62ppm (
3F) [0039] [Synthesis Example 5] 4, 5. 6. 7-tetrafluoro1. 3.
3-trimethyl-spiro[indoline-2,3'-(
Synthesis of [3H)-naphtho(2,1-b) (1,4)oxazine] [From 25 g of 004012,3,4,5-tetrafluoroaniline, the indicated compound was synthesized using the same method as in Synthesis Examples 1 to 4. 4.1g of was obtained. [00411λmax=600nm HNMR (CD3 CI): δ1.4ppm (s
, 6H), 2. 7ppm (s, 3
H), 6. 4-7. 8ppm (m, 6H
), 8. 5ppIl(m, LH)19FN
MR (CD3 C1, CFCl3 standard): δ-148p
pn+ (IF), -155ppm (IF), -
158ppn+(IF), -160ppm(IF)
[0042] [Comparative Synthesis Example 11 5-fluoro-1,3,3-trimethyl-spiro[inzadrine-2. 3'-(3H)-naphtho(2,1-b
) (1,4) Oxazine] Synthesis of [0043] The described compound was synthesized from 5-fluoro-1,2,3,3-tetramethylindoleninium iododide in the same manner as in Synthesis Example 4. [0044] λmax=605 nm [0045] [Comparative Example 2]

[Chemical Formula 11] Spirooxazine compound represented by Chemical Formula 11 (λmax=
605 nm). [0046] [Examples 1-2. Comparative Examples 1 to 2] The spirooxazine compound obtained in Synthesis Example 4 as Example 1, obtained in Synthesis Example 5 as Example 2, obtained in Comparative Synthesis Example 1 as Comparative Example 1, and the above spirooxazine compound as Comparative Example 2 The following test was conducted using [0047] 30% toluene of polyvinyl butyral:
A toluene solution of a spirooxazine compound was added to a mixed solution of isopropyl alcohol (42:58) (spirooxazine compound/polyvinyl butyral = 0.15 mm).
ol/g) was stirred. Cast film is formed from this solution for about 50 minutes.
A film with a thickness of 0μ was obtained. Air dry for 2 hours at room temperature, 4
It was dried at 0°C for 1 hour. [00481 When irradiated continuously for 30 hours using a 150W xenon lamp, discoloration was significant in Comparative Examples 1 and 2, but almost no discoloration was observed in Example 142. [0049]

Effects of the Invention The novel photochromic material of the present invention is characterized by extremely excellent durability against repeated decolorization, and has sufficient light resistance at a practical level. [00501 Such photochromic materials can be used as light control materials for windows, curtains, sunglasses, ski goggles, etc., photosensitive materials for printing such as recyclable copy paper, copying materials, or various types of recording/memory. It is used as a display material, a photosensitive material for lasers, a photosensitive material for holography, an optical filter, a masking material, a light meter, a display material, or a material for clothing and decorative items.

Claims (1)

[Claims] [Claim 1] [Claim 1] ▲ Numerical formulas, chemical formulas, tables, etc. R^1, R^2, R^3, and R^4 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 25 carbon atoms, or an alkoxy group, a halogen atom, an ester group, a cyano group,
Nitro group, ether group, thioether group, carbonyl group, sulfonyl group, amino group, substituted amino group, imino group,
A hydrocarbon group having at least one group selected from an amide group, a thioamide group, a urethane group, a urea group, an isocyanate group, an azo group, or a hydroxy group, a thiol group, a carboxyl group, a sulfonic acid group, and a metal base thereof. R^1, R^2, R^3, and R^4 are the same or different substituents, respectively, and R^2 and R^3 may be bonded to each other and cyclized. ) is a spirooxazine-based photochromic material.