JPH01106887A - Photochromic compound - Google Patents

Abstract

NEW MATERIAL:compounds of formulas I-III [R<1>-R<10> are H, alkyl, alkoxy, benzyl, aryl, halogen, nitro, alkoxyalkyl, cyano, alkylamino, carboxy(alkyl), polymerizable or condensable substituent: R<2> and R<3> may incorporate to form a hydrocarbon ring]. EXAMPLE:1,3, 3-Trimethylspiro[benz[g] indolino-2,3'-[3H]pyrido[3,2-f](1,4) benzoxazine]. USE:A photochromic material for clothing and ornamental purposes, a photochromic material for recording and optical purposes. It can be applied to sun glass, recording material, fibers and ornaments. PREPARATION:For example, 1,2,3,3-tetramethylbenz[g]indolium iodide and 5-nitroso-6-quinoline are added to ethanol and the mixture is refluxed together with triethylamine.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel photochromic compound useful as a photochromic material for clothing, ornaments, a photochromic material for recording materials, or an optical device.

[Conventional technology]

Among photochromic substances, indolinospiropyran compounds containing spirocarbons have an excellent speed of color development and fading, a large molar extinction coefficient, and show a wide variety of color changes, which is why many studies have been reported. has been done.

[Problem that the invention seeks to solve]

However, the above-mentioned spiropyran compound has a major problem in durability.The reason for this is that the a, a double bond in the pyran skeleton is easily attacked by singlet oxygen and decomposed. On the other hand, the (3,N double bond in the oxazine skeleton is strong against oxygen decomposition reactions.

Therefore, the present invention aims to solve these problems.
The objective is to provide a photochromic compound that can arbitrarily control the rate of color development and fading, has a large molar extinction coefficient, exhibits a wide variety of color changes, and is highly durable. .

[Means for solving problems]

That is, the present invention relates to a photochromic compound represented by the following general formula.

Box [wherein R1 to HIO are hydrogen, an alkyl group, an alkoxy group, a benzyl group, an aryl group]-logen.

Nitro group, alkoxyalkyl group, cyano group, alkylamino group, carboxy group, carboxyalkyl group 1 Substituent that can be polymerized or condensed R2 and R3 are the same or different selected from saturated hydrocarbon rings or unsaturated hydrocarbon rings Indicates one or more substituents. ] The photochromic compound of the present invention has an oxazine skeleton of 0. Durability is improved because the N double bond is less likely to react to attack by -heavy ring oxygen. Furthermore, since the substituents are various, including electron-withdrawing groups and electron-donating groups, it is possible to change the color tone by bathochromic effect and hypsochromic effect. Furthermore, when a substituent that can be polymerized or condensed is added to the molecule, it becomes polymerized by reaction with other components or with itself, and it becomes possible to prevent the outflow of the photochromic substance.

In this way, the present invention has solved the above-mentioned problems.

The photochromic substance of the present invention can be produced by kneading or dipping into synthetic resin or paper, by sublimation transfer, by dissolving or dispersing it in a coating material (primer, binder, hard foot, etc.) and applying it to a base material, or by applying a polymer. There are various methods of application, such as dissolving or dispersing it in a solution to form a film, or adding it to other polymers or copolymers and polymerizing or copolymerizing it.

Furthermore, the substituents capable of polymerization or condensation in the present invention include vinyl groups, allyl groups, and acrylic groups.

Examples include polymerizable substituents such as methacrylic groups and epoxy groups, and substituents capable of condensation reactions with other components such as hydroxyl groups, mercapto groups, and halogens.

Polymerization reactions for photochromic compounds include radical polymerization, ionic polymerization, isomerization polymerization, cyclization polymerization, elimination polymerization, double condensation, and addition condensation reactions. There are application methods such as copolymerization of

Additionally, photochromic substances and antioxidants.

-Addition of heavy ring oxygen quencher and ultraviolet absorber is effective in extending the lifespan and changing color tone of photochromic materials.

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these.

[Example 1] 1,3.5-)limethylsuviro[benz[1]indolino-2,3'-(5.H]pyrido[3,2-/)(i1
4) Synthesis of benzoxazine] and its application example 1. Iodine salt of 2,3,3-tetramethylbenz[1] indolium 557? (l O1mot) and 5-nitrone-6-chiralinol L 74 t ([L 01
m04) to 100 d of ethanol, and then add 212 ft of triethylamine (,0,012 mo
t) was added and refluxed in a nitrogen stream for 5 hours.

After removing the solvent, water was added and extraction was performed with methylene chloride. After treating this methylene chloride solution with activated carbon, the solvent was removed, a small amount of ethanol was added, and the mixture was cooled to -30°C.
The precipitated crystals were collected. These crystals were subjected to preparative liquid chromatography using chloroform as a solvent.
15.5-)limethylspiro[benz[da]indolino-2,3'-(!IH)pyrido(5,2-f)(1,4
) benzoxazine] was obtained in 2.08S' (yield 55%).
A 0vt% solution was prepared and heated to 100°C. In this solution,
A flat plate made of diethylene glycol bisallyl carbonate resin having a thickness of 2 trrm was immersed for 30 minutes.

The obtained flat plate was colorless indoors and colored blue by irradiating it with ultraviolet rays, and became colorless 10 minutes after the irradiation was stopped.

Evaluation of photochromic performance was carried out as follows and is shown in Table 1.

(1) Transmittance Table 1 shows the average transmittance of 400 to 700 nm before and after light irradiation. The light source for light irradiation is a 500W ultra-high pressure mercury lamp (
(manufactured by Ushio Electric Co., Ltd.), and the temperature at the time of measurement was 25°C.

(2) Durability Performance evaluation of transmittance after 50 hours was performed using a xenon long life fade meter (FAI, -25AI manufactured by Suga Test Instruments Co., Ltd.) and the results are shown in Table 1.

[Example 2] 1-Pentasulfobenzyl-3-methy/l/-! 1-
Engineering fA/Spiro [Benz (f) Indolino-2゜5'
Synthesis of -(3K)pyrido(-5,2-f)(1,4)benzoxazine] and its application example C2.5-dimethyl-3-ethylbenz(f)indolenine4.46 ? (0,02mob) and pentafluorohenecylobromide 5.22t (l O2mot
) and 10 m of ethanol in a sealed tube and reacted at 80°C for 4 hours, the precipitated crystals were washed with ether and 1-pentafluorobenzyl-2,3-dimethyl-3-ethylbenz(f) indolium bromide 7.93 f (
Yield: 82%). This salt and 5-nitrone-6-chiralinol were reacted in the same manner as in Example 1. ) pyrido[:3
．． 2-f)(114)benzoxazine was obtained in a yield of 28%.

This oxazine compound (L558f) was dissolved in the following coating solution.

, r-glycidoxypropyltrimethoxysilane 252
, Cl, 05 N hydrochloric acid 72 was gradually added dropwise to a solution consisting of 13v of colloidal silica (catalysts Kasei Kogyo Co., Ltd. 1 ethanol silica sol, solid content 30%) and methyl cellosolve 45F to perform hydrolysis. After aging at 0°C for 24 hours, glycerin diglycidyl ether (manufactured by Nagase Sangyo ■ 1 dena: 1-kF2X313'')
9? , 0.79% of perchloric acid was added at room temperature and stirred to make it homogeneous. Furthermore, several drops of a flow control agent ("L-7001" manufactured by Nippon Unicar Co., Ltd.) were added.

Diethylene glycol bisallyl carbonate resin, whose surface had been previously treated with a 4% aqueous sodium hydroxide solution, was immersed in this coating solution, and the film thickness after curing was 5 μm.
It was applied by dipping so that The curing conditions were heat curing at 80° C. for 1 hour and at 130° C. for 1 hour.

The obtained lenses were colorless indoors, but were colored reddish-purple by irradiation with ultraviolet light.

Evaluation of photochromic performance was carried out in the same manner as in Example 1, and the results are shown in Table 1.

[Example 3] Synthesis of 1-[P-allylbenzyl)-5,3-dimethylspiro[benz[θ]indolino2,3'-[3H]pyrido(5,2-f)(it4)benzoxazine] and its application examples 2.3.5-) Limethylpenz (e) Indolenine 4.
18? (α02mot), P-rioo methylstyrene 505°t (0,02mot), hydroquinone a
, 4? and ethanol2. The Od tube was sealed and the reaction was carried out at 80° C. for 3 hours. The precipitated crystals were washed with ether,
1-(P-allylbenzyl)-2,5,3-trimethylspiro[benz(8)indolium chloride 5.6
4fC yield 78%). This salt and 5-nitron-6
- chiralinol and hydroquinone (5 wt% based on salt)
) in the same manner as in Example 1 to produce 1-(P-allylbenzyl)-3,3-dimethylspiro[benz(e)indolino-2,5'-(3H)pyrido[3゜2-f )(
1,4) Benzoxazine] was obtained in a yield of 42%.

The obtained oxazine compound 11F, 2,2-bis(3,
5-dibromo-4-methacrylooxyethoxyphenyl)propane 252. Styrene 20f, diethylene glycol bisallyl carbonate 5f, and tert-butyl peroxyneodecanate α51 were mixed and poured into a mold with a center thickness of 21111 mm consisting of a vinyl acetate-polyethylene copolymer gasket and a flat glass mold. Polymerization was carried out at 40°C for 3 hours, 60°C for 8 hours, and 80°C for 2 hours. The obtained flat plate was colorless indoors, but turned reddish-purple when irradiated with ultraviolet light.

Evaluation of photochromic performance was carried out in the same manner as in Example 1, and the results are shown in Table 1.

[Example 4] S was applied to the flat plate produced in Example 1 by vacuum deposition.
A film with an optical thickness of TE'/4 (λ=s 20 nm) was formed in the order of In, ZrO, and Sin□. The photochromic performance of this flat plate was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

[Example 5] The coating solution containing no oxazine compound prepared in Example 2 was applied to the flat plate prepared in Example 3, and
It was cured in the same manner as in Example 2. The photochromic performance of this flat plate was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

[Example 6] The same vapor deposited film as in Example 4 was provided on the flat plate produced in Example 5. The photochromic performance of this flat plate was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

[Comparative Example 1] A solution of 1,3,3,4,6-hexamethylindolino-7'-methoxybenzobilirosvirane 20F having the above structure dissolved in diethylene glycol 80F was heated to 100°C, and this solution was heated to 100°C. A flat plate made of diethylene glycol bisallyl carbonate resin having a thickness of 2 fields was immersed for 30 minutes, and then washed with isopropyl alcohol. By vacuum deposition on this flat plate, 5in2, zro, Sin,
The optical film thickness is 2/4 (λ = 520 r
A membrane of Lm) was provided. This flat plate was colorless indoors, but turned orange when irradiated with ultraviolet light.

Evaluation of photochromic performance was carried out in the same manner as in Example 1, and the results are shown in Table 1.

Table 1 [Effects of the Invention] As described above, the present invention has excellent durability because it has an oxazine skeleton. Furthermore, a compound having a substituent that can be polymerized or condensed in its molecule can solve the problem of outflow of photochromic substances by polymerizing other components or itself.

For this reason, the present invention provides a sash glass and a window glass.

It can be applied to recording material 1w4 fiber and decorative items.

that's all Applicant: Seiko Epson Corporation Agent: Patent Attorney Mogamisuji (1 other person) l')

Claims (1)

[Scope of Claims] A photochromic compound characterized by being represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲Mathematical formulas, chemical formulas,
There are tables, etc.▼ or▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1 to R^1^0 are hydrogen, alkyl group, alkoxy group, benzyl group, aryl group, halogen, nitro group, Alkoxyalkyl group, cyano group, alkylamino group, carboxy group, carboxyalkyl group, substituent that can be polymerized or condensed, R^2 and R^3 are the same type selected from saturated hydrocarbon rings or unsaturated hydrocarbon rings, or Indicates one or more different substituents. ]