JPH01106888A - Photochromic compound - Google Patents

Abstract

NEW MATERIAL:A compound of formula I [R<1>-R<16> are H, alkyl, alkoxy, benzyl, aryl, halogen, nitro, alkoxyalkyl, cyano, alkylamino, carboxy(alkyl), SO3M (M is alkali metal), R<2> and R<3> may incorporate to form a hydrocarbon ring or polymerizable or condensable substituent]. EXAMPLE:1,3,3-Trimethylspiro[benz[e] indolino-2,3'-[2H]-(9'-methoxynaphtho)[2,1- b](1,4)oxazine. USE:A photochromic material for clothing and ornamental purposes, a photochromic material for recording materials and optical appliances. It can be applied to sun glass, window panes, recording materials, fibers and ornaments. PREPARATION:For example, 1,2,3,3-tetramethylbenz[e]indolium iodide and 1-hydroxy-2-nitroso-7-methoxynaphthalene are combined with ethanol and the mixture is refluxed in the presence of 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 the 7 otochromic substances, many studies have been reported on indri/spiropyran compounds, which have spirocarbons, because they have excellent color development and fading speed, large molar extinction coefficients, and show a wide variety of color changes. There is.

[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 C, C double bond in the pyran skeleton is easily attacked by the t-heavy ring oxygen and decomposed. On the other hand, the C9N double bond of the oxazine skeleton is strong against oxygen decomposition reactions.

Therefore, the present invention solves the problems as described above.
The purpose is to provide a highly durable 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.

In the R″C formula, R1-R16 are hydrogen, alkyl 2!!i-,
Alkoxy group, benzyl group, aryl group, halogen.

Nitro group, alfukidialkyl group, cyano group, alkylamino group, carboxy group, carboxyalkyl group, sa
+, u (M is an alkali metal), R2 and R3 together form a saturated hydrocarbon ring or an unsodated hydrocarbon ring.

The 7 otochromic compounds of the present invention represent one or more substituents of the same type or of the XA type selected from substituents capable of polymerization or condensation.
-Durability is improved because it is difficult to react to attacks by heavy ring oxygen. In addition, the substituent is an electron-withdrawing group, 'r! Due to the child-donating group and various, color tone changes due to bathochromic effect and hypsochromic effect are possible. Furthermore, when a substituent that is capable of polymerization or condensation is added to the molecule, it becomes polymerized by reaction with other components or with itself, making it possible to prevent the outflow of the 7-otochromic substance.

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

The seven otochromic substances of the present invention can be applied by kneading or dipping into synthetic resin or paper, by sublimation transfer, by dissolving or dispersing in coach ink materials (brimer, binder, heart coat, etc.) and applying to the substrate, There are various application methods, such as dissolving or dispersing molecules in a solution to form a film, or adding them to other monomers or copolymers and polymerizing or copolymerizing them.

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 that can undergo condensation reactions with other components such as hydroxyl groups, mercapto groups, and halogens.

Glymerization reactions of photochromic compounds include radical polymerization, ionic polymerization, isomerization polymerization, cyclization polymerization, elimination polymerization, monopolycondensation, and addition condensation reactions. There are application methods such as copolymerization with

Additionally, photochromic substances and antioxidants.

- Adding a biapical oxygen quencher and ultraviolet absorber is effective for prolonging the life of hemorrhoids and changing the color tone of photochromic substances.

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

〔Example〕

Example 1 Synthesis of 1.3.3-)limethylspiro[benz(El)indolino-2λ,5'-(2H)-(9/-meth),xinaphtho)(2,t-b)i+4)oxazine] and Application example 1.2,3.3-tetramethylbenz(,3) indolium iodine salt A 37 f (0,01mat) and 1-hydroxy-2-nitroso-7-medoxynaphthalene 2.03L? ([Lolmot) and ethanol 1
After adding 00d, add 1.212 more triethylamine
? (1 O1 mot) 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, and preparative liquid chromatography was performed to obtain the desired 1,3°6-drimethylspiro[benz(
e) 3.242 (yield: 60%) of indolino-2,3'-(2H)-(9'-methoxynaphtho)(2,1-b)(1,4)oxazine] was obtained.

The obtained oxazine compound o, 1? , methyl methacrylate 49.9 fiI and AlBNO, IS' were polymerized at 60° C. for 20 hours, and the resulting polymer was molded into a film having a thickness of cLllrrm. This film was colorless indoors, but turned blue when irradiated with ultraviolet light.

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

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

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

Example 2 1-benzyl-3,3-dimethylspiro[benz(e)
Synthesis of indolino-2,5'-(:2H)-(gumemethacrylooxina7)) (2,1-b) (1,4)oxazine] and its application example 2! 1.5-) Limethylpenz[e]intrilene 2.099 (0,01mot
-) and benzyl bromide t 71 f ((L 01
mot) and 10 m of ethanol in a sealed tube and heated at 80°C for 4 hours.
After reacting for an hour, the product was washed with ether and crystals of the bromine salt of 1-benzyl-2,S,5-trimethylbenz(e)indolium were obtained from A5B? (yield 89%).

1-Nitrone-2,7-hydroxynaphthalene synthesized from 2,7-hydroxyna 7talene and sodium nitrite 945? (5X 10-3 mot) and 1.91 of the above bromine salt were added to ethanol 50-, and then triethylamine [1,606r (6X 10-3 mol)
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 and the solution was purified using preparative liquid chromatography.
1-benzyl-3,3-dimethylspiro[benz[θ]
Indolino2,5'-(2H)-(9'-hydroxynaphtho)(2t1-11',: (1,4)oxazine) was obtained with IIL9421 (yield 40%).This oxazine compound 0.471if ( I Xi O-”
mot) and methacrylic acid chloride a 1045?
(I x 10-3 mol) and dry benzene for 10 s.
After adding to l, triethylamine cL1212? (
1,2Xl 0-” mob) in a nitrogen stream.

Stirring was performed at room temperature for 1 hour. After that, water was added, the organic layer was separated, the solvent was removed, and the target 1-benzyl-3,3-dimethylspiro[benz[e]indolino-2°5'-(2H )−(9'
-methacrylooxynaf)) (2$1-b) (1+4)
oxazine], 512f (yield 95%) was obtained.

Obtained oxazine compound 0.1? , 2, 2-bis(5,5-dibromo-4-methacrylooxyethoxyphenyl)propane 251. Styrene 202, diethylene glycol bisallyl carbonate) 5 S',
tart-butylbaroxyneocarbonate) (L5f
The mixture was poured into a mode A-do with a center thickness of 2R, which was purchased from a vinyl acetate-polyethylene copolymer gasket and two flat glass molds, and heated at 40°C for 3 hours at #60°C.
Polymerization was carried out for 8 hours and 80'' for 2 hours.The obtained flat plate was colorless indoors, but colored bluish-purple when irradiated with ultraviolet rays.Evaluation of photochromic performance was carried out in the same manner as in Example 1, and the results were as follows. are shown in Table 1.

Example 6 l-(P-allylbenzyl)-3,3-dimethylspiro[benz(e)indolino-2,3/-(2H)-(8
Synthesis of '-bromonaphtho)(2,1-1))(1,4)oxazine] and its application example OH=OH,.

2.5.5-) Limethylbenz (e) Indolenine2.
Otp y (o, o 1mot) and P-chloromethylstyrene t 525 ? (CL 01 mot), 0.2P of hydroquinone and 10ml of ethanol in a sealed tube,
After reacting at 80°C for 4 hours, the product was washed with ether and the crystals of the chlorine salt of 1-(P-allylbenzyl)-2,3,5-trimethylbenz(,3)indolium were collected by ho
yy<yield 85%).

Above chlorine salt +, 808 f (5X 10″’mob
) and 1-nitrone-2hydroxy-6-phyromonaphthalene t 26 ? After adding (5x 10-3 mot) hydroquinone [1,11 to 50 d of ethanol, an additional 0.606 r of triethylamine (6x lo''''3 mol
t) was added and refluxed for 2 hours in a nitrogen stream. 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, and the desired 1-(P-
allylbenzyl)-3,3-dimethylspiro[benz(
8) Indolino-2,3'-(2E[)-(8'-bromonaphtho)(2*1-1))(114)oxazine] was obtained at 0.924 P (yield 36%).

Obtained oxazine compound Q, IP, styrene 499
1. Screw 7z/-le A11? and AIBNO, 1
1 was polymerized at 80°0 for 20 hours, and the resulting polymer was molded into a film having a thickness of cLlMn. It was pale green indoors, but turned green-blue when exposed to 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 1-<r-acryloxypropyl)-5,5-dimethylspiro[benzC'e)indolino-2,3
'-(2H) -su 7 to (2,1-'b)(1
゜4) Synthesis and application example of oxazine] aOH.

βH1 OH2 0-00H-(!H.

2.5.5-trimethylbenz[e]indolenine2.
09F (0.01 mol) and 3-bromo-1-propatool 1.59? (101mob) and 10ml of roform were sealed in a sealed tube and reacted at 60°C for 200 hours,
The product was washed with ether to obtain 2.611 crystals of bromine salt of 1-(r-hydrodipropyl)-2,3,3-trimethylbenz[θ]indolium (yield: 75%).

The above bromine salt 1.74? (5X 10-3mot) and 1-nitrone-2-naphthol Q, 865r (5X10
-3mot) to 50m of ethanol, then goodbye triethylamine a606f (6X10''-3mot)
was added and refluxed for 2 hours in a nitrogen stream. 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, and preparative liquid chromatography was performed on 1-(γ-hydroxypropyl)-3,5-dimethylspiro[benz(8)indolino-2,3′-(2H )-naphtho(2,1-1)(1
t4) Oxazine] was obtained as (1739f (yield 35%).

This oxazine compound 0°422 f (l x 10
-3mot) and acrylic acid glolide 1091f (IX1
After adding 0″″’mot) to 10 m of dry benzene,
Triethylamine 0.1219 (I X 10-3m
ot') was added thereto, and the mixture was stirred at room temperature for 1 hour in a nitrogen stream. After this, water was added, the organic layer was separated, the solvent was removed, and the desired 1-(γ-acryloxypropyl)-1,3-dimethylspiro[benz[e]indolino-2, 3'-(2H)-naphtho(2
, 1-b) (1,4)oxazine] at 0.382 r
(yield 8o%).

0.11 of this oxazine compound was dissolved in 100r of Diabeam (manufactured by Mitsubishi Rayon ■), applied to an acrylic plate, and irradiated with a high-pressure mercury lamp (80 W/cm ) for 30 seconds. The resulting coating film had a thickness of 25 μm and was colorless indoors, but was colored 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 5 1, 3, 3. obtained in Example 1. -) IJ methylspiro[benz[θ]indolino2,3'-(2H)
-(9'-methoxynaphtho)(2,1-b)(1t4
) A solution of 20 ml of oxazine dissolved in 80 ml of diethylene glycol was heated to 100°C.
The head diethylene glycol bisacrylic carbonate resin flat plate was immersed for 30 minutes and washed with isopropyl alcohol. On this flat plate, by vacuum evaporation,
A film with an optical thickness of λ/4 (λ=520 rLm) was installed in the order of 5i02, ZrO, and Sin□.

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

Example 6 1,3.3-) obtained in Example 1! J Methylspiro[benz(e)indolino-2ts' (2H)-
(9'-methoxynaphtho)(2,1-b)(1,4)oxazine]1? , r-glycidoxypropyltrimethoxysilane 28y, ethanol 64r, 0.05N hydrochloric acid 72. Flow control agent 1021. It was dissolved in a coating solution prepared with o and o 7 y of stannous chloride. Apply this solution to a polycarbonate plate and
It was dried at ℃ for 6 hours (film thickness: 5 μm).

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. In addition, a compound having a polymerizable or condensable R substituent in its molecule can solve the problem of outflow of photochromic substances by polymerizing other components or itself.

Therefore, the present invention provides sunglasses and window glass.

It can be applied to 2m fibers as a recording material and decorative items.

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

Claims (1)

[Claims] A photochromic compound characterized by being represented by the following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 to R^1^0 are hydrogen, an alkyl group, Alkoxy group, benzyl group, aryl group, halogen, nitro group, alkoxyalkyl group, cyano group, alkylamino group, carboxy group, carboxyalkyl group, SO_3
M (M is an alkali metal), R^2 and R^3 represent one or more of the same or different substituents selected from saturated hydrocarbon rings, unsaturated hydrocarbon rings, and substituents capable of polymerization or condensation. ]