JPS63250381A - Photochromic compound - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R1 represents H or meth yl; R2 represents 1-30C alkylene, etc.; R3-R6 and R10-R15 represent lower alkyl, lower alkoxyl, 2-21C alkoxyalkyl, H, halogen atom., nitro, cyano, amino, OH, etc.; R7 and R8 represent H, lower alkyl, lower alkoxyl, 2-21C alkoxyalkyl, aryl, benzyl, etc.; R9 represents lower alkyl, lower alkoxyl, 2-21C alkoxyalkyl or H). EXAMPLE:1-( 3''-Methacryloyloxypropyl )-3,3-dimethylspiro{indolin o-2,3'-naphtho[2, 2-b][1,4]-oxazine}. USE:An image displaying material and optical recording material, exhibiting high variety color change and having great molar extinction coefficient. PREPARATION:An indole derivative expressed by formula II is reacted with a halogenated alcohol expressed by the formula X-R2-OH to form a salt expressed by formula III, which is further reacted with a compound expressed by formula IV to afford a compound expressed by formula V. The resultant compound is reacted with a compound expressed by formula VI.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel photochromic compound.

[Conventional technology]

Among photochromic substances, substances with spirocarbon exhibit a wide variety of color changes, and many have large molar extinction coefficients.As representative substances, they are expressed by the general formula +I) # (n) ? Substances having the basic skeleton shown in (4) can be listed.

(I) (I[)0[I) (R is an arbitrary substituent) Such photochromic materials are often used in a form dispersed or dissolved in a binder such as a polymer compound. is known as an image display material or an optical recording material.

In addition, for the purpose of improving the thermal stability of the photochromic compound in the coloring state, general formulas (ff), (V)
Attempts have been made to copolymerize a heptamer having a spiropyran skeleton as shown in the figure below with other monomers.

(,r,i3mets:J,POlym,Sci,.

Polym, Ohem, Ed, 12,2511 ((ff
) Seki (R is an arbitrary substituent) [Problems to be solved by the invention] However, the substance represented by the above-mentioned general formula (I) has a major problem in durability, and the reason for this is 5/, 41-position 0
．． This is because the zero double bond is easily attacked by singlet oxygen and decomposed. In contrast, the general formula II) p CmJ
Since the substance represented by the formula has double bonds of O and N at the 3/ and 41-positions, it is difficult to be attacked by oxygen and has excellent durability. However, when such photochromic substances are used after being dispersed, dissolved, or impregnated in a polymer, there is a problem that the photochromic substance flows out due to long-term use, resulting in a change in density during color development.

On the other hand, by copolymerizing the monomer represented by the general formula (IV) # (V) with other components, it is possible to prevent the outflow of the photochromic substance, and at the same time it is also possible to improve thermal stability. It is. However, as mentioned above, in the case of a spiropyran compound having a C,O double bond at the 37,4/- position, the durability is poor, so the general formula (f
Durability cannot be obtained with a photochromic monomer represented by fJ, (V).

The present invention aims to solve these problems, and aims to exhibit a wide variety of color tone changes, have a large molar absorption coefficient, be excellent in durability, and be compatible with other component monomers. An object of the present invention is to provide a photochromic compound that can be polymerized.

[Means for solving the gap]

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

L=.

death.

[In the formula, R1 is a hydrogen atom or a methyl group, R3 is a carbon number of 1
~3a41s alkylene group or general formula 1 ・-COH
2>m-g>(OH2)n-(where m and n are each 0
(representing an integer of ~15) or derivatives having these substituents as the basic skeleton, R3, R4, R5, R
6, RIO, R11, FL12, Rlm.

R14 and RlB are a lower alkyl group, a lower alkoxy group, or an alkoxyalkyl group having 2 to 21 carbon atoms.

A carboxyalkyl group having 1 to 20 carbon atoms or a derivative having a substituent thereof as a basic skeleton, or a hydrogen atom, a halogen atom, a nitro group, a cyano group, an amide group, a hydroxyl group, -
303M (M is an alkali metal), R7 and R8 are hydrogen atoms, lower alkyl groups, lower alkoxy groups, carbon number 2-
21 alkoxyalkyl groups, aryl groups, benzyl groups or derivatives having these substituents as the basic skeleton, or substituents in which R7 and R8 form an unsaturated or saturated hydrocarbon ring, Rll is a lower alkyl group, a lower alkoxy group,
Represents an alkoxyalkyl group having 2 to 21 carbon atoms or a derivative having these substituents as the basic skeleton, or a hydrogen atom,
] The 7 otochromic compound of the present invention has O at the 3/ and 4/ positions.
, N double bonds, it becomes less susceptible to attack by −m-term oxygen and improves durability. Furthermore, since it has a polymerizable acrylic or methacrylic group in the molecule, it can be used with other ingredients!
By performing copolymerization with -, it is possible to prevent the outflow of the photochromic substance, and at the same time it is also possible to improve thermal stability. Furthermore, since the substituents are various, including electron-withdrawing groups and electron-donating groups, it has rich bathochromic and hypsochromic effects and changes in color tone. In this way, the present invention has solved the above-mentioned problems.

In the present invention, as the photochromic compound and other component monomers that can be copolymerized with the product, any commonly used polymerizable monomers can be used. For example, acrylic acid, methacrylic acid, acrylic ester, methacrylic acid Examples include acid esters, styrene M vinyl, acrylonitrile, diethylene glycol bisallyl carbonate, and the like. Furthermore, it is also possible to use two or more of these other component monomers at the same time.

Furthermore, adding an antioxidant, a stacked oxygen quencher, and an ultraviolet absorber to the mixture of the photochromic compound and the above-mentioned other ingredients in the present invention is effective in extending the life of the photochromic performance and changing the color tone. be.

Furthermore, as a polymerization initiator for copolymerizing the above-mentioned 7-mer, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxydicarbonate, peroxyester, etc. In addition to organic peroxides, polymerization initiators such as azobisisobutyronitrile are suitable.

The proportion of the seven otochromic compounds of the present invention in the copolymer is desirably changed as appropriate depending on the intended use.

Here, the photochromic compound in the present invention was synthesized as follows.

First, an indole derivative represented by the general formula (b) is synthesized by Fisher's indole synthesis method, and then this is reacted with a halogenated alcohol represented by the general formula (b) in a solvent under airtight conditions to form the indole derivative represented by the general formula (b). (Obtain the salt of vl4.

(vl (b) 0H adjacent (R1, R3, R4, R5, R6, R7, R8, Rj are the same as above, X represents a halogen atom) Next, the salt of general formula (4) and the general formula ( The compound represented by (b) is reacted in a solvent in the presence of a catalyst to obtain a compound represented by general formula (3).

H (4) (b) H (X) (RIO, R11, R12, R13, R14, and R15 are the same as above) The compound of general formula (X) thus obtained was dissolved in a solvent, and in the presence of a catalyst, The photochromic compound of the present invention is obtained by dropping the compound of formula (xl) and reacting.

H (X) (R) M=0 0=CH2 The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto [Examples] (Example 1) 1-( 3"-methacryloyloxypropyl)-5,5
-dimethylspiro[indolino-2,3'-naphthol:
2.1-1)) CI, 4)-Oxazine] Synthesis 2' (ll(! !!' 0f12 〇2.

0=OH2 Product 3 Phenylhydrazine 5.409 5-methyl-2-butanone 520] and concentrated sulfuric acid 157as in ethanol
After heating under reflux for an hour, the solvent was distilled off and the residue was made alkaline with an aqueous sodium hydroxide solution. Then, after extraction with ether and distillation of the solvent, vacuum distillation (α01+ga+Hf, 4
7°C) and 2,3°3-trimethylindolenine 7.
．． 2s? (yield 919%).

Subsequently, the above 2,3.5-)limethylindoledine and 3
A reaction was carried out with 9.58 f of -bromo-1-propertool in chloroform at 60° C. for 24 hours under sealed conditions. After distilling off the solvent, benzene was added and the precipitate was filtered to obtain 1-(3'-hydroxypropyl)-2,3,3-
Bromine salt of trimethylindolenine IQ, 14P (yield 7
! 1L6%) was obtained.

Next, the bromine salt of indolenine and 1-nitroso-2-
7 toll'5.88F and triethylamine &871
was dissolved in ethyl alcohol and heated under reflux for 3 hours under a nitrogen stream. After the reaction, the solvent was removed and extraction was performed with methylene chloride/water to separate the organic layer into a thin layer. As a result, 1-(3 '-Hydroxypropyl)-5,5,-dimethylspiro[indolino-2°3'-su7)[:2,1-1))I:1.
4)-Oxazine] Matakuchi 41 (yield 557%) was obtained.

Finally, the oxazine compound and triethylamine 2.
862 was dissolved in dioxane, and while stirring, 1.98 t of methacrylic acid chloride was gradually added dropwise at room temperature and the reaction was carried out for about 5 hours. After the reaction was completed, the precipitated triethylamine salt was filtered, and then The solvent was distilled off. By recrystallizing the obtained crystals several times with methanol, 1-
(5!-methacryloyloxypropyl)-5,5-dimethylspiro[indolino-2,5'-su7[:2,
1b) (1*a)-oxazine)&49F (yield 7aO%) was obtained. This crystal was a pale yellow crystal and had a melting point of 167-168°C.

Thus obtained oxazine compound 151 and methyl methacrylate tomo/! -49,5F Furthermore, diimpropyl peroxydicarbonate 1. as a polymerization initiator. Of
After mixing, in a flat mold glass (center thickness 5 Ia
The resulting synthetic resin plate, which was injected at a temperature of 100 t) and polymerized from 30 t+ to 90 tF at a heating rate of fOυ/1 hour, was colorless and transparent indoors, but was colored blue by irradiation with ultraviolet rays.

The performance of this photochromic synthetic resin plate was evaluated as follows, and the results are shown in Table 1.

(1) Transmittance Transmittance was measured by irradiating light using a 500 W ultra-high pressure mercury lamp (manufactured by Ushio Electric Co., Ltd.) at 25°C. Indicated.

(2) Thermal stability Light irradiation was performed in the same manner as in the measurement of transmittance in (1), and the temperature was left in an environment of 50°C. Table 1 shows the time required for post-irradiation transmittance)/2).

(3) Durability After being exposed to a xenon long-life fade meter (PAL-25AI manufactured by Suga Test Instruments Co., Ltd.) for 50 hours, the transmittance performance of (1) was evaluated and shown in Table 1. (4) Chemical resistance After being immersed in ethanol for a day and night, the transmittance performance of (1) was evaluated and shown in Table 1.

(Example 2) 1-<5”-acryloyloxypropy/I/)
-3,3-dimethylspiro[indolino-2,5'-(
Synthesis of Z''QfZ2 3''Ql(!8=0 ■ Water (S5CH with 1.55 f of sodium hydroxide and 6-bromo2-su7 After dissolving Toll a52?, this aqueous solution was cooled to 0°C, then sodium nitrite Z75? was added under stirring, and while keeping the liquid temperature at 0°C, concentrated sulfuric acid I CL2 was added.
After the completion of 1 reaction in which cc was gradually added dropwise, the precipitate was filtered to obtain 6-bromo-1-nitroso-2.
-S7 Thor 9.25? (yield 919%).

6-bromo-1-nitroso-2-su7tol obtained by the above method and the same bromine salt of 1-(3'-hydroxypropyl)-2,5,5-trimethylindolenine as synthesized in Example 1. 1α91? and triethylamine 7,59 were reacted and purified in ethanol in the same manner as in Example 1,
1-(3”-hydroxypropyl)-3,5-dimethylspiro[indolino-2* 5'(8'-bromonaphtho)[:2.1-1))C8,4)-oxazine]
9.98t (yield 6 [L 3%)] was obtained.

Furthermore, the oxadi/compound and triethylamine 53
52 and Acry I'&II! ! ! ! Chloride 2. O
1 was reacted and purified in the same manner as in Example 1, and 1-(31
-acryloyloxypropyl)-3,3-dimethylspiro[in-tri/-2,3'-(8'-bromonaphtho)[2,1-1))[1,4)-oxazine]7.
67f (yield 6a6%) was obtained. This crystal was a pale yellow crystal and had a melting point of 197-199°C.

The thus obtained oxazine compound α5 and the methyl acrylate monomer 49.5? Furthermore, diisopropyl peroxydicarbonate (diisopropyl peroxydicarbonate) is used as a polymerization initiator.1. O
f was mixed and polymerization was carried out in the same manner as in Example 1 above. The obtained synthetic resin plate was colorless and transparent indoors, but was colored blue by irradiation with ultraviolet light.

The performance of this photochromic synthetic resin plate was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

(Example 5) 1-(P-methacryloyloxymethyl 7eniN)-5
,3-dimethylspiro[indolino-2,S'-(9
'-methoxyna7)) (2,1-1:+) Ct-t
4)-Oxazine] C=0 0=OH2 Crystal 3 The same 2,5.5-)limethylindoleene 1cLOy synthesized in Example 1 and P-bromobenzyl alcohol 11.8F were synthesized in Example 1. React and purify in the same manner as 1
-(P-hydroxymethylphenyl)-2,5,5-)
19.38 t (yield: 9α1%) of the bromine salt of remethyly/drenin was obtained.

Next, 7-medoxy-1-nitrone-2-naphthol was synthesized by the following method.

16f of 2,7-hydroxynaphthalene in 500cc of water
and 4.50 r of sodium hydroxide were dissolved and cooled to 10°C. While stirring this mixture, dimethyl sulfate & 32
was gradually added dropwise, and after the completion of the addition, the mixture was heated under reflux at 60° C. for 2 hours. Finally, this mixture was cooled to 0°C, the precipitate was filtered, and 7-medoxy 2-su7tol 1α13t
(yield: 511L, 2%).

Next, add 100 square meters of water and 2. i5f and the above 7-medoxy-2-naphthol were dissolved and cooled to 0°C9.Next, 4.1SP of sodium nitrite was added, and after stirring thoroughly, concentrated sulfuric acid 1a51m was added with stirring for 1.5 hours. The mixture was further stirred for 1 hour while keeping the liquid temperature at 0°C. Finally, filter the precipitate and wash it with water.
-nitrone-2-su7)-#IQ, 97P (yield 92.
8%).

Bromine #1 of 1-(P-hydroxymethylphenyl)-2,5,5-)limethylindolenine obtained by the above method
111L48F and 7-medoxy 1-nitrone-2-naphthol IQ, 97F and triethylamine IQ, 91
F was reacted and prepared in ethanol in the same manner as in Example 1, and 1-(P-hydroxymethylphenyl)-s,s-dimethylspiro[indolino-2,5'-(9'-methoxynaphtho)C2 , 1-b) [:1,4)-oxazine) 15.342 (yield: 651%).

Furthermore, the oxazine compound and triethylamine5.
Example 1: 16f and methacrylic acid chloride 5562
was reacted and purified in the same manner as 1-CP-methacryloyloxymethylphenyl)-3,3-dimethylspiro[
indri/-2,5'-(9'-methoxyna7))[:
2.1-1)) CI, 4]oxazine) 11.90f(
The yield was 67.4%). The crystals were brownish-white crystals and had a melting point of 209 to 210°C.

The oxazine compound thus obtained (L5r and methyl methacrylate monomer 49.5 P and diisopropyl peroxydicarbonate as a polymerization initiator) 1.
Or was mixed and polymerization was carried out in the same manner as in Example 1 above. The obtained synthetic resin plate was colorless and transparent indoors, but was colored blue by irradiation with ultraviolet light.

The performance of this photochromic synthetic resin plate was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

(Comparative Example 1) 1-(!l''-hydroxypropyl)-3,5-dimethylspiro[indolino-2,5
'-su;ytoC2,1-b)(1,4)-oxazine)
Ilsr was dissolved in toluene 2 (H), then mixed with methyl methacrylate monomer 49,5 r, and further polymerized in the same manner as in Example 1 by adding 1.0 l diisopropyl peroxydicarbonate as a polymerization initiator. I did it.

The obtained synthetic resin plate was colorless and transparent indoors, but was colored blue by irradiation with ultraviolet light.

The performance of this photochromic synthetic resin plate was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

(Comparative Example 2) Diethylene glycol bisallyl carbonate monomer 50r and polymerization initiator diisopropyl baroxydicarbonate) 1. Polymerization was carried out in the same manner as in Example 1 by adding Of to obtain 7-rat plates of diethylene glycol bisallyl carbonate resin. This flat plate was used as the 1-(31-hydroxypropyl)-
5,5-dimethylspiro[indolino-2,3'-nat[2tl-1))C1t4)-oxazine)s, or
And diethylene glycol 100? 1 to a mixture consisting of
A photochromic synthetic resin board was obtained by immersing it at 10°C for 15 minutes and washing it in ethanol to wash away the attached diethylene glycol.The obtained synthetic resin board was colorless and transparent indoors, but turned blue when irradiated with ultraviolet light. Colored.

The performance of this photochromic synthetic resin plate was evaluated 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 an oxazine skeleton and therefore has excellent durability, and furthermore, since it has a polymerizable double bond in the molecule, it can be copolymerized with other components. According to
It is possible to improve thermal stability and prevent outflow of photochromic substances, and to obtain stable dimming performance over a long period of time. Therefore, the present invention has a wide range of applications including recording materials, sunglasses, and ornaments, and is expected to be further developed in the future.

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

1゜

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 is a hydrogen atom or a methyl group, R_2 is an alkylene group having 1 to 30 carbon atoms, or the general formula -(CH_2)m (CH_2)n (here, m , n each represents an integer of 0 to 15) or derivatives having these substituents as the basic skeleton, R_3, R_4
, R_5, R_6, R_1_0, R_1_1, R_1_
2. R_1_3, R_1_4 and R_1_5 are a lower alkyl group, a lower alkoxy group, an alkoxyalkyl group having 2 to 21 carbon atoms, a carboxyalkyl group having 1 to 20 carbon atoms, or a derivative having these substituents as the basic skeleton, or a hydrogen atom , halogen atom, nitro group, cyano group, amino group, hydroxyl group, -SO_3M (M is an alkali metal), R_
7 and R_8 are hydrogen atoms, lower alkyl groups, lower alkoxy groups, alkoxyalkyl groups having 2 to 21 carbon atoms, aryl groups, benzyl groups, derivatives having these substituents as the basic skeleton, or unsaturated or saturated with R_7 and R_8 The substituent R_9 forming a hydrocarbon ring represents a lower alkyl group, a lower alkoxy group, an alkoxyalkyl group having 2 to 21 carbon atoms, a derivative having these substituents as a basic skeleton, or a hydrogen atom. )