JPS61291678A - Photochromic composition - Google Patents

Abstract

PURPOSE:To titled novel composition, containing a compound having a specific structure, capable of exhibiting phototropism of coloring to be a colored material by irradiation with light and returning to the original color by stopping the irradiation with light and assuming a hue different from blue and having a high decoloring rate. CONSTITUTION:A photochromic composition containing a compound expressed by formulab I (one of R1-R3 is lower lakoxy; another is lower alkyl; another is lower alkyl, H or halogen; at least one of R4-R7 is lower alkyl; the reset are H or halogen; R8 is lower alkyl), e.g. 1, 3, 3, 4, 5, 5', 8'-heptamethyl-9'- methoxyspiro [indoline-2,3'-[3H]-naphtho[2,1-b][1,4] oxazine]. The spirooxazine expressed by formula I can be obtained by heating a compound expressed by formula II and comoound expressed by formula III in absolute ethanol while refluxing.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention is directed to photochromic compositions, particularly photochromic compositions which are colorless in themselves and have photoreversibility, which develops color when irradiated with light and returns to the original colorless state when irradiation with light is stopped. The present invention relates to photochromic compositions shown in the accompanying drawings.

[Conventional technology]

Many substances exhibiting photochromic phenomena are known, including organic substances, crystalline inorganic substances, and glasses, and spiropyran is a typical photochromic compound of organic substances.

Spiropyran absorbs ultraviolet light and develops a color rather than being colorless, but because it has excellent properties such as vivid colors and high photosensitivity, attempts have been made to apply it to photochromic sunglasses, intermediate films for printing, ultra-micro films, etc. ing. And Spiro [Indoline-2, J/- (Jdan)-
7) [2,/-b)-(/,40-oxazine is known as one of the spiropyrans that has a fast decoloring speed, and is disclosed in U.S. Pat. No. 3,57g, 602, 3
．． ! ;62. /72; It is described in Japanese Patent Application Publication No. 2003-120003.

Photochromic sunglasses using spiropyran are already commercially available and turn blue under bright light. However, it takes more than 7 hours for the blue color to disappear and return to colorless.

[Problem that the invention seeks to solve]

However, a photochromic composition that exhibits a high decolorization rate and exhibits a color tone other than blue has not yet been reported.

An object of the present invention is to provide a novel photochromic composition that has a high decolorization rate and exhibits a color tone different from blue.

[Means for solving problems]

The present invention is a photochromic composition containing a compound represented by the following general formula (Il).

(However, in the above formula, one of R1, R2tR3
one is a lower alkoxy group, the other one is a lower alkyl group, the other one is a lower alkyl group, hydrogen atom or halogen atom: at least one of R4+R5+R6rR7 is a lower alkyl group , the others are hydrogen atoms or halogen atoms, and R8 is a lower alkyl group. ) Among the compounds represented by the above general formula (I), preferred are compounds in which the novel R1 in the general formula (I) is a methoxy group, N R2 + R3 + R4y R5 and R8 are methyl groups, and R6 and R7 are hydrogen atoms. Compound(
Ia) + R1 is a methoxy group, R2, R31R51R
6. Compound (Ib) in which R8 is a methyl group and R4 and R7 are hydrogen atoms, and R1 is a methoxy group +
Examples include compounds (IC) in which R21R31R4, R5, R6 and R8 are methyl groups and R7 is a hydrogen atom.

- The spirooxazine represented by the general formula (I) is a compound represented by the following general formula (II) and the general formula (11
The compound represented by No. 11 is produced by heating and refluxing the compound in an anhydrous erator.

N.

When this reaction is carried out in an anhydrous state and in the presence of triethylamine, the yield and purity are high. Recrystallization is generally carried out from a7ton. This method is described, for example, in US Pat J,
362. /72, J, 371,602 and Da, 2/3
, 010K is described.

Here, the compound represented by the general formula (Ill) can be generally synthesized from commercially available methyl isopropyl ketone and N-methyl-substituted phenylhydrazine by the ir'i, 5cher indyl synthesis method. However, it is also possible to directly add hydroiodic acid and heat it.For example, JAC3η5.39'llC102)
A suitable example is given in . Further, N-methyl-substituted phenylhydrazine can be easily obtained by reducing the corresponding nitroso compound with Zn powder by a known method. This is Org, 5
ynth,, col, Vol, If, p, l
It is described in l#.

In addition, in the general formula (II) required when synthesizing spirooxazine (IC), a compound (IIC) in which R41R5#R61R8 is a methyl group and R7 is a hydrogen atom,
It is new.

The compound represented by the general formula (It) can be obtained by nitroning the corresponding substituted corner 7 toll with nitrous acid in a known manner. This method is explained by Org, 5ynth, Gol,
Vol.

1, p'l//.

In addition, spirooxadi> (Ia), (It)),
The compound (It[s) in which R1 is a methoxy group + R2+R3 are a methyl group in the general formula (ffi) necessary for synthesizing (IC) is novel.

The photochromic composition of the present invention contains various compounds added to improve the durability of the photochromic compound represented by general formula (I) - a 112+ complex which is a singlet oxygen quencher, a peroxide decomposer, etc. There are cases where

The photochromic composition of the present invention, like other conventionally known photochromic compositions, can be used in various forms such as resin, solution, and vapor deposited film, and in solid or liquid form.

Poly(diethylene glycol bisallyl carbonate) (hereinafter abbreviated as R-39 resin), methyl methacrylate, polycarbonate, polystyrene polyvinyl butyral, polyvinyl chloride, vinyl acetate,
polyvinyl butyral, polyurethane, epoxy resin,
Ethyl cellulose etc. can be used. Particularly preferred are CjR-39 resin, polymethyl methacrylate, and polycarbonate, which are colorless and transparent and have properties suitable for plastic eyeglass lenses and sunglasses.

Examples of organic solvents that dissolve the compound represented by formula (I) include toluene, xylene, benzene, carbon tetrachloride, chloroform, ethyl alcohol, and methyl alcohol.

[Action and effect of the invention]

It is known that the photochromic mechanism of spiropyran compounds is ring opening of the biran ring and cis-trans isomerization by light. Color development is due to absorption of colored species (trans type).

Figure 1 shows the absorption spectrum measured at a sweep speed of 11,000 nm per minute after irradiating a sample with a compound (more) dispersed on the surface layer of an 0R-39 resin plate with light from a xenon lamp (300 W). The in-situ decolorization speed is shown in FIG. Note that the above sample turned greenish blue under sunlight.

As described above, by using the photochromic composition containing the compound represented by the general formula (1) of the present invention, it is possible to achieve an unprecedented high decolorization speed and a greenish blue color tone during color development.

The composition of the present invention can be used for plastic lenses, sunglasses, ski goggles, S1+, SnoJ
+ hit M + folding → always, Sumsu 7 Reef Δ female benefits.

〔Example〕

Next, specific examples of the present invention will be described, but it goes without saying that the scope of the present invention is not limited thereby.

Example 1/, 3, 3. μ,! ;, 31. ZaI-heptamethylta-I-methoxyspiro[indoline-2,3'-C3ta-
naf) (J, /-b) (/, #), txane> (I
a) (R1-CH30-' Rz , R3r R41R
51R6= CH3-; R6+ R7-H- Synthesis of compound (I)) 3.6-dimethyl-7-methoxy-2-su7tol l
Dissolve O.G. and sodium hydroxide 39 in 200ml of water, and add the sodium nitrite while stirring vigorously at O'C.After the addition is complete, coarsely stir at O'C.
1 of concentrated sulfuric acid/hour, yellow crystals precipitate out.

After filtration, the crystals were recrystallized from ligroin, and the crystals of 7.
A compound (■) of R2+ R3-CH3- was obtained.

The results of melting point, nuclear magnetic resonance absorption, infrared absorption, and elemental analysis of this crystal were as follows.

Melting point Ilon 113℃ Nuclear magnetic resonance absorption (CDcJ3) (60MH2) δppm
2.20, 2.2! ; (6H, S) +J
, 72 (JH, s), Otsu-<' (t H+ m)
+7,. 2 (JH, m) Infrared absorption (KBr) (cm-1) 3033.2ri63. /30! , /270,101.0
,790 elemental analysis value Calculated value Actual value C (%) 67,! ;2 67.7gH(%
) j, 47 j, J/Hiodide synthesized by a known method 2.3.3. lI,! ;-hexamethylindolenium (I[a) (R4yR5, Ra-C
H3-, R6, R7-H- compound (II))/(7) and the above compound (1113)/j in 200 ml paste9.
5%, dissolved in lr-tanol, and added triethylamine to this solution under a nitrogen gas stream. ;ml and reflux for 3 hours. After repulsion, a yellow-brown precipitate is obtained when the mixture is cooled to room temperature. After filtration, washing with a small amount of ethanol gives a pale yellow solid. Recrystallization from acetone yields 2 g of crystals.3. ．． 3. 'l
,! , 51. Zal-hebutamethyl-91-methoxyspiro [indolinco, 3'-(J-su-7) (,
2,/-b) (/, Il) oxazine (Ia) was obtained. The measurement results for this crystal were as follows.

Melting point /31~/g o'c Nuclear magnetic resonance absorption (CDOA'3) (40MHz) δpp
m /, Jj (4H, S), 7.9j (JH, S
)j,tI(/12H,m),J,7j(JH,S).

,4:,J(/H,m),7. J (jH, m) Infrared absorption (KBr) (cm-1) 30ψ! ;, 2973. /1130. /370,10!
;! ;, 7zaO elemental analysis value Calculated value Actual value C (%) 7g, 23 77.9! ;H(%
) 7.29 7.00 A CJR-39 resin plate of 30 mm x 20 mm x 8 mm was placed in a toluene solution of photochromism compound (Ia) of about 2 omg and 7 mJ, and after refluxing for about an hour, the 0R-39 resin plate was placed. was removed from the toluene solution, washed with toluene, and thoroughly wiped with paper soaked in acetone. Toluene that had penetrated into the CR-39 resin surface layer was removed by leaving it in the air in a dark place for a long time. This CjR-39 resin plate was almost colorless under a fluorescent light, but developed a greenish blue color under sunlight. After irradiation with sunlight, it became substantially colorless when left under a fluorescent light for 5 minutes. When exposed to sunlight again, the color developed into a greenish blue color. Note that a greenish blue color was also developed when irradiated with a xenon lamp (300W).

Example/! , 3. ! ;,6. ! ;', Zal-heptamethyl-
91-methoxyspiro[indoline-2,3/-(jH
)-su7)(,?,/-ri(/,#)oxazine)
(It))(R1-CH30-; R2+ R3+ R
5+ Rs + R8-CH3-: R41R7-H-
Synthesis of compound (I)) of iodination/, -i! synthesized by known methods. ＋ J ＋
J v j , 6-hexamethylindolenium (I
[')) (R5+R6+RB-CH3-R41R7-H
Compound (■)) of - and Compound of Example 1 Cm5)/
3 was dissolved in 0 ml of anhydrous ethanol, triethylamine 4 (m/) was added thereto in a nitrogen gas stream, and the mixture was refluxed for 3 hours. After repulsion, the mixture was warmed to room temperature to obtain a yellowish brown solid.

After filtration, wash with a small amount of ethanol and recrystallize from acetone to obtain pale yellow crystals.

3,! ,! , otsu,! ! , ZaI-hebutamethyl-91-methoxyspiro [Indolinco, j/-(JH)-su7) (2°/-b) (/, II] Oxazine (Ib)
/, 1 was obtained.

The measurement results of this crystal were as follows.

Melting point i? Helgj℃ Nuclear magnetic resonance absorption (CDC43) (Otsu (7MH2) δpp
m /, 2II (6H,S), 8qs (3H,S
).

2.11C/2H, m'), 3.70C3H,S'').

44 (/H, m, ), 7.7 (jH, m) infrared absorption (K
Br) (Cm-1) 30'lO,2970,/gtI! ;, /3 Otsu 0,
IQ! ;0, 790 elemental analysis value Calculated value Actual value C (%) 7g, 5377.9! ;H (%)
7.29 7.00 Photochromism As in Example 1, it was confirmed that 7 otochromism was exhibited.

Example 3 /, 3. j, (l,!;,6,3/,II-octamethylqr-methoxyspiro [indoline-2,3'-
(JH) -su7to (j, 1-b) (/4) Oxazi:
/ (IC) (R1-0H30-; R2+R31R4,
R5, R6+R8-CH3-, R7-H- compound (I
Synthesis of )) A mixture of 10 g of N-methyl-N-(3,g,!-triphenyl)hydrazine and 7 g of methyl isopropyl ketone is heated at 50° C. for 3 hours. The corresponding phenylhydrazone precipitates out as a white solid. Excess methyl impropyl ketone is distilled off under reduced pressure, and 30 ml of absolute ethanol is added to the residue, followed by further addition of hydriodic acid/j9. If this mixture is left at room temperature for 2 days, crystals will precipitate.After filtration, cold ether! ;Wash with Oml! yellow crystalline iodide/2,3°3,'1. ! ;, Otsu-hebutamethylindolenium (Inc) (R41R5+R6+R8-
A compound (■) of CH3-+R7-H- was obtained.

The measurement results for this crystal were as follows.

Melting point /l! 117℃ Nuclear magnetic resonance absorption (D20) (40MHz) δppm
/, (7j (4H, S), /, 9o (JH, S).

2.110 (riH, m), 2.7za (JH2S)y7,
oo(/H,S) Infrared absorption (KBr) (cm-1) 30! ;/ , 3020.29zaj, /#lIj , 1
37! ;, IO'13.

20 Elemental analysis value Calculated value Actual value C (%) jj, *9 j'2.7gH
(%) 6. a6t, /p The above compound (II
and the compound (Il[s)r synthesized in Example 1
The solution was dissolved in 70 ml of absolute ethanol, 22 g of triethylamine was added under a nitrogen gas stream, and the mixture was refluxed for 3 hours. After repulsion, the precipitated solid was cooled to room temperature, filtered, washed with a small amount of cold ethanol, and recrystallized from acetone to give about 19 pale yellow crystals. ;.

Otsu,! /, the I-octamethyl-9/-methoxyspiro [indoline-2,3l-(jgina7) (,j.

l-(/,4')oxazine (IC) was obtained. The measurement results for this crystal were as follows.

Melting point 735~/31℃ Nuclear magnetic resonance absorption (CDC13) (4(7MH2)δpp
m/,,to(6H,S),7.93(3H,
S).

r, 30 (/; H, m), 3.7 g (JH, S).

Otsu, 30 (/H, m), 7. <co(IIH, m) infrared absorption (KEr) (cm-1) 303! ;, ko93;0.14j', /3za091
03, 7zaO elemental analysis value Calculated value Actual value C (%) 7g, Il7 7g, 15H (%
) 7JJ 7.21I Photochromism Example/It was confirmed that photochromism was exhibited similarly to 7JJ 7.21I Photochromism Example/.

[Brief explanation of the drawing]

The drawings show examples of the present invention, and FIGS. 1 and 2 show the optical characteristics of a CR-39 resin plate containing a photochromic substance. Figure 1 5 representative (mm)

Claims (5)

[Claims] (1) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (However, in the above formula, one of R_1, R_2, R_3 is a lower alkoxy group, and the other One is a lower alkyl group, and the other one is a lower alkyl group, hydrogen atom or halogen atom; R_4, R_5, R_6, R
At least one of _7 is a lower alkyl group,
The others are hydrogen atoms or halogen atoms, and R_8 is a lower alkyl group. ) A photochromic composition comprising a compound represented by: (2) In the general formula (I), R_1 is a methoxy group, R_2, R_3, R_4, R_5 and R_8
The photochromic composition according to claim 1, wherein is a methyl group, and R_6 and R_7 are hydrogen atoms. (3) In the above general formula, R_1 is a methoxy group, R_
2. The photochromic composition according to claim 1, wherein R_3, R_5, R_6 and R_8 are methyl groups, and R_4 and R_7 are hydrogen atoms. (4) In the above general formula, R_1 is a methoxy group, R_
2. The photochromic composition according to claim 1, wherein R_3, R_4, R_5, R_6 and R_8 are methyl groups, and R_7 is a hydrogen atom. (5) The photochromic composition according to claim 1, wherein the medium containing the compound represented by the general formula (I) is a transparent plastic such as poly(diethylene glycol bisallyl carbonate), polymethyl methacrylate, polycarbonate, or polystyrene. .