JPH0126634B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a photochromic material, and more particularly to a photochromic material made of a compound that repeatedly changes color or discoloration under the action of light. [Prior art and its problems] Photochromism is a phenomenon that has attracted attention over the past few years, and is a phenomenon in which when a certain compound is irradiated with light containing ultraviolet light, such as sunlight or light from a mercury lamp, its color rapidly changes. This is a reversible effect in which the color changes and returns to its original color when the light irradiation is stopped and the color is placed in a dark place. Compounds having this property are called photochromic compounds, and although various compounds have been synthesized to date, no particular common structure has been recognized among them. In recent years, among these various photochromic compounds, the following structural formula () (However, R ₁ and R ₂ are various substituents.) The 1,3,3-trimethylindolinobenzospiropyran derivative represented by the following has been attracting the most attention. The compound of the above formula () changes rapidly from colorless to blue when exposed to sunlight or ultraviolet light in a nonpolar solvent such as benzene or toluene, and returns to its original colorless state when left in a dark place or when exposed to visible light.
However, when these compounds are dissolved in polar solvents such as ethyl alcohol, methyl alcohol, acetone, acetonitrile, and dimethylformamide, they are generally red or reddish-purple in color, and even when this solution is irradiated with ultraviolet light, there is no noticeable photochromic effect. It has no effect. In addition, even in solid polymer matrices, the above compounds () do not exhibit a very remarkable photochromic effect, and in particular in polar polymer matrices such as polymethyl methacrylate, polycarbonate, and poly(allyl diglycol carbonate), they exhibit red or It has a reddish-purple color, and even when irradiated with ultraviolet light, sufficient photochromic action is not observed. In addition, in the polymer matrix as described above, the compound () above is
Since the coloring structure is stabilized in the matrix, there is a drawback that the speed of fading becomes extremely slow. Also, U.S. Patent Nos. 3562172, 3578602, and
Spiro(indoline) naphthoxazine compounds such as those described in the specifications of No. 4215010 and No. 4342668 are not affected by the solvent or polymer matrix shown above, and their color fading speed is fast. However, the photochromic action of this spiro(indoline) naphthoxazine compound is remarkable in a solvent or in a polymer matrix at around 10 to 15°C, but not so much at around room temperature (20 to 30°C). The present inventor has discovered that, except for the effects of the spiropyran compound in the polymer matrix as described above,
We have conducted intensive research to make the photochromic effect more noticeable near room temperature and to improve the photochromic performance in terms of color development and fading speed. As a result, it was discovered that a compound represented by the following general formula () satisfies the above characteristics, and based on this knowledge, the present invention was accomplished. That is, the present invention provides general formula () (Here, R ₁ , R ₂ and R ₃ are alkyl groups having 1 to 10 carbon atoms, R ₄ , R ₅ , R ₆ and R ₇ are hydrogen atoms,
It is a photochromic material made of a compound represented by a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl group. For R ₁ , R ₂ and R ₃ in the above general formula (), the same or different alkyl groups having 1 to 10 carbon atoms can be suitably employed, and specifically, methyl, ethyl, propyl, and butyl groups. , pentyl group, hexyl group,
These are heptyl group, octyl group, nonyl group, and decyl group. Further, R ₄ , R ₅ , R ₆ and R ₇ in the general formula () are preferably the same or different hydrogen atoms, halogen atoms, alkyl groups having 1 to 5 carbon atoms, or alkoxy groups. The halogen atom may be a chlorine atom, a bromine atom, or an iodine atom without particular limitation. As the alkyl group, a lower alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group is preferably used. Furthermore, the alkoxy group is preferably a lower alkoxy group having 1 to 5 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, or a pentoxy group. The compound represented by the above general formula () of the present invention generally exists as a pale yellow solid at room temperature and normal pressure. Further, the compounds represented by the above general formula () of the present invention can generally be confirmed to be each compound of the general formula () by the following methods (a) to (c). (b) By measuring the infrared absorption spectrum ( ^IR ), aromatic −
Absorption due to expansion and contraction of CH, 3000 to 2800 cm ^-1 - Absorption due to expansion and contraction of CH, 1640
Absorption due to expansion and contraction of C=N bonds at ~1600cm ^-1
Absorption due to aromatic C=C bonds appears at 1600 to 1580 cm ^-1 , and strong absorption due to stretching and contraction of spiro C-O bonds appears at 970 to 950 cm ^-1 . (b) Proton nuclear magnetic resonance spectrum (H-
By measuring NMR, we can determine the type and number of protons present in a molecule. Aromatic proton-based peaks around 7-9.3ppm, − around 6.3-6.7ppm
Peak based on proton of CH=N- bond, 1.2
Pino based on the proton of the N-R ₁ (R ₁ represents an alkyl group having 1 to 10 carbon atoms) bond at around 3.0 ppm, and around 1.0 to 2.0 ppm

〔Effect of the invention〕

The photochromic resin obtained by dispersing the compound of the above general formula () in the polymer matrix shown above is colorless and transparent in all cases, and develops a blue color when irradiated with ultraviolet rays. When ultraviolet rays are removed, it returns to its original colorless state within seconds. It was found that the photochromic effect in the present invention is more pronounced near room temperature (20 to 30° C.) than the above-mentioned spironaphthoxazine compound, and its coloring density is greater. The photochromic material of the present invention can be used in a wide range of fields, including various recording and storage materials in place of silver salt photosensitive materials, copying materials, photoreceptors for printing, recording materials for cathode ray tubes, photosensitive materials for lasers, and holographic materials. It can be used as various recording materials such as photosensitive materials. In addition, the photochromic material of the present invention can also be used as a material for photochromic lenses, optical filter materials, display materials, photometers, decorations, and the like. For example, when used in a photochromic lens, there is no particular restriction as long as it provides uniform dimming performance. To give a specific example, the compound represented by the above general formula () may be uniformly dispersed. sandwiching a polymer film of
There is a method of impregnating the lens surface with this compound for 10 hours at ℃, and then coating the surface with a curable substance to make a photochromic lens. Furthermore, a method of applying the above-mentioned polymer film to the lens surface and coating the surface with a curable substance to make a photochromic lens may also be considered. As described above, the compound represented by the general formula () of the present invention is hardly affected by the type of matrix in a solid polymer matrix, and exhibits a stable colorless color in a general state, but when irradiated with ultraviolet rays, It immediately develops a blue color when exposed to ultraviolet rays, and returns to its original colorless state within seconds after irradiation with ultraviolet rays, and its color density remains high even in the high temperature range (20 to 30 degrees Celsius) above room temperature, and it has the characteristic of repeating these color changes. are doing. [Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. Production example 1 1,3,3-trimethyl-2-methyleneindoline (6.9 g, 40 mmol) and 1-nitroly-2-anthrol (8.92 g, 40 mmol) were dissolved in 100 ml of ethanol and refluxed for 2 hours while passing nitrogen gas. After the reaction, about one fourth of the excess ethanol was distilled off, and when the mixture was left to stand at room temperature, brown crude crystals were precipitated. When recrystallized with ethyl alcohol,
2.1 g of pale yellow crystals were obtained. When measuring the melting point,
The temperature was 186-188℃. When the infrared absorption spectrum was measured, it showed an absorption at 1610 cm ^-1 due to the stretching and contraction of the C=N bond, and a strong absorption at 970 cm ^-1 due to the stretching and contraction of the spiro C-O bond. Its elemental analysis value is C82.43
%, H5.79% _{, N7.46} %, and _C26H22N2O
C82.55%, H5.82, which is the calculated value for (378.26)
%, N7.40%. In addition, when proton nuclear magnetic resonance spectra were measured, 7
12H peak based on aromatic protons around ~8.8ppm, 1H peak based on -CH=N- bond protons around 6.6ppm, 3H peak based on N- _CH3 bond protons around 2.7ppm, 1.5 ~ around 1.6ppm

[Formula] shows the peak based on the proton of the bond. From the above results, the isolated product is It was found that it is a compound shown by the structural formula. The yield was 13.88%. Production example 2 5-chloro-1,3,3-trimethyl-2-methyleneindoline (8.3 g, 40 mmol) and 1-nitroly-2-anthrol (8.92 g, 40 mmol) were reacted, isolated, and purified in the same manner as in Example 1, and 3.2 g of pale yellow crystals were obtained.
I got it. When the melting point was measured, it was 176-179°C. When the infrared absorption spectrum was measured, it was 1610 cm.
^-1 absorption due to expansion and contraction of -C=N- bond, 970cm ^-1
showed strong absorption due to the stretching and contraction of spiro C-O bonds. Its elemental analysis values are C76.03%, H5.14%,
N was 6.66%, which was in excellent agreement with the calculated values of C 75.59%, H 5.09%, and N 6.78% for C ₂₆ H ₂₁ ClN ₂ O (412.76). In addition, when proton nuclear magnetic resonance spectra were measured, the 11H peak based on aromatic protons was measured around 7 to 8.8 ppm, the 1H peak based on -CH=N- bond protons was around 6.6 ppm, and the N peak was found around 2.7 ppm. 3H peak based on proton of −CH ₃ bond, 1.5-1.6 ppm
nearby

[Formula] shows the peak based on the proton of the bond. From the above results, the isolated product is It was found that it is a compound shown by the structural formula. The yield was 19.38%. Production Examples 3 to 7 Reaction, isolation, and purification were performed in the same manner as in Example 1. The structural formulas, melting points, and yields of the reaction starting materials and reaction products are shown in Table 1. The structure was confirmed using infrared absorption spectroscopy, elemental analysis, and proton nuclear magnetic resonance spectroscopy.

【table】

[Table] Application example 1 The compound shown was dissolved and dispersed in polymethyl methacrylate using benzene, and a cast film was made on a slide glass (11.2 x 3.7 cm). The concentration of the above compound contained in this film was adjusted to 1.0×10 ⁻⁴ mol/g, and the thickness was adjusted to 0.1 mm. This photochromic film was irradiated with Toshiba's mercury lamp SHL-100 at 25° C.±1° C. at a distance of 10 cm for 60 seconds to develop color, and the photochromic properties were measured. The photochromic characteristics were expressed as follows. The results are shown in Table-2. Maximum absorption wavelength (λ _nax ): The λ _nax of this coloring film was determined using a spectrophotometer 220A manufactured by Mei Seisakusho Co., Ltd. ε (60 seconds): Absorbance at the maximum absorption wavelength corrected for film thickness during 60 seconds of light irradiation for this film under the above conditions. ε (0 seconds): Absorbance corrected for the thickness of the unirradiated film at the maximum absorption wavelength during light irradiation. Half-life t ^1/2 : Time required for the absorbance of the film to decrease to 1/2 of {ε(60 seconds)−ε(0 seconds)} after irradiation with light for 60 seconds. Application example 2 Same as application example 1 A photochromic cast film of polymethyl methacrylate of the compound represented by was prepared. Its concentration is 1.0×10 ^-4 mol/g, and its thickness is 0.1
mm. Furthermore, the photochromic properties of this film were measured in the same manner as in Application Example 1. The results are shown in Table-2. Comparative example 1 Compounds used Everything was the same as in Application Example 1 except that the spiropyran shown in was used. The results are shown in Table-2. Comparative example 2 The same procedure as in Application Example 1 was carried out except that the spironaphthoxazine shown in was used. Table 2 of the results
Shown below.

[Table] Application example 3 As a compound The same procedure as in Application Example 1 was carried out except that the compound represented by was used and polycarbonate was used as the film matrix. The results are shown in Table-3. Application example 4 As a compound Application example 3 except for using the compound shown in
I did the same thing. The results are shown in Table-3. Comparative Example 3 As a compound All procedures were carried out in the same manner as in Application Example 3 except that the compound shown in was used. The results are shown in Table-3. Comparative Example 4 As a compound Application example 3 except for using the compound shown in
I did the same thing. The results are shown in Table-3. Application example 5 The compound represented by was dissolved in 100 c.c. of ethanol and impregnated onto the surface of a 0.1 mm thick poly(allyl diglycol carbonate) film at 70°C for 10 hours. The concentration at that time is 1.0×10 ^-4 mol/
g. The photochromic properties of this film were measured in the same manner as in Application Example 1. The results are shown in Table-3. Comparative example 5 The same procedure as in Application Example 5 was carried out except that the compound shown in was used. The results are shown in Table-3.

[Table] From the above results, when the compound of the present invention is used in a polymer solid matrix, the coloring density is high near room temperature (25°C), it is colorless in the decolored state, and the reversibility speed is also fast. This is obvious.

Claims (1)

[Claims] 1. A photochromic material comprising a compound represented by the following general formula (). (Here, R ₁ , R ₂ and R ₃ are alkyl groups having 1 to 10 carbon atoms, and R ₄ , R ₅ , R ₆ and R ₇ are hydrogen atoms, halogen atoms, and alkyl groups having 1 to 5 carbon atoms. group or alkoxy group).