JPH0470349B2 - - Google Patents

Description

[Detailed description of the invention]

<Industrial Application Field> The present invention relates to a reversible photochromic composition that develops color with light energy such as ultraviolet rays, decolors with application of thermal energy, and is capable of repeating coloring and decoloring. It is something. <Prior art> When a color develops by applying light energy and disappears by applying appropriate energy such as heat, an electric field, or light of a different wavelength, and this operation can be repeated many times, this This phenomenon is called photochromism, and materials that exhibit photochromism are called photochromic materials. Photochromic materials include spiropyran compounds, fulgide compounds, dithizone metal compounds, bis(triphenylmidazolyl) o-
Many compounds such as nitrobenzyl compounds are conventionally known. Photochromic materials have the characteristic that color changes are reversible, so their application to various image recording materials, such as photo printing, facsimiles, and photoresist plate-making materials, has been studied.Recently, in particular, reversibility and molecular The potential for recordable optical recording materials (EDRAW) is being explored, focusing on the possibility of recording densities on the same level. In addition, the possibility of applying the reversible change in hue to filters, dyes, paints, cosmetics, accessories, etc. is also being considered. However, for these applications mentioned above, none of the known photochromic materials has satisfactory properties. For example, spiropyran compounds develop color when irradiated with ultraviolet light, and discolor with visible light around 600 nm, and while the ratio of the concentration when coloring and the concentration when decolorizing is high, the repeatability of coloring and decoloring is 100 to 1000.
Furthermore, there are problems in that the thermal stability of the coloring state is short, ranging from several seconds to several days, and the coloring is usually limited to blue, red or purple. On the other hand, the dithizone mercury salt compound has good repeatability of coloring and decoloring and stability of the coloring state, but because it uses mercury, there are hygiene problems. Further, although the fulgide compound has good repeatability of coloring and decoloring and stability of the coloring state, it has a drawback that the types of coloring are limited. <Problems to be Solved by the Invention> The present invention improves the drawbacks of the conventional reversible photochromic compositions described above, has excellent stability of the coloring state and repeatability of coloring and decoloring, and has excellent color forming compositions. The present invention provides a wide variety of novel reversible photochromic compositions. <Means for Solving the Problems> As a result of studying a photochromic composition comprising an electron-donating organic compound and a photoactive agent that generates active species upon irradiation with ultraviolet energy, the present inventor found that It has been found that the present invention can be accomplished by a three-component composition using a dialkyl (4-hydroxyphenyl) sulfonium salt as an activator and adding a protonophilic compound as a new component. That is, the present invention provides a reversible photochromic composition comprising (A) a dialkyl(4-hydroxyphenyl)sulfonium salt, (B) an electron-donating color-forming organic compound, and (C) a proton-affinity compound; and (A) dialkyl (4-hydroxyphenyl) sulfonium salt,
This is a reversible photochromic composition in which (B) an electron-donating color-forming organic compound and (C) a proton-affinity compound are encapsulated in microcapsules. First, the materials constituting the reversible photochromic composition of the present invention will be explained. The dialkyl(4-hydroxyphenyl)sulfonium salt used in the present invention is represented by the following general formula. (Here, R ₁ and R ₂ may be different and each represents an electron-donating group such as hydrogen, an alkyl group, an alkenyl group, or an alkoxyl group, and R ₃ , R ₄ , R ₅ ,
R ₆ may be different, each having 1 to 9 carbon atoms
represents an alkyl group. Furthermore, (R ₁ and R ₃ ) and/or (R ₂ and R ₄ ) shown in the above general formula may cooperate with each other to form an aromatic ring, and R ₅ and R ₆ cooperate with each other to form an aromatic ring with a carbon number of 1 ~9 cycloalkyl groups may be formed. Also, X ^- is ClO ₄ ^- , BF ₄ ^- ,
Represents anions such as PF ₆ ^- , AsF ₆ ^- , and SbF ₆ ^- . ) Specific examples of dialkyl(4-hydroxyphenyl)sulfonium salts are shown below. Note that the compounds effective in the present invention are not limited to the following, and any common dialkyl (4-hydroxyphenyl) sulfonium salts can be used. In addition, dialkyl (4-hydroxyphenyl) sulfonium salts are reported in the Journal of
Polymer Science: Polymer Chemistry
It can be prepared using known synthetic methods such as those described in Ed. Vol. 18, p. 1021 (1980). The electron-donating color-forming organic compound used in the present invention is usually colorless or light-colored and has the property of developing color under the action of active species such as Brønsted acid and Lewis acid. Typical compounds include triphenylmethane phthalides, fluorans, phenothiazines, indolylphthalides, leucoauramines, rhodamine lactams, rhodamine lactones, indolines, triarylmethanes, azaphthalides, etc. Two or more of the same or different types of these compounds can be used in combination. Specific examples include crystal violet lactone, malachite green lactone, Michler hydrol, 3-diethylamino-7-chlorofluoran, 3-methylamino-6-chlorofluoran, 3-diethylaminobenzo-α- Fluoran, 3-diethylamino-6-aminofluoran, 3,6-dimethoxyfluoran, 3-diethylamino-7-dibenzylaminofluoran,
3-diethylamino-6-methyl-7-chlorofluorane, 3-N-methyl-N-n-propylamino-6-methyl-7-anilinofluorane, 3
-N-ethyl-N-isopentylamino-6-methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 2-
(Fluorophenylamine)-6-di-n-butylaminofluorane, N-(2,3-dichlorophenyl)-leucouramine, N-benzoyluramine, N-phenyluramine, Rhodamine B
lactam, rhodamine B lactone, 2-(phenyliminoethanezylidene)-3,3'-dimethylindoline, p-nitrobenzylleucomethylene blue, benzoylleucomethylene blue, 3,7
-bis(dimethylamino)-10-benzoylphenothiazine, 3,7-bisdimethylamino-10-
(4'-aminobenzoyl)phenothiazine, 3,
7-bisdimethylamino-10-(4'-pyrrolidinobenzoyl)phenothiazine, 3,7-bisdimethylamino-10-[4'-bis(4'',4''-dimethylaminophenyl)methylaminobenzoyl]phenothiazine , bis(4-diethylamino-2-
methylphenyl) phenylmethane, tris(4-
diethylamino-2-methylphenyl)methane,
Bis(4-diethylamino-2-fluorophenyl)phenylmethane, bis(4-diethylamino-2-methoxyphenyl)phenylmethane, bis(4-diethylamino-2-methylphenyl)(4
-diethylaminophenyl)methane, bis(4-
diethylamino-2-methylphenyl)(4-carboxyphenyl)methane, bis(4-dibenzylamino-2-methylphenyl)phenylmethane, bis(4-dibenzylamino-2-methylphenyl)(4-dibenzylaminophenyl) Methane, bis[4-di(p-tolyl)amino-2-methylphenyl]phenylmethane, 1,3,5-triphenyl-2-pyrazoline, 1-phenyl-
3,5-di-p-tolyl-2-pyrazoline, 1-
Phenyl-3,5-bis(p-methoxyphenyl)-2-pyrazoline, 1-phenyl-3-styryl-5-phenyl-2-pyrazoline, 1-phenyl-3-(p-methoxystyryl)-5- (p-
methoxyphenyl)-2-pyrazoline, 1-phenyl-3-(p-dimethylaminostyryl)-5-
(p-dimethylaminophenyl)-2-pyrazoline, 1-phenyl-3-(p-dimethylaminostyryl)-5(p-diethylaminophenyl)-2
-pyrazoline, 2-(4-dodecyloxy-3-
methoxystyryl) quinoline, etc. In addition, examples of proton affinity compounds include:
Alcohols, esters, ethers, ketones, etc. can be used. Specific examples of alcohol compounds include hexyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, lauryl alcohol, myricyl alcohol, cetyl alcohol, stearyl alcohol, eicosyl alcohol, docosyl alcohol, mericyl alcohol, and oleyl alcohol. , cyclohexanol, cyclopentanol, aliphatic alcohols such as triphenyl carbinol, aromatic alcohols such as benzyl alcohol, β-phenylethyl alcohol, cinnamyl alcohol, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monophenyl Ether, ethylene glycol monobenzyl ether, propylene glycol, propylene glycol monobutyl ether, propylene glycol monoacrylate, propylene glycol monophenyl ether, butylene glycol, hexylene glycol, 2-ethyl-1,3-hexanediol, glycerin, glycerin monolau rate, glycerin monopalmitate, glycerin monostearate, glycerin dilaurate, pentaerythritol, mannite, sorbitan,
Polyhydric alcohols such as sorbitan monolaurate, sorbitan monooleate, sorbitan tristearate, pentaerythritol, polyvinyl alcohol, polyvinyl acetal, polyvinyl butyral, cellulose acetate, hydroxyethyl cellulose, hydroxypropyl cellulose, cellulose acetate butyrate, cellulose acetate phthalate, Examples include polymeric alcohols such as methylcellulose, ethylcellulose, and polysiloxane polycarbinol. Specific examples of ester compounds include amyl acetate, octyl acetate, butyl propionate, octyl propionate, phenyl propionate, ethyl caproate, amyl caproate, ethyl caprylate, amyl caprylate, ethyl caprate, and caprin. amyl acid, octyl caprate, methyl laurate, ethyl laurate, butyl laurate, hexyl laurate, octyl laurate,
Dodecyl laurate, myristyl laurate, cetyl laurate, stearyl laurate, methyl myristate, ethyl myristate, butyl myristate, hexyl myristate, octyl myristate, lauryl myristate, myristyl myristate, cetyl myristate, myristic acid Stearyl, methyl palmitate, ethyl palmitate, butyl palmitate, hexyl palmitate, octyl palmitate, lauryl palmitate, myristyl palmitate, cetyl palmitate, stearyl palmitate, methyl stearate, butyl stearate, hexyl stearate, Octyl stearate, lauryl stearate, myristyl stearate, cetyl stearate, stearyl stearate, methyl behenate, ethyl behenate, propyl behenate, butyl behenate, ethyl benzoate, butyl benzoate, amyl benzoate, benzoic acid Phenyl, ethyl acetoacetate, methyl oleate, butyl oleate, butyl acrylate, diethyl oxalate, dibutyl oxalate, diethyl malonate, dibutyl malonate, dibutyl tartrate, dibutyl sebatate, dimethyl sebatate, dimethyl phthalate, phthalate Dibutyl acid, dioctyl phthalate, dibutyl fumarate, diethyl maleate, dibutyl maleate, triethyl citrate, 12-hydroxystearic acid triglyceride, dioxystearic acid methyl ester, 12-hydroxystearic acid methyl ester, ester wax, etc. be. Specific examples of ether compounds include butyl ether, hexyl ether, diisopropyl benzyl ether, diphenyl ether, dioxane, ethylene glycol, dibutyl ether, diethylene glycol dibutyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, and ethylene glycol diphenyl ether. , ethylene glycol monophenyl ether, polyethylene glycol monooleyl ether, polyethylene glycol mono-p-
Examples include nonyl phenyl ether, polyethylene glycol monolauryl ether, polymethyl vinyl ether, polyethyl vinyl ether, and the like. Specific examples of ketone compounds include diethyl ketone, ethyl butyl ketone, methylhexyl ketone, mesityl oxide, cyclohexanone, methylcyclohexanone, acetophenone, propiophenone, benzophenone, 2,4-pentadione, acetonyl ketone, There are acetone alcohol, ketone wax, etc. The composition of the reversibly photochromic composition of the present invention is such that (B) the electron-donating color-forming organic compound is contained in an amount of 0.01 to 100 parts by weight per 1 part by weight of (A) dialkyl (4-hydroxyphenyl) sulfonium salt. , preferably 0.1 to 10 parts by weight, (C) 0.1 to 1000 parts by weight of the proton affinity compound,
Preferably it is 1 to 100 parts by weight. The present invention can also be made more useful by encapsulating the reversible photochromic composition having the above structure in microcapsules using known microencapsulation techniques. That is, by encapsulating the constituent components of the present invention in microcapsules, the state of intermolecular contact between the molecules of the constituent components becomes closer, the photocoloring and thermal decolorization processes proceed more effectively, and the repeating characteristics are improved. Becomes good. Furthermore, since the constituent components are protected by the capsule wall, the color-forming properties will not deteriorate even if they come into contact with chemically active substances, and several types of photo-color-forming compositions with different color formations can be placed in close proximity at the same time. Moreover, advantages such as being able to maintain each function and effect independently can be exhibited. Known microencapsulation techniques used in the present invention include interfacial polymerization, in situ polymerization, in-liquid curing coating, phase separation from aqueous solutions, and phase separation from organic solutions. It can be selected and used as appropriate. The reversible photochromic composition of the present invention having the above structure is mixed with a binder and other additives in a solvent, dissolved or dispersed, and the resulting coating liquid is applied to paper, plastic film, metal, or metal. An ink or paint that can be used by coating or impregnating a support such as paper or plastic film on which an oxide or the like is vacuum-deposited or sputter-deposited, and which can be converted into an ink and has a reversible photochromic function. It can also be used as
Solvents that can be used here include water,
Methanol, ethanol, isopropanol, butyl alcohol, hexyl alcohol, methyl acetate, ethyl acetate, propyl acetate, isobutyl acetate, acetone, 2-butanone, cyclohexane,
Isophorone, 4-methyl-2-pentanone, ethyl ether, isopropyl ether, tetrahydrofuran, dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, n-hexane, isooctane, cyclohexane, solvent naphtha, methylene chloride, chloroform, dichloroethane, 1,1,2-trichloroethane, benzene, toluene, xylene, chlorobenzene, N,
N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, etc. are suitable, and as binders, ethyl cellulose, cellulose acetate, hydroxypropyl cellulose, nitrocellulose, carboxymethyl cellulose, etc. Acrylic resins such as cellulose derivatives, polyacrylic esters, polymethacrylic esters, and their copolymers, silicone resins, alkyd resins, polyester resins, phenolic resins, epoxy resins, urea resins, melamine resins, rosins,
Paint resins such as ceramics and dammar, vinyl polymers such as vinyl chloride resin, vinyl acetate resin, butyral resin, polycarbonate, polyarylate, polysulfone, polyethersulfone,
Solvent soluble engineering plastics such as aromatic polyesters are suitable. Furthermore, as other additives, masking agents such as titanium dioxide and zinc sulfide, fillers such as silica powder, color adjusting agents such as dyes and pigments, ultraviolet absorbers, and antioxidants may be added as necessary. I can do it. In this way, the reversible photochromic composition of the present invention can be used in various states depending on its intended use. <Function> The dialkyl (4-hydroxyphenyl) sulfonium salt of the present invention generates photoactive species such as Lewis acids and Bronsted acids when irradiated with active light such as ultraviolet rays. The production reaction is reversible. The electron-donating color-forming organic compound performs a color reaction with active species generated by irradiation with active light to develop color. If the proton affinity compound, which is the third component of the present invention, is not used, this coloring reaction is irreversible, and the coloring state cannot be erased. However, in the present invention, the color is erased by applying thermal energy to the colored state using a proton-affinity compound. Moreover, the decolorized state is the same as the initial state before irradiation with actinic light, and the phenomenon of developing color with actinic light and decoloring with thermal energy is completely reversible, and can be used repeatedly many times. The present invention is different from conventionally known photochromic compounds in that the coloring function and the color erasing function are divided into separate components. In other words, the color-forming species can be selected from electron-donating color-forming organic compounds, such as red, pink, orange, yellow, light blue, blue,
Any color is possible, such as green, brown, purple, or black. In addition, decolorization can be achieved by selecting the type of proton affinity compound and the blending ratio of all components.
It can be changed arbitrarily within the range of ℃ to +200℃. <Examples> Next, the present invention will be explained by examples, but these are not intended to limit the scope of the present invention. In addition,
Parts in the examples are parts by weight. Example 1 3-isoamylethylamino-6-methyl-7
-Anilinofluorane 1 part

[Formula] 1 part Lauryl stearate 4 parts Saturated polyester resin (manufactured by Toyobo Co., Ltd., Vylon)
200 used) 10 parts Toluene 70 parts 2-butanone 20 parts The solution obtained by stirring and dissolving the above formulation was coated on a polyester film to a dry coating weight of 10 g/m ² to form the present invention. A film having a reversibly photochromic composition was obtained. Next, this film was exposed entirely for 20 seconds from a distance of 30 cm using a high-pressure mercury lamp with an output of 80 W/cm, and the exposed area turned black. The stability of this coloring state was extremely good, and no change in density was observed even after one month at room temperature where ultraviolet rays were blocked. Next, the colored film was attached to a thermal head and heated to 120°C, and the color disappeared and the film returned to its pre-exposure state. The cycle of color development and decolorization is reversible, and even if this operation was repeated over 1000 times, the characteristics of color development and decolorization did not change at all. Examples 2 to 9 In Example 1, the electron-donating color-forming organic compound, photoactive agent, and proton affinity compound are shown in Table 1.
A sample of the present invention was prepared in the same manner as in Example 1, except for the following changes, and color development and decolorization tests were conducted in the same manner as in Example 1, and the results shown in Table 1 were obtained. These results show that the sample of the present invention has good color development and decolorization properties, and is also excellent in repeatability of color development and decolorization.

[Table] Example 10 1 part 2-(fluorophenylamino)-6-di-n-butylaminofluorane 1 part lauryl stearate 23 parts 25 g of the above mixture was heated to 80°C, and 5% of 80°C
Add dropwise to 80g of gelatin aqueous solution and stir to form fine droplets. Furthermore, 80 g of 5% gum arabic was added, acetic acid was added under constant stirring, the pH was lowered to 5, 200 g of water was added to cause coacervation, the pH was further lowered to 4.4, and then the cured film Add 1 g of 37% formalin to make the solution. In addition, the temperature was maintained at 50°C during the previous operations. Next, in order to gel the concentrated liquid film, it was cooled to 10° C., the pH was raised to 9, and it was left to stand for several hours to produce microcapsules containing the reversible photochromic composition of the present invention. Microcapsules containing the above reversible photochromic composition 1 part Butyral resin (manufactured by Sekisui Chemical Co., Ltd., Eslec BMS) 20 parts Toluene 70 parts 2-butanone 30 parts Obtained by uniformly mixing the above formulation The dry coating weight of the coating liquid on the polyester film is 15
g/m ² to obtain a film containing the reversible photochromic composition of the present invention. Next, the entire surface of this film was exposed for 5 seconds using the same light source as in Example 1 and keeping the distance between the light source and the film the same as in Example 1, and the exposed area developed a black color. Similar to Example 1, this coloring state was extremely stable. Next, the colored film was mounted on a thermal head and heated to 60°C, causing the colored areas to disappear and return to their pre-exposure state. Color development-
The decolorization cycle is reversible and this operation can be repeated 1000 times.
Even after repeating the process several times, the coloring and decoloring characteristics did not change at all. Examples 11 to 18 Microcapsules and samples were prepared in the same manner as in Example 10, except that the photoactive agent, electron-donating color-forming organic compound, and proton-affinity compound were changed as shown in Table 2. Then, coloring and decoloring tests were conducted in the same manner as in Example 10, and the results shown in Table 2 were obtained. These results show that the sample of the present invention has color forming and color erasing properties, and is also excellent in the repeatability of color development and color erasure.

【table】

[Table] Example 19 15 parts of the microcapsules obtained in Example 15 were uniformly mixed and dispersed with 150 parts of a 10% by weight solution of polyester resin (solvent: xylene/4-methyl-2-pentanone = 1/1). A reversible photochromic paint was obtained. This paint was applied onto glass using a roll coating method to obtain a glass having a reversible photochromic coating with a thickness of 30 μm. When this glass was then exposed to sunlight,
The exposed area turned black in about 20 seconds. When the sunlight was blocked, the colored area disappeared in about 30 seconds and returned to its pre-exposure state. It was found that this coloring-decoloring cycle is reversible, and that it can be used in light-shielding materials with reversible photochromic coatings. Example 20 1 part 3-diethylaminobenzo-α-fluorane
1 part Butyl stearate 23 parts Microcapsules were prepared in the same manner as in Example 10 using the above formulation. The decoloring temperature of the microcapsules in the photochromic state was 5°C. Using microcapsules containing this reversible photochromic composition,
A cosmetic white powder was prepared by mixing the following formulation. 2 parts of the above microcapsules 77 parts of talc 10 parts of titanium oxide 5 parts of zinc stearate 5 parts of zinc oxide 1 part of squalane
It turned red in 10 seconds. When the exposure was stopped, the colored area disappeared and returned to its pre-exposure state. It was found that the coloring-decoloring cycle is reversible, and that this product has potential as a reversible photochromic cosmetic. <Effects of the Invention> The reversible photochromic composition of the present invention develops color when irradiated with actinic light and decolors when heated,
It has excellent repeatability of coloring and decoloring and stability of the coloring state, and it has a wide variety of coloring species, and the coloring temperature can be selected arbitrarily, so it can be used as a useful material in a wide range of fields. That is, the reversible photochromic composition of the present invention can be used as writable and erasable high-density optical recording materials, plate-making materials, photographic materials, photoresist materials, filters, decorative materials, printed advertisements, stationery, toys, cosmetics, daily necessities, It can be applied to a wide range of other uses.

Claims (1)

[Claims] 1 (A) Dialkyl (4-hydroxyphenyl)
A reversible photochromic composition comprising a sulfonium salt (B) an electron-donating color-forming organic compound and (C) a proton-affinity compound. 2 (A) Dialkyl (4-hydroxyphenyl)
A reversible photochromic composition containing a sulfonium salt (B) an electron-donating color-forming organic compound and (C) a proton-affinity compound encapsulated in microcapsules.