JPS61204295A - Photochromic material - Google Patents

Abstract

PURPOSE:A photochromic material that contains, as essential components, an electron-donating and color-developing organic compound a specific photosensitizer, an oxyethylene group-containing compound and basic fine powder, thus developing a large variety of color with high resistance to heat and moisture and good storability. CONSTITUTION:The objective photochromic material contains, as essential components, (A) an electron-donating and color-developing organic compound such as triphenylmethane phthalide, fluoran or phenothiazine, (B) a photosensitizer of a condensate of triarylsulfonium salt such as of formula I or formula II and (C) a compound bearing oxyethylene group and/or (ii) a basic fine powder.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Application of the Invention) The present invention relates to a photochromic material that develops color when irradiated with light and disappears when irradiation with light is stopped.

(Prior Art and Problems) Many so-called photochromic materials have been known for a long time, which repeat reversibly coloring and discoloring in response to the presence or absence of light irradiation, but there is still no satisfactory material that can be used in many ways. In other words, the performance required for photochromic materials is color development sensitivity that allows rapid color development upon light irradiation, high color density of colored materials, decolorization sensitivity when light irradiation is stopped, durability that can withstand repeated use, and long-term storage. It is durable and comes in a wide variety of colors.

Silver halide, a typical inorganic photochromic material, has excellent performance, but is particularly poor in color variety.
Moreover, it cannot be used unless it is dispersed in the glass, which limits its applications, and it is expensive and is only used for sunglasses, so it is not adaptable to many fields. Also, azobenzene, N-
Organic substances such as salicylideneaniline, spiropyran, bis-(triphenylimidazole), thionin, viologen, and fulgide compounds are known, but all of them lack a variety of colors, as well as poor stability and color density.
It has not been put to practical use.

Furthermore, photosensitive color-forming materials are known in which an electron-donating color-forming organic compound is combined with a photoactive agent. This material has the advantage of being able to obtain a variety of color tones by changing the type of electron-donating color-forming organic compound, and some have good color density and color development sensitivity, but they may be colored before being irradiated with light or may be sensitive to light. A fatal drawback is that the colored material that develops color by irradiation does not return to its original colorless state even after the irradiation is stopped. Moreover, it also has the disadvantage of poor stability, so it cannot be used as a photochromic material.

(Objective of the Invention) The object of the present invention is to improve the drawbacks of the conventional photochromic materials described above and to obtain a new photochromic material that satisfies the required performance as a photochromic material.

(Structure of the Invention) The present invention comprises (A) an electron-donating color-forming organic compound;
) A photochromic material containing as essential components a photoactive agent which is a condensate of I-IJ arylsulfonium salt, and (C) a compound having an oxyethylene group and/or a basic fine powder.

The present inventor has discovered that when a material containing a combination of an electron-donating color-forming organic compound and a photoactive agent such as an organic halogen compound or a diazonium salt is irradiated with light, the coloring sensitivity and coloring density are excellent. We focused on the excellent performance that allows you to freely select 1M color (red, orange, yellow, green, blue, black, etc.) by changing the type, and we also aimed to give the coloring material the ability to disappear when the light irradiation is stopped. As a result of various studies, it was discovered that when a compound having an oxyethylene group and/or a basic fine powder is added to the above two components, a photochromic material can be obtained that imparts color erasing performance without impairing the above performance at all. Ta. This is the greatest feature of the photochromic material of the present invention.

Furthermore, if a photoactive agent that is a condensate of triarylsulfonium salt is used instead of the organic halogen compound or diazonium salt of the photoactive agent, in addition to the above performance, odor prevention,
It has been endowed with properties such as durability against heat and humidity, long-term storage stability, and repeated color development/decolorization, making it an excellent photochromic material that can withstand practical use.

The combination of materials whose essential components are the electron-donating color-forming organic compound of the present invention, a photoactive agent which is a condensate of triarylsulfonium salt, and a compound having an oxyethylene group and/or a basic fine powder is It has been discovered that it is novel and has excellent performance as a photochromic material as described above.The reason for exhibiting such excellent performance is not clear, but it is thought to be roughly as follows.

First, when a photochromic material is irradiated with light, a color-forming component such as a Brønsted acid or a Lewis acid is released from a photoactive agent, and this causes the electron-donating color-forming organic compound to develop color. Next, when the light irradiation is stopped, the release of color-forming components such as Brønsted acid and Lewis acid from the photoactivator stops, and at the same time, the compound having an oxyethylene group and/or the basic fine powder is released first, resulting in electron-donating coloring. It begins to absorb color-forming components such as Brønsted acid and Lewis acid, which are colored organic compounds. That is, the electron-donating color-forming organic compound that has developed a color accepts electrons, and ultimately all of the released color-forming components such as Brønsted acids and Lewis acids are transferred to compounds having oxyethylene groups and/or basic compounds. Fine powder will be absorbed. In the photochromic material of the present invention, the electron-donating color-forming organic compound accepts electrons depending on the presence or absence of light, and as a result, it is thought that color develops and disappears.

The electron-donating color-forming organic compound used in the present invention is usually
It is colorless or light-colored and has the property of donating electrons and developing color by the action of color-forming components such as prenestic acid and Lewis acid. Representative compounds include triphenylmethane phthalides,
Fluoranes, phenothiazines, indolyl phthalides, leucouramines, rhodamine lactams, rhodamine lactones, indolines, triphenylmethanes, azaphthalides, etc., and two or more of the same or different types are combined. Can be used. Next, a specific example will be shown. Crystal violet lactone, malachite green lactone, Michler's hydrose, 3-diethylamino-
α-Benzofluorane, 3-diethylamino-7-methylfluorane, 3-diethylamine-7-(〇-chlorophenyl)-aminofluorane, 3-N-ethyl-N-
P-) Lylamino-7-methyl-N-phenylaminofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, N-(2,3-dichlorophenyl)-leucoolamine, N-2,4,5 -Trichlorophenylleucouramine, 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-bis(dimethylamino)-1O-(
4°-aminobenzoyl)phenothiazine, 3,7-pisdimethylamino-1 O-(4°-pyridinobenzoyl)phenothiazine, 3,7-pisdimethylamino-1
O-(4'-bis-(4'',4''-dimethylaminophenyl)methylaminobenzoyl]phenothiazine and the like.

The photoactive agent, which is a condensate of a triarylsulfonium salt used in the present invention, is a colorless or light-colored Brønsted acid that causes an electron-donating color-forming organic compound to color when irradiated with light;
It is a compound that has the property of releasing color-forming components such as Lewis acids. For details, see J. Polym.

Sci-, Polym, Chem, Ed,, 22
1789 (1984), but since many of them are condensates, it is difficult to illustrate their chemical structures, so specific examples of identifiable compounds will be shown. Note that the photoactive agent in the present invention is not limited to the following compounds, and if it is a -m-type triarylsulfonium salt condensate, the compound having an oxyethylene group used in the present invention may be a colorless or light-colored liquid or solid. It is preferable to use a compound that is compatible with the electron-donating color-forming organic compound and photoactivator used in combination.
Incompatible materials can also be used. Next, specific examples of compounds will be shown. Diethylene glycol, diethylene glycol 7-methyl ether, diethylene glycol diethyl ether, diethylene glycol motsubutyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, triethylene glycol, triethylene glycol monobutyl ether, triethylene glycol monophenyl ether, triethylene glycol dioctyl ether, tetra Ethylene glycol, tetraethylene glycol monoethyl ether,
Tetraethylene glycol monobutyl ether acetate, polyethylene glycol, oxyethylene oxypropylene block polymer, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate , polyoxyethylene sorbitan monooleate,
Polyoxyethylene sorbitan triolate, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether,
Polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, polyethylene glycol diacrylate.

The basic fine powder used in the present invention is colorless or light-colored and is incompatible with the electron-donating color-forming organic compound or the photoactive agent.
It can be used with an average particle size of 100 μm or less, but preferably 10 μm or less, and a pH of 8 or higher is preferable. % or less.

Specific examples of basic fine powders include lithium,
These are hydroxides and carbonates of alkali metals such as sodium and potassium, and alkaline earth metals such as magnesium, calcium, and barium. Furthermore, fine powders such as fine powder silica, monomolinite, talc, basic lead sulfate, and basic lead carbonate, which become basic depending on the treatment method, can also be used.

The usage ratio of the electron-donating color-forming organic compound and the photoactive agent is in the range of 0.01 to 100 parts by weight of the photoactive agent per 1 part by weight of the electron-donating color-forming organic compound, but the optimum range is is 0.1 to 10 parts by weight.

The ratio of the electron-donating color-forming organic compound and the compound having an oxyethylene group is 0.01 part by weight of the electron-donating color-forming organic compound to 1 part by weight of the electron-donating color-forming organic compound.
~100 parts by weight, but the optimal range is 0.1~100 parts by weight.
It is 50 parts by weight.

The ratio of the electron-donating color-forming organic compound and the basic fine powder used is in the range of 0.01 to 100 parts by weight of the basic fine powder per 1 part by weight of the electron-donating color-forming organic compound. The range is 1-100 parts by weight.

The photochromic material of the present invention can be used as it is, or can be applied to, printed on, or rolled into various substrates. Various additive components can be added to the photochromic material in accordance with such various usage forms. For example, binder components such as natural resins and synthetic resins, exacerbating agents to increase color development sensitivity, masking agents such as titanium white and alumina, thickeners such as silica powder, pH 1J adjusters such as acids and alkalis, dyes, pigments, etc. Color tone adjusters, plasticizers, various stabilizers, etc. are added as necessary.

The photochromic material of the present invention can be prepared by adding an electron-donating color-forming organic compound, a photoactive agent, a compound having an oxyethylene group, and/or a basic fine powder, and additives if necessary, and can be used as is or in an appropriate solvent. Dissolve and disperse in
It can then be obtained by evaporating the solvent.

The photochromic material thus obtained was 400
Color develops when exposed to ultraviolet rays in the wavelength range of nm or less, especially 25 nm.
Colors are effectively developed by ultraviolet rays in the wavelength range of 0 to 350 nm. If a colored photochromic material is placed in a dark place, the color will begin to fade and eventually return to the same state as before the coloring. This color development/discoloration reaction can be repeated several dozen times or more. Furthermore, there is no performance deterioration even after long-term storage of one year or more.

By appropriately changing the type of electron-donating color-forming organic compound used in the present invention, it is possible to freely obtain a colored product having a desired color tone and a high density.

As described above, the photochromic material of the present invention is an excellent material that has improved all the drawbacks of conventional photochromic materials, and can be applied to paper, plastic sheets, metal foils, various fibers, glass, ceramics, etc., or printed. or
It can be used by impregnating it, sandwiching it between two base materials, or rolling it into a base material such as plastic, or it can be made into an ink and used as an ink or paint that has photochromic properties.

As a result, the photochromic material of the present invention can be applied to various industrial materials, decorative materials, printed advertisements, daily necessities, toys, and a wide range of other uses.

Next, the present invention will be explained by examples, but these are not intended to limit the scope of the present invention. Parts in the examples are parts by weight.

Example 1 OR-55 (manufactured by Yamada Chemical Industry Co., Ltd., electron-donating color-forming organic compound) 1 part bis[4-(
Diphenylsulfino) phenyl sulfide bis-
Tetrafluoroborate (photoactive agent)
5 parts PEG100O (manufactured by Sanyo Chemical Co., Ltd., polyethylene glycol, average molecular weight 1000) 4 parts MSK-P
O (manufactured by Maruo Calcium Co., Ltd., calcium carbonate)
10 parts S-LEC BX-L (Manufactured by Tanezu Kagaku Co., Ltd., butyral resin) 5 parts Methyl ethyl ketone 25 parts After stirring and dissolving all ingredients, solid content 2 on a polyester sheet or high-quality paper.
A white sheet with photochromic properties was obtained by applying the coating to a concentration of ~4 g/m''. When a photographic negative original was placed on this sheet and exposed to sunlight for 15 seconds, the exposed areas developed an orange color.

When the light irradiation was stopped, the color returned to its original white color. Although color development and decolorization were repeated 20 times, almost no deterioration in performance was observed.

This sheet had durability against heat and humidity and had good storage stability.

Example 2 In Example 1, S-205 (
Manufactured by Yamada Chemical Industry Co., Ltd., electron-donating color-forming organic compound)
A white sheet having photochromic performance was obtained in the same manner as in Example 1 using the following. When a photographic negative original was placed on this sheet and exposed to sunlight for 15 seconds, the exposed areas turned black. When the light irradiation was stopped, the color returned to its original white color. Although color development and decolorization were repeated 20 times, almost no deterioration in performance was observed.

This sheet had durability against heat and humidity and had good storage stability.

Example 3 Pergascript Red I-6B (manufactured by Ciba Geigy, electron-donating color-forming organic compound)
1-part bis[4-(diphenylsulfino) phenyl fusulfide bis-tetrafluoroborate (photoactive agent)
5 parts MS-1 (manufactured by Maruo Calcium Co., Ltd., calcium carbonate) 12 parts S-LEC B
X-L 5-part methyl ethyl ketone
25 parts A white sheet having photochromic properties was obtained in the same manner as in Example 1. When a photographic negative original was placed on this sheet and exposed to sunlight for 15 seconds, the exposed areas turned red and became colored. When the light irradiation was stopped, the color returned to its original white color.

Although color development and decolorization were repeated 20 times, almost no deterioration in performance was observed.

This sheet had durability against heat and humidity and had good storage stability.

Example 4 NC-0 (manufactured by Hodogaya Chemical Co., Ltd., electron-donating color-forming organic compound) 1 part bis[4-(
Diphenylsulfino) phenyl sulfide bis-
Hexafluorophosphate (photoactive agent)
5 parts PE01500 (manufactured by Sanyo Chemical Co., Ltd., polyethylene glycol, average molecular weight 1500) 6 parts Eslec BX-L 5 parts Methyl ethyl ketone 25 parts A white sheet having photochromic performance was obtained in the same manner as in Example 1. When a photographic negative original was placed on this sheet and exposed to sunlight for 15 seconds, the exposed areas developed a red color. When the light irradiation was stopped, the color returned to its original white color.

Although color development and decolorization were repeated 20 times, almost no deterioration in performance was observed.

This sheet had durability against heat and humidity and had good storage stability.

Example 5 NBP-1 (manufactured by Yamada Chemical Industry Co., Ltd., electron-donating color-forming organic compound) 1 part bis[4-(
Diphenylsulfino) phenyl] sulfide bis-hexafluoroantimonate (photoactive agent)
4 parts Odor TW-0120 (manufactured by Kao Soap Co., Ltd.)
Polyoxyethylene sorbitan monooleate) 1 part MSK-PO 10 parts Ethyl cellulose, N-4 (manufactured by Bercules, USA, cellulose resin) 6 parts Methyl ethyl ketone 30 parts A white sheet with photochromic performance was obtained in the same manner as in Example 1. . When a photographic negative original was placed on this sheet and exposed to sunlight for 15 seconds, the exposed areas developed a blue color. When the light irradiation was stopped, the color returned to its original white color.

Although color development and decolorization were repeated 20 times, almost no deterioration in performance was observed.

This sheet had durability against heat and humidity and had good storage stability.

Example 6 NC-BK (manufactured by Hodogaya Chemical Co., Ltd., electron-donating color-forming organic compound) 1-part bis[4-(diphenylsulfino)phenyl]sulfide bis-tetrafluoroborate (photoactive agent) 5th part PE0
600 (manufactured by Sanyo Kasei Co., Ltd., polyethylene glycol, average molecular weight 600) 3 parts MSK-PO 9 parts triphenyl phosphate 1 part ethyl cellulose, N-46 parts methyl ethyl ketone 35 parts White sheet having photochromic performance in the same manner as in Example 1 I got it. When a photographic negative original was placed on this sheet and exposed to sunlight for 15 seconds, the exposed areas turned black. When the light irradiation was stopped, it returned to its original white color.

Although color development and decolorization were repeated 20 times, almost no deterioration in performance was observed.

This sheet had durability against heat and humidity and had good storage stability.

Example 7 APT (manufactured by Yamada Chemical Industry Co., Ltd., electron-donating color-forming organic compound) 1 part bis[4-(
Diphenylsulfino)phenyl]sulfide bis-hexafluoroarsenate (photoactive agent)
4 parts Amit 302 (manufactured by Kao Soap Co., Ltd., polyoxyethylene alkylamine) 0.2 parts PE06
00 5 parts methyl ethyl ketone 25 parts methanol
After stirring, dissolving and dispersing all the components in 5 parts, the ink was filled into a pen body as an ink for a fiber pen. When this pen body was used to write on paper or plastic film, a latent image that was almost invisible to the naked eye was obtained. Next, when this latent image area was irradiated with sunlight for 15 seconds, a green image was developed.

When the light irradiation was stopped, it returned to its original colorless state. 20 colors
Although the test was repeated several times, there was almost no deterioration in performance.

(Effects of the Invention) The photochromic material of the present invention has a rich variety of coloring species, has excellent durability against heat and humidity, and has excellent preservability, and can be used as a useful material in a wide range of fields.

Claims (1)

[Claims] (A) an electron-donating color-forming organic compound, (B) a photoactive agent that is a condensate of a triarylsulfonium salt, and (C)
A photochromic material containing as essential components a compound having an oxyethylene group and/or a basic fine powder.