JPH0516472B2 - - Google Patents

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 fields. In other words, the performance required for photochromic materials is color development sensitivity that quickly develops color upon irradiation with light, high color density of colored materials,
These include sensitivity to decolorization when light irradiation is stopped, durability to withstand repeated use, stability to withstand long-term storage, and a wide variety of colors.

Silver halide, a typical inorganic photochromic material, has excellent performance, but its applications are limited because it lacks a variety of colors and cannot be used unless it is dispersed in glass.It is also expensive and is not used in sunglasses. It is used only to the extent that it is not adaptable to many areas. In addition, organic substances such as azobenzene, N-salicylideneaniline, spiropyran, bis-(triphenylimidazole), thionine, viologen, and fulgide compounds are known, but all of them lack a variety of colors and are not stable and color density. It has not been put into practical use due to the lack of and weak quality.

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 feature that various color tones can be obtained by changing the type of electron-donating color-forming organic compound, and some have good color density and color development sensitivity. A fatal drawback is that the colored material that develops color through irradiation does not return to its original colorless state even after the light irradiation is stopped. Moreover, it also has the disadvantage of poor stability, so it cannot be used as a photochromic material.

(Object 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;
(B) at least one photoactive agent selected from a sulfonium salt represented by the following general formula [] or [′], a phosphonium salt represented by the general formula [], and an iodonium salt represented by the general formula []; (C) A photochromic material containing as an essential component a polyhydric alcohol, ether or ester having an oxyethylene group.

General formula [] (Here, R ₁ , R ₂ , R ₃ are the same or different and are aromatic groups having 4 to 13 carbon atoms. Y is sulfur or CH ₂ group. ^{X -} is CIO ^- ₄ or It is a complex ion containing halogen and phosphorus, antimony, or arsenic.) General formula [′] (Here, R ₁ , R ₂ and R ₃ are the same or different and are aromatic groups having 4 to 13 carbon atoms ^.
is CIO ^- ₄ or a complex ion containing boron, phosphorus, antimony, or arsenic and a halogen. ) General formula [] (Here, R ₄ is an alkyl group having 1 to 8 carbon atoms, a monovalent aliphatic group selected from substituted derivatives thereof, or an aromatic fused ring structure having 5 to 13 carbon atoms, or an aromatic It is an organic group that forms a group group. X ^- is the same as X ^- in general formula [].) General formula [] (Here, R ₅ and R ₆ are monovalent aliphatic groups selected from hydrogen, a halogen atom, a nitro group, an alkyl group having 1 to 4 carbon atoms, or a substituted derivative thereof ^. (Same as X ^- in formula Moreover, by changing the type of electron-donating color-forming organic compound, you can freely create color tones (red, orange, yellow,
We focused on the excellent performance of being able to select a color (green, blue, black, etc.), and also conducted various studies to provide the ability to erase the color when the light irradiation was stopped. It has been found that when alcohol, ether or ester is added to the photochromic material, the photochromic material can be imparted with decoloring performance without impairing the above-mentioned performance at all.
This is the greatest feature of the photochromic material of the present invention. Furthermore, in place of the organic halogen compound and diazonium salt of the photoactivator, a sulfonium salt,
If a photoactivator selected from phosphonium salts and iodonium salts is used, in addition to the above performance, odor prevention,
It was 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 the electron-donating color-forming organic compound of the present invention, a photoactive agent selected from sulfonium salts, phosphonium salts, and iodonium salts, and a material containing an oxyethylene group-containing compound as an essential component is novel. As mentioned above, it was found that it has excellent performance as a photochromic material, but the reason why it exhibits such excellent performance is not clear, but it is thought to be roughly as follows.

First, when a photochromic material is irradiated with light, color-forming components such as Brønsted acid and Lewis acid are released from the photoactive agent, which 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, polyhydric alcohols, ethers, or esters having oxyethylene groups are released first, forming electron-donating color-forming organic compounds. It begins to absorb color-forming components such as Brønsted acid and Lewis acid that caused the compound to develop color. That is, the colored electron-donating color-forming organic compound accepts electrons, and finally all released color-forming components such as Bronsted acid and Lewis acid are converted into polyhydric alcohols, ethers, or esters having an oxyethylene group. absorbs it. 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 colorless or light-colored, and has the property of donating electrons and developing color under the action of a color-forming component such as Brønsted acid or Lewis acid. Typical compounds include triphenylmethane phthalides, fluorans, phenothiazines, indolylphthalides, leucoauramines, rhodamine lactams, rhodamine lactones, indolines, triphenylmethanes, azaphthalides, etc. and two or more of the same type or different types can be used in combination. Next, a specific example will be shown. Crystal violet lactone, malachite green lactone, Michler's hydrogen, 3-diethylamino-α-benzofluoran, 3-diethylamino-7-methylfluoran, 3-diethylamino-7-(o-chlorophenyl)-aminofluoran, 3-N-ethyl-N
-P-tolylamino-7-methyl-N-phenylaminofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, N-(2,3-dichlorophenyl)-leukoolamine, N- 2, 4,
5-Trichlorophenylleukoolamine, 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'-pyridinobenzoyl)phenothiazine, 3,
7-bisdimethylamino-10-[4′-bis-(4″,
4-dimethylaminophenyl)methylaminobenzoyl]phenothiazine, and the like.

The photoactive agent used in the present invention is a colorless or light-colored compound that, when irradiated with light, has the property of releasing a color-forming component such as Brønsted acid or Lewis acid that causes an electron-donating color-forming organic compound to develop a color, and includes sulfonium salts, They are phosphonium salts and iodonium salts.
Next, specific examples of photoactivators will be shown.

The polyhydric alcohol, ether, or ester having an oxyethylene group used in the present invention can be a colorless or light-colored liquid or solid, and is compatible with the electron-donating color-forming organic compound and photoactive agent used together. are preferred, but incompatible ones can also be used. Next, specific examples of compounds will be shown. diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol diethyl ether,
Diethylene glycol monobutyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, triethylene glycol, triethylene glycol monobutyl ether, triethylene glycol monophenyl ether, triethylene glycol dioctyl ether, tetraethylene 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, poly Oxyethylene sorbitan monooleate, polyoxyethylene sorbitan triolate, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, polyoxyethylene nonyl phenol ether , polyethylene glycol diacrylate.

The ratio of the electron-donating color-forming organic compound and the photoactive agent used 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.
The optimum range is 0.1-10 parts by weight.

The ratio of the electron-donating color-forming organic compound and the polyhydric alcohol, ether or ester having an oxyethylene group is based on 1 part by weight of the electron-donating color-forming organic compound. The ester ranges from 0.01 to 100 parts by weight, with the optimum range being 0.1 to 50 parts by weight.

The photochromic material of the present invention can be used as it is, or it can be applied to, printed on, or rolled into various substrates. Various additive components can be added to the photochromic material in accordance with these various usage forms. for example,
Binder components such as natural resins and synthetic resins, sensitizers that increase color development sensitivity, masking agents such as titanium white and alumina, thickeners such as silica powder, PH regulators such as acids and alkalis, color tones such as dyes and pigments. Conditioners, plasticizers, various stabilizers, etc. are added as necessary.

The photochromic material of the present invention can be prepared as it is or by adding an electron-donating color-forming organic compound, a photoactive agent, a polyhydric alcohol having an oxyethylene group, an ether or an ester, and additives as necessary, or by dispersing it in an appropriate manner. Alternatively, the solvent can be evaporated.

The photochromic material thus obtained develops color when exposed to ultraviolet light in the wavelength range of 400 nm or less, and particularly effectively develops color when exposed to ultraviolet light in the wavelength range of 250 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. It can be used by coating, impregnating, sandwiching between two substrates, or rolling into a substrate such as plastic, or it can be made into an ink and used as an ink or paint with photochromic performance. 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 R-DCF (manufactured by Hodogaya Chemical Co., Ltd., color-forming organic compound manufactured by Denshi Yodo Co., Ltd.) 0.25 parts Triphenylsulfonium tetrafluoroborate 0.5 parts Emanone 4110 (manufactured by Kao Atlas Co., Ltd., polyethylene glycol monooleate) 0.5 Part: ESLETSUKU BM-5 (manufactured by Sekisui Chemical Co., Ltd., butyral resin) 1.5 parts Methyl ethyl ketone 15 parts Toluene 5 parts Methanol 5 parts After stirring and dissolving all components, add to a polyester sheet so that the solid content is 5 g/m ² Apply it and
A white sheet with photochromic performance was obtained. Layer a photo negative original on this sheet and expose it to sunlight.
When exposed for 30 seconds, the exposed area turned red. When the light irradiation was stopped, the color returned to its original white color. Although color development and decolorization were repeated 20 times, there was almost no deterioration in performance.

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

Example 2 PSD-G (manufactured by Shin Nisso Kako Co., Ltd., electron-donating color-forming organic compound) 0.25 parts triphenylsulfonium hexafluorophosphate 0.5 parts Merge 52 (manufactured by Kao Atlas Co., Ltd., polyoxyethylene stear rate) 0.5 parts MS-300 (manufactured by Nippon Steel Chemical Co., Ltd., styrene methacrylic acid copolymer resin) 1.5 parts toluene 8 parts methyl ethyl ketone 12 parts methanol 3 parts After stirring and dissolving all components, solid content was added to a polyester sheet. A white sheet having photochromic performance was obtained by coating at a concentration of 4 to 5 g/m ² . An adhesive was applied to the back side of this sheet to form a label. Paste this label on stationery, toys, etc.
When exposed to sunlight for 20 seconds, it turned green. When the light irradiation was stopped, the color returned to its original white color.

This colored paper is resistant to heat and humidity.
It had a good shelf life.

Example 3 NBP-1 (manufactured by Yamamoto Kagaku Co., Ltd., a color-forming organic compound manufactured by Electron Donation) 0.25 parts Triphenylphenacylphosphonium tetrafluoroborate 0.5 parts Newpol 50HB-2000 (manufactured by Sanyo Kasei Co., Ltd.), poly( (oxyethylene oxypropylene) glycol monoether) 0.25 parts Toluene 7 parts Methyl ethyl ketone 10 parts Methanol 3 parts After stirring and dissolving and dispersing all components, high-quality paper was impregnated with a solid content of 2 to 3 g/m ² to determine photochromic performance. A photochromic paper having the following properties was obtained.

Turn this photochromic paper into black light for 30 minutes.
When exposed for a second, it 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, there was almost no deterioration in performance.

This photochromic paper was resistant to heat and humidity and had good storage stability.

Example 4 PSD-170 (manufactured by Shin Nisso Kako Co., Ltd., electron-donating color-forming organic compound) 0.25 parts diphenyliodonium tetrafluoroborate
0.25 parts PEG600 (manufactured by NOF Corporation, polyethylene glycol, average molecular weight 600) 0.5 parts Eslec BX-L (manufactured by Sekisui Chemical Co., Ltd., butyral resin) 2 parts methyl ethyl ketone 20 parts toluene 4 parts methanol 5 parts Stir all ingredients After dissolving and dispersing the mixture, letterpress printing was performed on high-quality paper to obtain white photochromic paper having photochromic performance. When this photochromic paper was exposed to sunlight for 30 seconds, the printed area 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, there was almost no deterioration in performance.

This photochromic paper was resistant to heat and humidity and had good storage stability.

Example 5 OP-55 (manufactured by Yamamoto Kagaku Co., Ltd., color-forming organic compound manufactured by Electron Dono) 0.25 parts triphenylsulfophonium hexafluoroborate 0.5 parts Uniox C-2300 (manufactured by Nippon Oil & Fats Co., Ltd., castor oil of polyethylene glycol) Ether) 0.5 parts Eslec BM-5 2 parts Methyl ethyl ketone 8 parts Toluene 2 parts Methanol 2 parts After stirring and dissolving all the components, printing was performed on high-quality paper using a stencil to obtain white photochromic paper with photochromic performance. . When this photochromic paper was exposed to sunlight for 30 seconds, the printed area turned orange. When the light irradiation was stopped, the color returned to its original white color. Although color development and decolorization were repeated 20 times, there was almost no deterioration in performance.

This photochromic paper was resistant to heat and humidity and had good storage stability.

Example 6 Red-40P (manufactured by Yamamoto Kagaku Co., Ltd., color-forming organic compound manufactured by Electron Dono) 0.25 parts Diphenyl-4-thiophenoxyphenylsulfonium tetrafluoroborate 0.5 parts Emulgen 903 (manufactured by Kao Atlas Co., Ltd.) Polyoxyethylene nonyl phenol ether) 0.5 parts Eslec BM-5 2 parts Methyl ethyl ketone 15 parts Toluene 5 parts Methanol 5 parts After stirring and dissolving all the ingredients, apply to a polyester sheet at a solid content of 5 to 6 g/m ² A white sheet with photochromic performance was obtained. When a photographic negative original was placed on this sheet and exposed to a chemical lamp for 30 seconds, the exposed areas turned red. When the light irradiation was stopped, the color returned to its original white color. Although color development and decolorization were repeated 20 times, there was almost no deterioration in performance.

This sheet is resistant to heat and humidity.
It had a good shelf life.

Example 7 PSD-HP (manufactured by Shin Nisso Kako Co., Ltd., electron-donating color-forming organic compound) 0.25 parts Triphenylsulfonium hexafluorophosphate 0.75 parts Tween 80 (manufactured by Kao Atlas Co., Ltd., polyoxyethylene sorbitan monomer) oleate) 0.5 parts Ethyl cellulose, N-4 (cellulose resin manufactured by Hercules, USA) 1.5 parts Methyl ethyl ketone 10 parts After stirring and dissolving all ingredients, apply to a polyester sheet at ^a solid content of 3 to 4 g/m2. A white sheet with photochromic performance was obtained. When a photographic negative original was placed on this sheet and exposed to sunlight or a chemical lamp for 30 seconds, the exposed areas turned red. When the light irradiation was stopped, the color returned to its original white color. Although color development and decolorization were repeated 20 times, there was almost no deterioration in performance.

This sheet is resistant to heat and humidity.
It had a good shelf life.

Example 8 TH-107 (manufactured by Hodogaya Chemical Co., Ltd., color-forming organic compound manufactured by Electron Dono) 0.25 parts diphenyliodonium hexafluorophosphate 0.75 parts Tween60 (manufactured by Kao Atlas Co., Ltd., polyoxyethylene sorbitan monomer) rate) 0.5 parts ESLETSUKU BX-L 1.5 parts Ethyl cellulose, N-4 (manufactured by Hercules, USA) 10 parts methyl ethyl ketone 2 parts methanol After stirring and dissolving all the ingredients, spread on high-quality paper so that the solid content is 4 to 5 g/m ² A white photochromic paper with photochromic performance was obtained by coating the photochromic paper on a sheet of photochromic paper. When a photographic negative original was placed on this photochromic paper sheet and exposed to sunlight or a chemical lamp for 30 seconds, the exposed area developed a red color. When the light irradiation was stopped, The color returned to its original white color. After repeating color development and fading 20 times, there was almost no deterioration in performance.

This photochromic paper was resistant to heat and humidity and had good storage stability.

Example 9 NG-100 (manufactured by Teikoku Kagaku Co., Ltd., color-forming organic compound manufactured by Denshi Dono) 0.25 parts triphenylsulfonium tetrafluoroborate 0.5 parts PEG-600 (manufactured by NOF Corporation, polyethylene glycol, average molecular weight 600 ) 0.5 parts Methyl isoburketone 12.5 parts Triene 12.5 parts After stirring and dissolving and dispersing all the components, the ink was filled into a pen body as an ink for a fiber pen.

When this pen was used to write on paper or plastic film, an almost invisible latent image was obtained.

Next, when this latent image area was irradiated with sunlight for 15 seconds, a blue image developed. When the light irradiation was stopped, it returned to its original colorless state. Although color development and decolorization were repeated 10 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)

[Scope of Claims] 1 (A) an electron-donating color-forming organic compound; (B) a sulfonium salt represented by the following general formula [] or [']; a phosphonium salt represented by the general formula []; At least one photoactive agent selected from iodonium salts represented by the formula [], and (C)
A photochromic material containing as an essential component a polyhydric alcohol, ether or ester having an oxyethylene group. General formula [] (Here, R ₁ , R ₂ , R ₃ are the same or different and are aromatic groups having 4 to 13 carbon atoms. Y is sulfur or a CH ₂ group. ^{X -} is CIO ^- ₄ or It is a complex ion containing halogen and phosphorus, antimony, or arsenic.) General formula [′] (Here, R ₁ , R ₂ and R ₃ are the same or different and are aromatic groups having 4 to 13 carbon atoms ^.
is CIO ^- ₄ or a complex ion containing boron, phosphorus, antimony, or arsenic and a halogen. ) General formula [] (Here, R ₄ is an alkyl group having 1 to 8 carbon atoms, or a monovalent aliphatic group selected from substituted derivatives thereof, or an aromatic fused ring structure having 5 to 13 carbon atoms, or an aromatic It is an organic group that forms a group group. X ^- is the same as X ^- in general formula [].) General formula [] (Here, R ₅ and R ₆ are monovalent aliphatic groups selected from hydrogen, a halogen atom, a nitro group, an alkyl group having 1 to 4 carbon atoms, or a substituted derivative thereof ^. It is the same as X ^- in formula [].)