JPS61163987A - Photochromic material - Google Patents

Abstract

PURPOSE:To provide a photochromic material having excellent sensitivity with respect to color development and color disappearance with excellent color density, durability and storage stability, which comprises an organic compound which is an electron donor capable of developing a color, a specific light activator and a compound having an oxyethylene group. CONSTITUTION:A desired photochromic material is prepared by mixing (A) 1pt.wt. of an organic compound which is an electron donor capable of developing a color (e.g. crystal violet lactone), (B) 0.01-10pts.wt. of at least one light activator selected from the group consisting of a sulfonium salt of the formula I (wherein R1-R3 are each an aromatic group having 4-13 carbon atoms; Y is S or CH2 group; n is 0 or 1; X<-> is a complex ion containing either ClO<->4 or a member selected from among B, P, Sb and As and a halogen), a phosphonium salt of the formula II (wherein R4 is a monovalent aliphatic group selected from among alkyl groups having 1-8 carbon atoms and substituted derivatives thereof, aromatic condensed ring compounds having 5-13 carbon atoms and an organic group capable of forming an aromatic nucleus) and an iodonium salt of the formula III (wherein R5-R6 are each H, a halogen, a nitro group or a monovalent aliphatic group selected from among alkyl groups having 1-4 carbon atoms and substituted derivatives thereof) and (C) 0.01-100pts.wt. of a compound having an oxyethylene group.

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 can reversibly change color and color depending on the presence or absence of light irradiation, but there are still no satisfactory materials that can be used in a variety of ways. In other words, the performances required of photochromic materials include color development sensitivity that allows rapid color development upon light irradiation, high color density of colored materials, difficulty in discoloring 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 glass, which limits its applications.It is also expensive and is only used in sunglasses, and is not adaptable to many applications.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 into 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) a color-forming organic compound and (B)
) at least one photoactive agent selected from a sulfonium salt represented by the following general formula CI), a phosphonium salt represented by the general formula (II), and an iodonium salt represented by the general formula [III]; It is a photochromic material whose essential component is a compound having an ethylene group.

General formula (1) Here, Ri, Rt, and Rs are the same or different and are aromatic groups having 4 to 13 carbon atoms. Y is sulfur or a CHz group, and n is 0 or l. X is CIO,,
Alternatively, it is a complex ion containing boron, phosphorus, antimony, or arsenic and a halogen.

General formula (II) Here, R4 is an alkyl group having 1 to 8 carbon atoms, a monovalent aliphatic group selected from substituted derivatives thereof, or an aromatic condensed ring structure having 5 to 13 carbon atoms. , or an organic group forming an aromatic group.

X is the same as X in general formula (1).

Here, Rs and Ri are hydrogen, halogen atom, nitro group,
A monovalent aliphatic group selected from alkyl groups having 1 to 4 carbon atoms or substituted derivatives thereof. X is the same as X in general formula (I).

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 the color tone (red, orange, yellow, green, blue, black, etc.) by changing the type, and we also developed a variety of products that have the ability to erase the color when the light irradiation is stopped. As a result of studies, it has been found that when a compound having an oxyethylene group is added to the two components, a photochromic material can be obtained which imparts color erasing performance without impairing the above-mentioned performance at all. This is the greatest feature of the photochromic material of the present invention.

Furthermore, if a photoactive agent selected from sulfonium salts, phosphonium salts, and iodonium salts is used instead of the organic halogen compound and diazonium salt of the photoactive agent, in addition to the above performance, odor prevention and durability against heat and humidity can be improved. It was endowed with properties such as 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. Although it has been found that it has excellent performance as a photochromic material as described in No. 111, 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, color-forming components such as Brønsted acid and Lewis acid are released from the photoactivator, which causes the electron-donating color-forming organic compound to develop color.Next, when the light irradiation is stopped, Brönsted acid, Lewis acid, etc., in which 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 is released first, causing the electron-donating color-forming organic compound to develop color. It begins to absorb coloring ingredients such as. That is,
The colored electron-donating color-forming organic compound accepts electrons,
Ultimately, the compound having an oxyethylene group absorbs all the released color-forming components such as Brønsted acid and Lewis acid. It is thought that chromatic organic compounds receive and receive electrons, and as a result, color develops and disappears.

The electron-donating color-forming organic compound used in the present invention is usually
Typical compounds that are colorless or light-colored and have the property of donating electrons and developing color by the action of color-forming components such as Brønsted acids and Lewis acids 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. Specific examples that can be used include crystal bioleft lactone, malachite green lactone, Michler's hydrogen, and 3-diethylamino-
α-Benzofluorane, 3-diethylamino-7-methylfluorane, 3-diethylamino-7-(.

-chlorophenyl)-aminofluorane, 3-N-ethyl-N-P-tolylamino-7-methyl-N-phenylaminofluorane, 3-pyrrolidino-6-methyl-7-
Anilinofluoran, N-(2,3-dichlorophenyl)-leucouramine, N-2,4,5-)dichlorophenylleucouramine, N-benzoyluramine,
N-Phenyluramine, Rhodamine B lactam, Rhodamine B lactone, 2-(phenyliminoethanedylidene)-3,3゜-dimethylindoline, P-nitropendyl icomethylene blue, benzoylleucomethylene blue, 3,7-bis( dimethylamino)-10-benzoylphenothiazine, 3.7-pisdimethylamino-1O-(4°-aminobenzoyl)phenothiazine, 3
．． 7-pisdimethylamino-10-(4'-pyridinobenzoyl)phenothiazine, 3.7-pisdimethylamino-1O-(4'-bis-(4'',4'''-
dimethylaminophenyl) methylaminobenzoyl] phenothiazine, etc.

The photoactive agent used in the present invention is a colorless or light-colored compound that has the property of releasing color-forming components such as Brønsted acid and Lewis acid, which color an electron-donating color-forming organic compound when irradiated with light. Specific examples of photoactive agents are shown below, which are salts, phosphonium salts, and iodonium salts.

C Mi゛Xu・BF-、YuX■゛X0・PF-6CH,O
+Pibe→・BP-.

CH, +1″+CH2・BF-4 CH mouth CH′″+CHs・PF-6 CH, (t1 (tear cHw・ASF-6t-C4H9+
The compound having an oxyethylene group used in the present invention can be a colorless or light-colored liquid or solid. Compatible compounds are preferred, but incompatible compounds can also be used.Next, specific examples of the compounds are diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol monophenyl ether, diethylene glycol mono Benzyl 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 oxy Probylene brosoc polymer, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, polyquinoethylene sorbitan tristearate, polyquine ethylene 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 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 O,1 ~
It is 50 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, exacerbants that increase color development sensitivity, soot removers such as titanium white and alumina, thickeners such as silica powder, pHff1 regulators such as acids and alkalis, dyes, and pigments. Color tone adjusting agents, plasticizers, various stabilizers, etc. may be added as necessary.

The photochromic material of the present invention is prepared by adding an electron-donating color-forming organic compound, a photoactive agent, a compound having an oxyethylene group, and additives as necessary, and then using the photochromic material as it is or by dissolving and dispersing it in an appropriate solvent. It can 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 2
Colors are effectively developed by ultraviolet rays in the wavelength range of 50 to 350 nm. If you place the colored photochromic material in a dark place,
The color begins to fade and eventually returns to the same state as before color development. 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 with 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, which are not intended to limit the scope of the present invention. Parts in the examples are parts by weight.

Example I R-DCF (manufactured by Hodogaya Chemical Co., Ltd., electron-donating color-forming organic compound) 0.25 parts triphenylsulfonium tetrafluoroborate
0.5 parts Emanone 4110 (manufactured by Kao Atlas Co., Ltd., polyethylene glycol monooleate) 0.5 parts Esuresoku BM-5 (manufactured by Tanezu Chemical Co., Ltd.,
butyral resin) 1.5 parts methyl ethyl ketone 15 parts toluene
5 parts methanol
After stirring and dissolving and dispersing all the components in 5 parts, the mixture was applied to a polyester sheet at a solid content of 5 g/m'' to obtain a white sheet with photochromic properties.

When a photographic negative original was placed on this sheet and exposed to sunlight for 30 seconds, the exposed areas developed a red color. When the light irradiation was stopped, the color returned to its original white color, which was repeated 20 times, but there was almost no deterioration in performance.

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

Example 2 PSD-C; (manufactured by Shin Nisso Kako Co., Ltd., electron-donating color-forming organic compound) 0.25 parts triphenylsulfonium hexafluorophosphate 0.5 parts Merge 52
(Produced by Positive Pressure Atlas Co., Ltd., polyoxyethylene stearate) 0.5 parts MS-300 (Nippon Steel Chemical Co., Ltd.)
Copolymer resin of styrene methacrylic acid) 1.5 parts toluene 8 parts methyl ethyl ketone 12 parts methanol
After stirring and dissolving and dispersing all three components, they were coated on a polyester sheet at a solid content of 4 to 5 g/m'' to obtain a white sheet with photochromic properties.A pressure-sensitive adhesive was applied to the back side of this sheet. This label was applied to stationery, toys, etc., and when exposed to sunlight for 20 seconds, it developed a green color. When the light irradiation was stopped, it returned to its original white color.

This colored paper was durable against heat and humidity and had good storage stability.

Example 3 NBP-1 (manufactured by Shiraki Chemical Co., Ltd., electron-donating color-forming organic compound) 0.25 parts Triphenylphenacylphosphonium tetrafluoroborate 0.5 parts Newball 50HB-2000 (Sanyo Chemical Co., Ltd.) Poly (oxyethylene oxypropylene) glycol monoether) 0.25 parts toluene
7 parts Methyl ethyl ketone 10 parts Methanol 3 parts After all the components were stirred and dissolved and dispersed, high-quality paper was impregnated with a solid content of 2 to 3 g/m'' to obtain a photochromic paper having photochromic properties.

When this photochromic paper was exposed to blank light for 30 seconds, 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, almost no deterioration in performance was observed.

This photochromic paper was durable against 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 PEG6
00 (manufactured by NOF Corporation, polyethylene glycol,
Average molecular weight 600) 0.5 part Srefuku BX-L
(Manufactured by Tanezu Kagaku Co., Ltd., butyral resin)
2 parts methyl ethyl ketone 20 parts toluene 4 parts methanol
After stirring and dissolving and dispersing all the components in 5 parts, letterpress printing was performed on high-quality paper to obtain white photochromic paper exhibiting 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, which was repeated 20 times, but there was almost no deterioration in performance.

This photochromic paper was durable against heat and humidity and had good storage stability.

Example 5 0P-55 (manufactured by Yamada Chemical Co., Ltd., electron-donating color-forming organic compound) 0.25 parts Triphenylsulfonium hexafluoroborate 0.5 parts Unionix C-2300 (manufactured by NOF Corporation) , castor oil ether of polyethylene glycol) 0.5 parts Eslesoc BM-52 parts Methyl ethyl ketone 8 parts Toluene
2 parts methanol
After stirring and dissolving and dispersing all the components in the two parts, printing was performed on high-quality paper using a stencil to obtain white photochromic paper having photochromic performance. When this photochromic paper was exposed to sunlight for 30 seconds, the printed area 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 photochromic paper was durable against heat and humidity and had good storage stability.

Example 6 Red-40P (manufactured by Shiraki Kagaku Co., Ltd., electron-donating color-forming organic compound) 0.25 parts Diphenyl-4-thiophenoxyphenylsulfonium tetrafluoroborate 0.5 parts Emulgen 903 (Seiho Atlas Co., Ltd.) ), polyoxyethylene nonylphenol ether)
0.5 parts Eslenok BM-52 parts Methyl ethyl ketone 15 parts Toluene
5 parts methanol
Part 5 After stirring and dissolving and dispersing all the ingredients, the mixture was coated on a polyester sheet at a solid content of 5 to 6 g/m'' to obtain a white sheet with photochromic properties.A photographic negative original was placed on this sheet. When exposed to a chemical lamp for 30 seconds, the exposed area turned red, and when the light irradiation was stopped, it returned to its original white color.This process was repeated 20 times, but there was almost no deterioration in performance.

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

Example 7 PSD-HR (manufactured by Shin Nisso Kako Co., Ltd., electron-donating color-forming organic compound) 0.25 parts Triphenylsulfonium hexafluorophosphate 0.75 parts Twee
n80 (manufactured by Seisei Atlas Co., Ltd., polyoxyethylene sorbitan monooleate) 0.5 parts Ethyl cellulose, N-4 (cellulose resin manufactured by Vercules, USA) 1.5 parts Methyl ethyl ketone 10 parts After stirring and dissolving all components A white sheet with photochromic properties was obtained by coating a polyester sheet with a solid content of 3 to 4 g/m. A photographic negative original was placed on this sheet and exposed to sunlight or a chemical lamp for 30 seconds. When the light irradiation was stopped, the color returned to its original white color, and the decolorization process was repeated 20 times, but almost no deterioration in performance was observed.

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

Example 8 TH-107 (manufactured by Hodogaya Chemical Co., Ltd., electron-donating color-forming organic compound) 0.25 parts diphenyliodonium hexafluorophosphate 0.75 parts 'l'w
een60 (manufactured by Seisei Atlas Co., Ltd., polyoxyethylene sorbitan monostearate) 0.5 parts Srefuku BX-L 1.5 parts Ethyl cellulose, N-4 (manufactured by Vercules, USA, methyl ethyl ketone 10 parts methanol
After stirring and dispersing all the components in Part 2, they were coated on high-quality paper to a solid content of 4 to 5 g/m'' to obtain white photochromic paper with photochromic performance. A photographic negative original was placed on this photochromic paper. When exposed to sunlight or a chemical lamp for 30 seconds, the exposed area developed a black color.When the light irradiation was stopped, the original white color returned to the original white color, which was repeated 20 times, but there was almost no deterioration in performance. .

This photochromic paper was durable against heat and humidity and had good storage stability.

Example 9 NG-100 (manufactured by Teikoku Kagaku Co., Ltd., electron-donating color-forming organic compound) 0.25 parts Triphinidactyl sulfonium tetrafluoroborate 0.5 parts PEG-6
00 (manufactured by NOF Corporation, polyethylene glycol,
Average molecular weight 600) 0.5 part methyl isopluketone
12.5 parts toluene
12.5 parts All the ingredients were stirred, dissolved and dispersed, and then filled into a pen body as an ink for a fiber pen.

When this pen was used to write on paper or plastic film, a latent image was obtained that was almost invisible to the naked eye.

Next, when this latent image area was irradiated with sunlight for 15 seconds, a blue image was developed. When light irradiation was stopped, it returned to its original colorless state 0
Although the decoloring process was repeated 10 times, almost no deterioration in performance was observed.

(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.

Patent applicant: Pilot Mannen Pen Co., Ltd. Procedural amendment May 20, 1985 Manabu Shiga, Commissioner of the Patent Office 1. Indication of case: 1985 Patent Application No. 4736 2. Title of invention: Photochromic material 3. Make amendments. Person Relationship to the case Patent applicant Showa
Year, month, date (shipment date: Showa, month, day) 6. Contents of the amendment (1) General formula CIII on page 6, line 3) is corrected as follows.

(2) Correct "humidity" in line 4 of page 7 to "humidity".

Claims (1)

[Scope of Claims] (A) an electron-donating color-forming organic compound; (B) a sulfonium salt represented by the following general formula [I]; a sulfonium salt represented by the general formula [II];
A photochromic material comprising as essential components at least one photoactive agent selected from the phosphonium salt represented by the formula [III] and the iodonium salt represented by the general formula [III], and (C) a compound having an oxyethylene group. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ Here, R_1, R_2, and 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, and n is 0 or 1. X^- is C
It is a complex ion containing lO4^-, or boron, phosphorus, antimony, or arsenic and a halogen. General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Here, R_4 is an alkyl group with 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 organic group forming an aromatic group. X^- is the same as X^- in general formula [I]. General formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Here, R_5 and R_6 are hydrogen, a halogen atom, a nitro group, an alkyl group having 1 to 4 carbon atoms, or a substituted derivative thereof. is a valent aliphatic group. X
^- is the same as X^- in general formula [I].