JPS6242149A - Photosensitive color developing composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive color developing composition capable of developing various colors and having superior durability and shelf stability by using an electron donative org. compound causing coloration and at least one kind of optical activator selected among aromatic halonium salts and the aromatic onium salts of the group VIa and Va elements as essential components. CONSTITUTION:When an electron donative org. compound causing coloration is used in combination with an optical activator selected among aromatic halonium salts and the aromatic onium salts of the group VIa and Va elements, the org. compound is allowed to color at high density in a movement. The org. compound used is generally colorless or light-colored, and when the compound undergoes the action of a color developing component such as Br..onsted acid or Lewis acid, it donates electrons and develops color. Triphenylmethanephthalide is typically used as the compound. Two or more similar or different kinds of electron donative org. compounds may be used. For example, triphenylmethanephthalide is combined with crystal violet lactone. The optical activator is a compound which is colorless or light-colored and releases a color developing component such as Br..onsted acid when irradiated with light. The color developing component makes the electron donative org. compound develop color.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Application of the Invention) The present invention relates to a photosensitive color-forming composition that develops color upon irradiation with light.

(Prior Art and Problems) Conventionally, photosensitive color-forming compositions in which an electron-donating color-forming organic compound and a photoactive agent are combined include an electron-donating color-forming organic compound and an organic halogen compound (U.S. Pat. No. 3,042,515).
Specification No. 3042519, Special Publication No. 40-37
Publication No. 3), quinonediazide compound (Japanese Patent Publication No. 45-30
No. 885), or diazonium salt (Japanese Patent Publication No. 49-5
No. 21 Publication) is known, but it has color development sensitivity that quickly develops color upon light irradiation, high color density of the colored product, no odor, and does not generate gas during light irradiation.
There has been no effective product that can be used in many industrial applications because there is not enough material in terms of performance, such as durability against heat and humidity, stability for long-term storage, and a wide variety of colors. for example,
When a quinone diazide compound or diazonium salt is used as a photoactivator, gas is generated during light irradiation, resulting in bubbles; when an organic halogen compound is used, the vapor pressure is high, resulting in a strong odor;
Products using quinonediazide compounds and diazonium salts are unstable to heat and humidity, and therefore have drawbacks such as lack of durability and instability in long-term storage.

(Object of the Invention) The object of the present invention is to improve the drawbacks of the conventional photochromic compositions described above and to obtain a novel photosensitive color-forming composition that satisfies the required performance.

(Structure of the Invention) The present invention comprises (1) (A) an electron-donating color-forming organic compound; (B) an aromatic halonium salt, a Group VIa element, or a Group VIa element;
At least one selected from aromatic onium salts of group a elements
(2) (A) an electron-donating color-forming organic compound; and (B) an aromatic halonium salt, a Group VIa element, or a Group Va element; This is a photosensitive color-forming composition containing as essential components at least one photoactive agent selected from aromatic onium salts of elements and (C) a compound having an alcoholic hydroxyl group.

The inventors of the present invention found that all of the conventional photoactivators have practical drawbacks, and as a result of various studies on how to improve them, the inventors found that the above-mentioned aromatic halonium salts, Group Vra elements, or Group Va elements were used as photoactivators. It has been found that the intended purpose can be achieved when at least one selected from aromatic onium salts is used in combination with an electron-donating color-forming organic compound. This point is the greatest feature of the present invention.

Furthermore, it has been found that when a compound having an alcoholic hydroxyl group is added to the photosensitive color-forming composition, the color-forming sensitivity is further improved without impairing the above-mentioned performance. This point is another feature of the present invention.

That is, when the present inventors used an electron-donating color-forming organic compound in combination with at least one salt selected from an aromatic halonium salt, an aromatic onium salt of a Group VIa element or a Group Va element, Even when irradiated with light, the salt quickly releases color-forming components such as Brønsted acids and Lewis acids without generating gas or bubbles, and instantaneously causes the electron-donating color-forming organic compound to develop color at a high concentration. Heading, furthermore, the salt itself has no odor and is highly resistant to heat and humidity;
We have discovered that it is an excellent photoactive agent with good long-term storage stability, and the combination of the photoactive agent with an electron-donating color-forming organic compound is an excellent new photosensitizer that completely solves the drawbacks of the conventional ones. It has been found that the composition can be used as a color-forming composition. The present invention further provides that when a compound having an alcoholic hydroxyl group is added to the photosensitive color-forming composition, it has a coloring speed-improving effect that causes the electron-donating color-forming organic compound to develop color from the moment of light irradiation without impairing the performance. It was discovered that it exhibits excellent properties. (In other words, when irradiated with light, color-forming components such as Brønsted acid and Lewis acid, which color an electron-donating color-forming organic compound with high sensitivity, are generated very quickly due to the interaction between a photoactive agent and a compound having an alcoholic hydroxyl group. As a result, it is thought that the electron-donating, color-forming organic compound donates electrons and develops color instantly.

) A photosensitive color-forming composition that combines such a photoactive agent, an electron-donating color-forming organic compound, and a compound having an alcoholic hydroxyl group, and a photosensitive color-forming composition in which a compound having an alcoholic hydroxyl group is added to the photosensitive color-forming composition. All of the photosensitive color-forming compositions were new and could be satisfactory photosensitive color-forming compositions with no defects in all respects.

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 Brønsted acids and Lewis acids. Representative compounds include triphenylmethane phthalides,
Fluoranes, phenothiazines, indolylphthalides, leucouramines, rhodamine lactams, rhodamine lactones, indolines, triphenylmethanes, azaphthalides, chromenoindoles, triazenes, etc., and may be of the same or different types. Two or more of these can be used in combination. Next, a specific example will be shown. Crystal violet lactone, malachite green lactone, Michler's hydrogen, 3-diethylamino-α-benzofluorane, 3-diethylamino-7-methylfluoran,
3-diethylamino-7-(o-chlorophenyl)-aminofluorane, 3-N-ethyl-NP-tolylamino-7-methyl-N-phenylaminofluorane, 3-
pyrrolidino-6-methyl-7-, anilinofluorane,
N-(2,3-dichlorophenyl)-leucouramine, N-2,4,5-trichlorophenylleucouramine, N-benzoyluramine, N-phenyluramine, rhodamine B lactam, rhodamine B lactone, 2
-(phenyliminoethanedylidene)-3,3" -dimethylindoline, P-nitrobenzylleucomethylene blue, benzoylleucomethylene blue, 3.7-bis(dimethylamino)-10-penzoylphenothiazine, 3.7 -Pisdimethylamino-1O-(4°-aminobenzoyl)phenothiazine, 3.7-pisdimethylamino-1O-(4'-pyridinohendiyl)phenothiazine, 3.7-pisdimethylamino-1O-(4
'-bis-(4'',4''-dimethylaminophenyl)methylaminobenzoyl]phenothiazine, and the like.

The photoactivator used in the present invention is a colorless or light-colored compound that, when irradiated with light, releases a color-forming component such as Brønsted acid or Lewis acid that colors an electron-donating color-forming organic compound. Halonium salts, aromatic onium salts of group Vla elements or group Va elements. Preferred are aromatic halonium salts (aromatic halonium Sb,
Fe, Sn, B15Al, Ga, In, Ti, Zr,
halogen-containing complex ion salts of B, P, As) Group VIa elements (0, S, Se, Te) or Group Va elements (N, P, As, Sb, Bi) of the Periodic Table of the Elements Aromatic onium sb, Fe, Sn, F3i, AI, Ga, I
n, Ti.

These are halogen-containing complex ion salts of Zr, B, P, and As, or aromatic onium perchlorates. Details can be found in the following document:

Macron+olecules, 10(6) 13
07 (1977) J, Org, Chem, 43 (
15) 3055 (1978) J, Radiat, Cur.
ir+g, 5(1)2 (1978) J, Po ly
, Sci, , Poly+n, chem, E
d, , 17.977, 1047 (1979) J
, Po Iy, Sci, , Poyn+, ch
em, Ed, , 18.2677, 2697 (1
980) J, Polym, Sci, Polym, che
m, Ed, 22.1789 (1984) Adv, Po
lymer, Sci, 62.1 (1984) Materials Technology, 2 (10) 553 (1984) Next,
Specific examples of photoactivators are shown below. Note that the photoactive agent in the present invention is not limited to this.

Aromatic halonium salt Aromatic onium salt of group Vla element S b F-6 Aromatic onium salt of group Va element, the compound having an alcoholic hydroxyl group used in the basic invention is a colorless or light-colored liquid or solid that does not donate electrons. When coexisting with a color-forming organic compound and a photoactivator component, it has the property of increasing the rate of color development upon irradiation with light. Preferred examples include aliphatic alcohols and polyhydric alcohols with 6 or more carbon atoms and a boiling point of 150°C or more, aromatic alcohols with I37 or more carbon atoms and a boiling point of 150°C or more, and polymeric alcohols with a molecular weight of about 10,000 to 300,000. Next, specific examples of compounds will be shown. Hexyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, eicosyl alcohol, tocosyl alcohol, mericyl alcohol, oleyl alcohol, cyclohexanol, cyclopentanol, triphenyl carpineau Lunato aliphatic alcohols, aromatic alcohols such as benzyl alcohol, β-phenylethyl alcohol, cinnamyl alcohol, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monophenyl ether, ethylene glycol monohensyl 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 monolaurate, glycerin monopalmitate, glycerin monostearate, glycerin dilaurate, pentaerythritol, mannitol, sorbitan, sorbitan monolaurate, sorbitan monooleate, sorbitan tristearate, pentaerythritol Polyhydric alcohols such as erythritol, polyvinyl alcohol, polyvinyl acecool, polyvinyl butyral, cellulose acetate, hydroxyethyl cellulose, hydroxypropyl cellulose, cellulose acetate butyrate, cellulose acetate phthalate, methyl cellulose, ethyl cellulose, polysiloxane polycarpinol and other polymer alcohols .

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 usage ratio of the photoactive agent and the compound having an alcoholic hydroxyl group is in the range of 0.01 to 200 parts by weight of the compound having an alcoholic hydroxyl group per 1 part by weight of the photoactive agent, but the optimal range is 0.1 to 200 parts by weight. It is 100 parts by weight.

The photosensitive color-forming composition of the present invention can be used as it is, or can be applied to various substrates, printed, or rolled into it. Various additive components can be added to the photosensitive color-forming composition according to 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 adjusters such as acids and alkalis, color tone adjusters such as dyes and pigments, plasticizers,
Various stabilizers may be added as necessary.

The photosensitive color-forming composition of the present invention can be prepared as it is by adding an electron-donating color-forming organic compound, a photoactive agent, and optionally additives, or can be dissolved and dispersed in a suitable solvent, and then the solvent can be evaporated. Alternatively, an electron-donating color-forming organic compound, a photoactive agent, a compound having an alcoholic hydroxyl group, and optionally additives may be added thereto, either as is or dissolved and dispersed in an appropriate solvent. It can then be obtained by evaporating the solvent.

The photosensitive color-forming composition thus obtained had a wavelength of 40Qnm.
The starting color is affected by ultraviolet rays in the following wavelength range, especially 250~
Colors are effectively developed by ultraviolet light in the wavelength range of 350 nm and 350 nm. Suitable light sources include sunlight, mercury lamps, planocrite, xenon lamps, and ultraviolet lasers. Furthermore, this material is spectrally enhanced by adding a suitable aggravating agent, such as a dye, and becomes capable of producing color even with visible light of 400 m or more (sunlight, tungsten lamp). 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, it is possible to freely obtain a colored product with a desired color tone and high density.

As described above, the photosensitive coloring composition of the present invention is an excellent product that has improved all the drawbacks of conventional photosensitive coloring compositions, and can be used for paper, plastic sheets, metal foils, various fibers, glass, ceramics, etc. An ink that can be used by coating, printing, impregnating, sandwiching between two substrates, or rolling into a substrate such as plastic or wax, or can be converted into an ink and has photosensitive coloring performance. Or it can be used as a paint. As a result, the photosensitive color-forming composition 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 I NC-BK (manufactured by Hodogaya Chemical Co., Ltd., electron-donating color-forming organic compound) 5 parts Esresoku B
X-L (manufactured by Block Chemical Co., Ltd., butyral resin (compound with alcoholic hydroxyl group))
14 parts Methyl ethyl ketone 71 parts All ingredients were stirred, dissolved and dispersed, and then coated on a polyester sheet or high-quality paper to a solid content of 2 to 4 g/m" to obtain a sheet having a photosensitive coloring composition. This sheet When a photographic negative original was placed on top of the paper and exposed to sunlight for 20 seconds, the exposed areas turned black.

This sheet was odorless, resistant to heat and moisture, had good storage stability, did not generate gas or bubbles during exposure, and had high color development sensitivity and density.

Example 2 ATP (manufactured by Yamada Chemical Industry Co., Ltd., electron-donating color-forming organic compound) 5-part phenoxyethanol (compound having an alcoholic hydroxyl group)
4-part tricresyl phosphate
1 part MS-300 (manufactured by Nippon Steel Chemical Co., Ltd., styrene methacrylic acid copolymer) 6 parts methyl ethyl ketone 50 parts toluene
30 parts A sheet containing a photosensitive color-forming composition 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 20 seconds, the exposed areas developed a green color.

This sheet was odorless, resistant to heat and moisture, had good storage stability, did not generate gas or bubbles during exposure, and had high color development sensitivity and density.

Example 3 NBP-1 (manufactured by Yamada Chemical Industry Co., Ltd., electron-donating color-forming organic compound) 5 parts Esuresoku B
M-3 (manufactured by Miki Kagaku Co., Ltd., butyral resin (compound having alcoholic hydroxyl group)) 6 parts methyl ethyl ketone 30 parts toluene
20 parts A sheet having a photosensitive color-forming composition 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 20 seconds, the exposed areas developed a blue color.

This sheet was odorless, resistant to heat and moisture, had good storage stability, did not generate gas or bubbles during exposure, and had high color development sensitivity and density.

Example 4 Pergascript Red I-6B (manufactured by Ciba Geigy, electron-donating color-forming organic compound)
5 parts ethyl cellulose, N-4 (manufactured by Bercules, USA, cellulose resin (compound having alcoholic hydroxyl group)) 5 parts methyl ethyl ketone
40 parts A sheet containing a photosensitive color-forming composition 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 20 seconds, the exposed areas developed a red color.

This sheet was odorless, resistant to heat and moisture, had good storage stability, did not generate gas or bubbles during exposure, and had high color development sensitivity and density.

Example 5 OR-55 (manufactured by Yamada Kogyo Kagaku Co., Ltd., electron-donating color-forming organic compound) 5 parts MS-3006
Part methyl ethyl ketone 50 parts Toluene
20 parts A sheet containing the photosensitive coloring composition 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 20 seconds, the exposed areas developed an orange color.

This sheet was odorless, resistant to heat and moisture, had good storage stability, did not generate gas or bubbles during exposure, and had high coloring sensitivity and intensity.

Example 6 PSD-HR (manufactured by Nisso Chemical Co., Ltd., electron-donating color-forming organic compound) 5 parts Esresoku B
M-S (manufactured by Miki Kagaku Co., Ltd., butyral resin (compound having an alcoholic hydroxyl group)) 10 parts Methyl ethyl ketone 40 parts A white sheet having photosensitive coloring 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.

This sheet was odorless, resistant to heat and moisture, had good storage stability, did not generate gas or bubbles during exposure, and had high color development sensitivity and density.

Example 7 S-205 (manufactured by Yamada Chemical Industry Co., Ltd., electron-donating color-forming organic compound) 5 parts OCR3 cuttriphenyl phosphate 1 part toluene
30 parts methyl ethyl ketone
After stirring and dissolving all 50 parts of the ingredients, this ink was filled into a fiber pen to obtain a writing instrument. When this writing instrument was used to write on a plastic sheet, the handwriting could not be read with the naked eye, but when exposed to sunlight for 20 seconds, the handwritten area turned black, proving that it is useful as a hidden ink and has a rating of 2B. .

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

Claims (2)

[Claims] (1) (A) an electron-donating color-forming organic compound; and (B) at least one photoactive agent selected from aromatic halonium salts, aromatic onium salts of Group VIa elements or Group Va elements; A photosensitive color-forming composition containing as an essential ingredient. (2) (A) an electron-donating color-forming organic compound; and (B) at least one photoactive agent selected from aromatic halonium salts, aromatic onium salts of Group VIa elements or Group Va elements; , (C) a compound having an alcoholic hydroxyl group as an essential component.