JPS62106449A - Coloring photosensitive composition - Google Patents

Abstract

PURPOSE:To improve a coloring density by incorporating a specific coloring auxiliary to the titled composition contg. leucotriarylmethane dye and hexaarylbiimidazole. CONSTITUTION:The titled composition contains a compd. which has at least one of an aromatic ring in a same molecule, and directly binds at least two carboxyl groups to the same aromatic ring, and hexaarylbiimidazole shown by formula I wherein R1-R9 are each 1-6C lower alkyl group and the oxidizable leucotriarylmethane dye. As said compd., phthalic acid, etc., can be used. As the hexaarylbiimidazole, 2,2'-di(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'- biimidazole, etc., are exemplified. As the oxidizable leucotriarylmethane dye, tris(4-diethylamino-o-tolyl)methane, etc., are exemplified.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a novel color-forming photosensitive composition that provides colored images by irradiation with light.0 [Prior Art and Problems] Conventionally, color-forming photosensitive compositions Many compositions are known. One such method is already known as free radical photography, that is, a method using a mixture of arylamines and organic halogen compounds that generate radicals when exposed to light. Here, carbon tetrabromide, iodoform, etc. are often used as the organic halogen compound. However, since these substances tend to be toxic and have sublimation properties, there is a problem in the storage stability of color-forming photosensitive compositions.

On the other hand, a color-forming photosensitive composition using a leukotriarylmethane dye as a color former and a hexaarylbiimidazole as a photo-oxidizing agent solves these problems, but has the drawback of low color density.

[Means for solving problems]

In view of the above-mentioned problems, the present inventors conducted extensive research and found that the coloring density can be improved by adding a specific coloring aid to a coloring photosensitive composition containing a leucotriarylmethane dye and a hexaarylbiimidazole. This discovery led to the present invention.

That is, the present invention provides (1) a compound having at least one aromatic ring in the same molecule and having at least two carboxyl groups directly bonded to the same aromatic ring; (2) a compound represented by the general formula (1); Hexaaryl biimi (wherein R1-R3 are selected from the group consisting of a lower alkyl group having 1 to 6 carbon atoms, a lower alkoxyl group having 1 to 6 carbon atoms, a chloro atom, a bromo atom, and a fluoro atom) (2) It may be a phenyl loam residue, and two adjacent substituents may be bonded to form a benzo ring.) (3) Contains an oxidizable leukotriarylmethane dye. This invention relates to a color-forming photosensitive composition.

In the present invention, compounds having at least one aromatic ring in the same molecule and having at least two carboxyl groups directly bonded to the same aromatic ring include phthalic acid, isophthalic acid, terephthalic acid, and trimellidic acid. , 3.3',
4. Examples include, but are not limited to, 4'-benzophenonetetracarboxylic acid, trimellitic acid monomethyl ester, trimellitic acid monoethyl ester, pyromellitic acid, pyromellitic acid monomethyl ester, pyromellitic acid diethyl ester, etc. 〇 Hexaary As the rubiimidazole, for example, compounds described in Japanese Patent Publication No. 5545/1982 and Japanese Patent Application Laid-open No. 12879/1988 can be used. Specifically, 2,2'-di(2-
chlorophenyl) -'+5+4't5'-tetraphenyl-1,2'-biimidazole, 2,2'-di(2-
Chlorophenyl) -4,5,4',5'-? Trakis(3-methoxyphenyl)-1,2'-biimidazole, 2,2'-di(2-chloro-4-methoxyphenyl)-4,4',5.5'-tetraphenyl-1,2'
-Biimidazole and the like can be used, but are not limited to these.

Further, as oxidizable leucotriarylmethane dyes, for example, Japanese Patent Publication No. 45-40150, Japanese Patent Publication No. 47-178
Compounds described in Publication No. 55 can be used. Specifically, tris(4-diethylamino-0-tolyl)methane, bis(4-diethylamino-0-lyl)phenylmethane,
Bis(4-diethylamino-0-)lyl)chenyl-2
- Triarylmethane compounds such as methane, bis(2-chloro-4-diethylaminophenyl)phenylmethane, leucomalachite green, and leuco crystal violet can be used. In addition, mineral acid salts or aromatic sulfonate salts of the oxidative color-forming leukotriarylmethane dyes described above can also be used, but the invention is not limited to these.

The color-forming photosensitive composition of the present invention can be actually used as a photosensitive layer by dissolving the above-mentioned components in a suitable solvent, impregnating it into paper or cloth, and drying it, or by dissolving it together with an organic polymer compound in a solvent. A method of forming a photosensitive layer by subsequently coating the surface of a suitable support such as paper, cloth, metal, polymer film, ceramic, or other material that does not adversely affect the present invention can be considered. Such an organic polymer compound preferably has film-forming ability, for example,
Polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, styrene =
Examples include (meth)acrylic acid copolymer, (meth)acrylic acid-methyl methacrylate copolymer, polyvinyl butyral, cellulose ester, polyacrylamide, and saturated polyester, which are appropriately selected and used depending on the purpose. It is also advantageous to add flexibility to the photosensitive layer by mixing a suitable plasticizer with the organic polymer compound.

When such an organic polymer compound is used, it is desirable to use the coloring photosensitive composition of the present invention in an amount of 0.01 to 500 parts by weight per 100 parts by weight of the organic polymer compound.

In addition, active light sources to be used include deep ultraviolet light sources (Hg-Xe lamps, low-pressure mercury lamps) and excimer lasers that have a strong emission spectrum in the range of 200 to 30 cm, as well as Hg lamps, xenon lamps, and high-pressure lamps that have emission spectra of 30 cm or more. Mercury lamp,
Furthermore, N2 laser, argon laser, He+-N
o laser, etc.

〔Example〕

Next, the present invention will be specifically explained using examples.

However, the present invention is not limited to these Examples.

Example 1 A coloring photosensitive composition was obtained by mixing the following components.

Phthalic acid 0.1t Leuco crystal violet 0.3t Methyl enal ketone 201 Toyo F paper A2 was impregnated with this and dried at 50°C to obtain a photosensitive paper. Half of this photosensitive paper was covered with aluminum foil, and then exposed to light from a distance of 50 cm using a 2 kW ultra-high pressure mercury lamp for 10 seconds, so that the portion not covered with aluminum foil developed a deep blue color.

Example 2 A coloring photosensitive composition was obtained by mixing the following components.

Poly(methyl methacrylate) 80v Phthalic acid 0.1f Leuco crystal violet 0.32 Methyl ethyl ketone 100v This was uniformly applied onto a 50 μm thick polyethylene glycol terephthalate film support using an applicator, dried at 70°C, and exposed. Got layers. The thickness of the photosensitive layer was 25 μm.

This concentration was measured using a transmission type densitometer (TD-528 manufactured by Macbeth).
Then, the turret color tod was set to orange (the filter was set to VISUAL), and the measurement was taken as the "pre-exposure density." Next, a 2 kW ultra-high pressure mercury lamp was used at a distance of 50 m.
Exposure for seconds, measure the density of the dark blue colored area in the same way,
This was defined as the "post-exposure density." The difference between the "pre-exposure density" and the "post-exposure density" was defined as the "coloring density."

The color density was 0.17.

Example 3 A coloring photosensitive composition was obtained by mixing the following components.

Poly(methyl methacrylate) 80t trimellidic acid 0.1f leuco crystal violet l-0,3f methyl ethyl ketone
100 was then treated in the same manner as in Example 1 to obtain a photosensitive layer having a thickness of 25 μm. A mask film having the film density of the 21st stage Osho of the Straffer Step Tablet was placed on top of this and exposed in the same manner. The pattern of the mask was transferred onto the photosensitive layer as a dark blue visible image.

The color density was 0.21. Comparative example 1 A coloring photosensitive composition was obtained by mixing the following components.

Poly(methyl methacrylate) 80f benzoic acid 0.1f leuco crystal violet 0.5f methyl ethyl ketone
1002 Next, a photosensitive layer was prepared in the same manner as in Example 1.

The color density was 0.11.

Claims (3)

[Claims] (1) having at least one aromatic ring in the same molecule;
and a compound in which at least two carboxyl groups are directly bonded to the same aromatic ring (2) Hexaarylbiimidazole represented by general formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (I) (Here, R_1 to R_9 are lower alkyl groups having 1 to 6 carbon atoms, and 1 to 6 carbon atoms. lower alkoxyl group, chlorine atom,
It is a residue selected from the group consisting of a bromo atom and a fluoro atom, and two adjacent substituents on the phenyl ring may be bonded to form a benzo ring. ) (3) A color-forming photosensitive composition containing an oxidizable leukotriarylmethane dye.