JPS6070444A - Nonsilver salt type photosensitive material - Google Patents

Abstract

PURPOSE:To enable formation of a colored image through irradiation of light without development by mixing a specified ketone compd., a substance capable of reacting with said ketone compd. on irradiation of light and forming a dye, and a specified amt. of sensitizer. CONSTITUTION:A compsn. contains a alpha-(arylsulfonyl)-methylarylketone represented by the formula in which R1, R2 are each aryl, capable of releasing a free radical on irradiation of light, a substance capable of reacting with this ketone compd. on the irradiation of light and forming a dye, and a sensitizer in an amt. of 0-300pts.wt. per 100pts.wt. of said ketone compd. As this compd., alpha-phenylsulfonylacetophenone, alpha-phenylsulfonyl-p-chloroacetophenone, alpha-(4-dimethylaminophenyl-sulfonyl)-p-dimethylamino-acetophenone, etc. are usable. As said dye forming compd., various kinds. of compds. colorable by loss of H, such as leuco dyes, or their derivs., especially, triarylmethane type leuco dyes, and their salts are high in coloring density and useful.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel non-silver salt photosensitive composition that allows colored images to be obtained without development by irradiation with light.

Conventionally, as a non-silver salt photosensitive composition for producing colored images, free radical photography, that is, a mixture of an arylamine and an organic compound as a substance that generates free radicals when exposed to light, has been known.

In this case, carbon tetrabromide is used as the organic halogen compound.

Iodoform and the like have been widely used. However, since these substances are volatile, they have the disadvantage that they have poor stability and that the working environment is contaminated with these substances that are harmful to the human body.

Further, as a method for obtaining a colored image by removing hydrogen from a triarylmethane-based leuco dye, there is a method described in U.S. Pat. No. 3,102,810, but when using a leuco dye, Organic halogen compounds are also often used, and the fundamental problems mentioned above remain. Furthermore, since leuco dyes generally easily abstract hydrogen to form pigments, coloration occurs as the organic compound decomposes over time.
Particularly when it is stored as a coating solution, it has the disadvantage that such a dark reaction causes coloring even if it is stored in a dark place at room temperature, resulting in poor stability. Therefore, there is an inconvenience that it must be prepared immediately before use.

Therefore, the present inventors replaced it with an organic halogen compound. As a result of intensive research into substances that generate free radicals when exposed to light, we discovered that the radicals generated by light irradiation of α-(arylsulfonyl)-methylarylketone compounds are surprisingly effective. It has arrived.

That is, the present invention provides (A) an α-(arylsulfonyl)-methylarylketone compound represented by the general formula CR, where R2 is an unsubstituted or substituted aryl group as a compound that releases free radicals by light irradiation. , φ) (A) A substance that reacts with the α-(arylsulfonyl-methylaryl ketone compound shown in 0 per 100 parts by weight of the sulfonyl)-methylarylketone compound
The present invention relates to a non-silver salt photosensitive composition containing up to 500 parts by weight of a sensitizer.

The present invention will be specifically explained below.

The α-(arylsulfonyl)-methylaryl ketone compound of the present invention is described, for example, in the Journal of the American Chemical Society.

71, 3511 (1949) or Journal of the American Chemical Society +77+5
os (1955) and other known methods. Examples of the α-(arylsulfonyl)-methylarylketone compound are α-phenylsulfonylacetophenone and α-phenylsulfonyl-p-chloroacetophenone.

α-Phenylsulfonyl-m-chloro-acetophenone, α-phenylsulfonyl-〇-chloroacetophenone, α-phenylsulfonyl-p-promoacetophenone, α-phenylsulfonyl-p-methyl-acetophenone, α-phenylsulfonyl-m- 71thyl-acetophenone, α-phenylsulfonyl-O-methylacetophenone, α-phenylsulfonyl-p-methoxy-
Acetophenone, α-phenylsulfonyl-p-amino-acetophenone, ff-phenylsulfonyl-m-amino-acetophenone, α-phenylsulfonyl-p-
Dimethylamino-acetophenone, α-(phenylsulfonyl)-methyl-(a-naphthyl)ketone.

α-(phenylsulfonyl)-mef-Cβ-,3 naphthyl)ketone, α-(4-aminophenylsulfonyl)-acetophenone, α-(4-aminophenylsulfonyl)-p-”ro-acetophenone, α -(4-aminophenylsulfonyl(4-aminophenylsulfonylxy-acetophenone, α-(4-aminophenylsulfonyl)-1)-amino-acetophenone, a -
(4-dimethylaminophenylsulfonylaminophenylsulfonyl) p-shimef #7
It is possible to mention minnow acetopheno 7 and the like. Of course, the present invention is not limited to these. Note that these may be used alone or in combination.

α-(arylsulfonyl) by irradiation with light
- As the substance that reacts with the methylarylketone compound to form a dye, there can be used various substances that color by losing hydrogen, such as leuco dyes or derivatives thereof. Especially the reduced form of triarylmethane dyes!
Cuccitriarylmethaneleuco dyes or salts thereof are useful because of their high coloring density. An example of such a leuco dye or a salt thereof is tris(p-N,N-diethylamine-〇-tolyl)methane.

Bis(p-N,N-diethylamine-〇-tolyl)chenylmethane, bis(p-N,N-diethylamine/o
-) IJru)-phenylmethane, bis(p -N,
N-diethylamino-0-tolyl)benzylthiophenylmethane, leucomalachite clean, leuco crystal violet, or their hydrochlorides, sulfates, Lewis acid salts, p-toluenesulfonates, and the like. Of course, the present invention is not limited to these. Note that these may be used alone or in combination. It is preferable that these be used in an amount of 10 to 400 parts by weight per 100 parts by weight of the α-(arylsulfonyl)-methylarylketone compound, depending on the desired degree of color development.

Although a sensitizer is not necessarily required, it is advantageous to mix it when a higher color density is required with the same amount of light or when it is desired to expose with light in a longer wavelength range. Many such sensitizers can be used, including benzyl.

Michler's ketone, p, p'-tetraethylaminobenzophenone, p-dimethylaminobenzophenone, p-diethylaminobenzophenone and other alkyl aminobenzophenones, p-dimethylaminobenzaldehyde,
Alkylaminobenzaldehydes such as p-diethylaminobenzaldehyde, alkylaminobenzoic acid esters such as methyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate, thioxanthone, 2-
Examples include chloro-thioxanthone. Various sensitizing dyes, such as acridine dyes, cyanine dyes, and merocyanine dyes, can also be used.

These may be used alone or in combination.

The present invention is not limited to the sensitizers mentioned herein.

In the present invention, other components such as a stabilizer and an organic polymer binder can be added as necessary. Examples of the stabilizer include triethylamine, triethanolamine, triphenylamine, triphenylphosphine, hydroquinone, hydroquinone monomethyl ether, and t-butylcatechol. These can be added within a range that does not inhibit the photocoloring reaction.

Examples of the organic polymer binder include vinyl polymers such as polyvinyl alcohol, polyvinyl acetate, and polystyrene, polymethacrylates such as polymethyl methacrylate, and copolymers thereof, celluloses such as acetylcellulose and nitrocellulose, and the like. Examples include polymeric compounds with film-forming ability. These may be used alone or in combination. Furthermore, when using an organic polymer binder, a plasticizer can be added to impart appropriate flexibility. Examples of the plasticizer include phthalic acid esters such as diethyl phthalate, dibutyl phthalate, diheptyl phthalate, and dioctyl phthalate, and fatty acid esters such as dioctyl adipate and diptyl diglycol adipate.

Phosphate esters such as trimethylphosphine.

Sulfonic acid amides such as toluenesulfonic acid amide,
Examples include.

The composition of the present invention can be dissolved or dispersed in a suitable solvent, coated or impregnated onto a support, and then the solvent can be evaporated to form a photosensitive layer. The support in this case may be any material that does not adversely affect photopolymerization, such as various plastics, various films, paper, and glass.

Any solid substance can be selected, such as various metals and ceramic products.

A colored image can be obtained by overlaying the original image on the thus prepared photosensitive layer and exposing it to a suitable light source, such as an ultra-high pressure mercury lamp.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

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

α-(Phenylsulfonyl)-acetophenone 1.0
Taro Crystal Violet) CO? p-Toluenesulfonic acid 0.22 Methyl ethyl ketone 205' This was placed in a test tube for 5 me, and then exposed for 10 seconds from a distance of 50 (Tn) using a 2 kW ultra-high pressure mercury lamp.

A blue colored solution was obtained after exposure.

Example 2 Toyo filter whetstone 2 was impregnated with the solution prepared in Example 1 and heated to 75°C.
The solvent was evaporated and dried to obtain a photosensitive paper. 1 c for this
A negative mask with transparent letters rDJ of rnX 1 cm was overlaid and exposed in the same manner as in Example 1. The words ``DJ'' appeared in blue on the filter paper.

Example 6 A photosensitive composition was obtained by mixing the following components.

Poly(methyl methacrylate) 50. Of dibutyl phthalate 10.0' α-(phenylsulfony)-acetophene/7 2.
(1 Michler Ketone 0.59 0 Ico Crystal Violet) 1.0? p-) Luenesulfonic acid 0.22 Methyl ethyl ketone 1152 This was uniformly coated on a 25 μm polyethylene glycol terephthalate film support and dried at 75° C. to obtain a photosensitive film. The thickness of the photosensitive layer was 25μ. This was measured using a transmission type densitometer (TD-528 manufactured by Macbeth) with the turret color tod set to orange (the filters were V and T).
SUAL K&RU) was measured and defined as "exposure agent concentration". Next, a mask film having a film density equivalent to the 21st stage of a stuffer step tablet was overlapped at a distance of 50 mm using a 2 kW ultra-high pressure mercury lamp and exposed for 10 seconds.

The mask brim pattern was transferred onto the film as a blue visible image. The density of the colored portion was measured in the same manner, and this was defined as the "post-exposure density." The difference between the "exposure agent concentration" and the "post-exposure density" was defined as the "coloring density." The color density was 0.06.

Example 4 A photosensitive composition was obtained by mixing the following components.

Poly(methyl methacrylate) 50. Of dibutyl phthalate 10. Of α-(phenylsulfonyl)-acetophenone 2.0
f2-Chlor-thioxanthone 2.020 Icocrystal Violet 1. (1p-) Luenesulfonic acid □, 21 Methyl ethyl ketone 115f Using this composition, a -C photosensitive film was prepared in the same manner as in Example 3 and evaluated.

The mask pattern was transferred as a dark blue visible image. The color density was 0.10.

Example 5 A photosensitive composition was obtained by mixing the following components.

Poly(methyl methacrylate) 50. Of dibutyl phthalate 10.0 f α-(phenylsulfonyl)-acetophenone 2.0
1 Thioxanthone 2.0 Taloyco Crystal Violet 1. Otp-toluenesulfonic acid 0.2 f Methyl ethyl ketone 1152 Using this composition, a photosensitive film was prepared and evaluated in the same manner as in Example 6.

The mask pattern was transferred as a dark blue visible image. The color density was 0.12.

Applicant's agent Kaoru Furutani

Claims (1)

[Claims] 1) α-(arylsulfonyl)-methyl represented by the general formula (wherein R1 and R2 are unsubstituted or substituted aryl groups) as a compound that releases free radicals by light irradiation. Aryl ketone compound, (B) α-(arylsulfonyl) represented by (A)
- A substance that reacts with a methylarylketone compound to form a pigment when irradiated with light, and α-(arylsulfonyl) represented by (0) (A)
100 methyl aryl ketone compounds! A non-silver salt photosensitive composition containing 0 to 300 parts by weight of a sensitizer based on parts ft. 2. The non-silver salt photosensitive composition according to claim 1, wherein the component (B) is a leuco dye or a derivative thereof that becomes a dye by losing hydrogen. 3. The non-silver salt photosensitive composition according to claim 1, wherein component (B) is a triarylmethane leuco dye or a salt thereof.