JPH06295042A - Photographic material for silver complex salt diffusion transfer - Google Patents

Abstract

PURPOSE:To obtain a picture image of cool black tone in an image receiving layer by incorporating a specified compd. into layers which constitute a photosensitive element including a silver halide emulsion layer and a halation preventing layer, and performing silver complex salt diffusion transfer. CONSTITUTION:This photosensitive material has a silver halide emulsion layer and a halation preventing layer as layers which constitute the photosensitive element, and these layers contain a compd. expressed by formula I or formula II. In formula I, R1 and R2 are methyl or ethyl groups. The compd. (color controlling agent) is preferably incorporated into the halation preventing layer of the photosensitive element layers, and the amt. of the color controlling agent is preferably 0.1mg/m<2>-10mg/m<2>, more preferably 0.5-5mg/m<2>. In the halation preventing layer, carbon black having high absorption of light as the halation preventing agent is preferably used. The carbon black is used as a dispersed state with an anionic surfactant such as higher alcohol sulfate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light-sensitive material used in a silver image forming method using a silver complex salt diffusion transfer method.

[0002]

2. Description of the Related Art The principle of the silver complex salt diffusion transfer method (referred to as the DTR method) is described in US Pat. No. 2,352,014 and is well known. In the DTR method, silver complex salts are imagewise transferred from the silver halide emulsion layer to the image receiving layer by diffusion and they are often converted to a silver image in the presence of physical development nuclei. To this end, the image-wise exposed silver halide emulsion layer is brought into contact with, or brought into contact with, the image-receiving layer in the presence of a developing agent and a silver halide complexing agent, and unexposed silver halide To a soluble silver salt.

In the exposed parts of the silver halide emulsion layer the silver halide is developed into silver (chemical development) so that it cannot be dissolved anymore and therefore cannot diffuse.

In the unexposed portions of the silver halide emulsion layer, the silver halide is converted to a soluble silver salt, which is transferred to the image receiving layer where they normally form a silver image in the presence of development nuclei. In a direct positive silver halide emulsion, the effects of the silver halide in the exposed and unexposed areas are reversed.

In the DTR method, there is a so-called "two-sheet" type in which a silver halide emulsion layer and an image receiving layer are brought into close contact with each other to form a silver image on the image receiving material. In general, the "two-sheet" type is an image-receiving material that produces a silver image, such as a book,
It is used as a recycled product such as printed matter, and a master plate material for plate making. In order to obtain more excellent regenerated products, printed matter, etc., it is important that the quality of the silver image formed by the DTR method, such as image density, color tone, contrast, sharpness and resolution, is good.

In the diffusion transfer method using such a silver salt such as silver halide, it is generally known that the silver image transferred to the image receiving layer is not black but brown or other unacceptable color. There is. Therefore, in such a diffusion transfer method, a toning agent is used to eliminate the drawbacks.

A typical example of a conventionally known color tone agent is 1
-Phenyl-5-mercapto-1,2,3,4-tetrazole is known. Besides, US Pat. No. 3,75
S-substituted pyrimidine derivatives as described in 6,825 are known and reported to give dark blue images with high optical density.

However, the color tone of the silver image thus formed is not always preferable, and its improvement is desired. No satisfactory toning agent has been obtained which gives an image with a cold black tone, reduces the metallic luster of the image and increases the maximum density.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a cold black tone image on the image receiving layer by silver salt diffusion transfer.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver complex salt diffusion transfer light-sensitive material having at least a silver halide emulsion layer and an antihalation layer as layers constituting the light-sensitive element, wherein the light-sensitive element constituting layer contains This can be achieved by a silver salt diffusion transfer light-sensitive material characterized by containing at least one compound represented by the following Chemical formula 2 or Chemical formula 4.

[0011]

[Chemical 3]

(In the formula, R ₁ and R ₂ represent a methyl or ethyl group.)

[0013]

[Chemical 4]

Examples of the compounds represented by Chemical formulas 3 and 4 (hereinafter referred to as "toning agent") used in the present invention are shown below.

[0015]

[Chemical 5]

[0016]

[Chemical 6]

[0017]

[Chemical 7]

The layers constituting the light-sensitive element in the present invention include a silver halide emulsion layer, an antihalation layer and a protective layer.

The toning agent represented by Chemical Formula 3 or Chemical Formula 4 may be contained in any one of the layers constituting the photosensitive element.
Considering the transfer characteristics and the stability of the silver halide emulsion, it is most preferable to incorporate it in the antihalation layer.

The amount of the toning agent used in the present invention is 0.1 m.
g / m ^{2 to} 10 mg / m ² , preferably 0.5 mg /
a m ² ~5mg / m ^2. The present invention will be described in more detail below.

The support of the light-sensitive material of the present invention may be one normally used as a photographic film base or polyethylene-coated paper. Examples of the film base include cellulose acetate, cellulose acetate butyrate,
A transparent support such as a plastic film of polyethylene terephthalate, polystyrene, polypropylene or the like, a laminated film thereof, or a film obtained by coating both surfaces or one surface of the film with polyolefin such as polyethylene is used.

The hydrophilic binder which is advantageously used for preparing the silver halide emulsion of the light-sensitive material of the present invention includes lime-processed gelatin, acid-processed gelatin and gelatin derivatives (for example, Japanese Patent Publication Nos. 38-4854 and 39-39). No. 5514,
No. 40-12237, No. 42-26345, U.S. Patent Nos. 2,525,753 and 2,594,29.
No. 3, No. 2,614,928, No. 2,763,6
No. 39, No. 3,118,766, No. 3,132,
No. 945, No. 3,186,846, No. 3,31
2,553, British Patents 861,414, 1,
033, 198 etc.), proteins such as albumin and casein, cellulose compounds such as carboxymethyl cellulose and hydroxyethyl cellulose, agar, natural polymers such as sodium alginate, polyvinyl alcohol, poly-N-vinylpyrrolidone and polyacryl. There are synthetic hydrophilic binders such as acid copolymers, polyacrylamides or their derivatives, and partial hydrolysates, and these hydrophilic binders are dyes and / or pigments that absorb light in the photosensitive wavelength region of the emulsion layer. It is also advantageously used to form a so-called antihalation layer containing a. Further, it is advantageously used for forming other layers such as a backing layer, an intermediate layer, a protective layer and a non-photosensitive layer such as an image receiving layer.

Carbon black having a high degree of light absorption is preferably used as an antihalation agent in the antihalation layer. Carbon black can be used in a state of being dispersed with various surfactants. The surfactant used is preferably one which does not adversely affect the photograph, and any of those known to be used in the coating solution for the photographic layer is used. Examples thereof include anionic surfactants such as higher alcohol sulfate salts, higher alkyl aryl sulfonates, higher alkyl naphthalene sulfonates, higher alkyl phosphates and dialkyl sulfosuccinates.

The silver halide emulsion layer is generally coated with silver halide in terms of silver nitrate in the range of 0.5 to 5 g / m ² . The silver halide may be any of silver chloride, silver bromide, silver chlorobromide or a combination of these with silver iodide.

Silver halide emulsions can also be blue, green and red spectral sensitized. It can be a merocyanine, a cyanine dye or other sensitizing dye. Further, the silver halide emulsion can be chemically sensitized with various sensitizers. For example, sulfur sensitizers (eg hypo, thiourea, gelatin containing unstable sulfur, etc.), noble metal sensitizers (eg silver chloride, gold rhodanide, ammonium chloroplatinate,
Silver nitrate, silver chloride, palladium salt, rhodium salt, iridium salt, ruthenium salt, etc.), US Pat. No. 2,518,6
98, polyalkylene polyamine compounds described in
Imino-amino-methanesulfinic acid described in German Patent No. 1,020,864, reduction sensitizers (for example, first chloride
Etc. are advantageously used.

Various additives may be further incorporated in the constituent elements of the light-sensitive material of the present invention. For example, hardeners such as formalin, mucochloric acid, chromium alum, vinyl sulfone compounds, epoxy compounds, and ethyleneimine compounds, mercapto compounds, antifoggants or stabilizers such as tetraazaindene, saponin as a surfactant, alkylbenzene sulfone. Sodium acid, sulfosuccinate salts, anionic compounds such as alkylaryl sulfonates described in US Pat. No. 2,600,831, and amphoteric compounds such as described in US Pat. No. 3,133,816, and the like. Also, optical brighteners such as JP-B-34-7127, waxes, wetting agents such as glycerides of higher fatty acids or higher alcohol esters, N-
Guanylhydrazone compounds, quaternary onium compounds, 3
Primary amine compounds such as mondant, diacetyl cellulose, styrene-fluoro-alkylene sodium maleate copolymer, styrene-maleic anhydride copolymer and P
An antistatic agent such as an alkali salt of a reaction product with aminobenzenesulfonic acid, a film physical property improving agent such as various latexes, glycerin, a gelatin plasticizer such as JP-B-43-4939, a styrene-maleic acid copolymer, Japanese Patent Office Sho 36
A thickener such as No. 21574, an antioxidant pH adjusting agent, and the like can be used.

The treatment liquid used in the diffusion transfer method is an alkaline substance such as sodium hydroxide or potassium hydroxide.
Lithium hydroxide, sodium triphosphate, etc., silver halide solvents such as sodium thiosulfate, ammonium thiocyanate, cyclic imide compounds, thiosalicylic acid, etc., preservatives such as sodium sulfite, thickeners such as hydroxyethyl cellulose, carboxy. Methyl cellulose and the like, antifoggants such as potassium bromide, 1-phenyl-5-mercaptotetrazole and the like, development modifiers such as polyoxyalkylene compounds, onium compounds and developing agents such as hydroquinone and 1-phenyl-3-pyrazolidone. It may include alkanolamines and the like.

However, there is a drawback in that the developing agent in the highly alkaline processing liquid containing the developing agent is aged due to air oxidation, and therefore the developing agent is ineffective in the DTR material, that is, in the silver halide emulsion layer or It is known that the disadvantage can be largely avoided by the method of incorporating the hydrophilic colloid layer into the hydrophilic colloid layer having water-permeable relationship therewith.

In such a diffusion transfer material containing a developing agent, an alkaline active liquid containing no or substantially no developing agent is usually used. The DTR method using an alkali activating solution is disclosed in Japanese Examined Patent Publications No. 39-27568 and No. 47.
The specifications such as -30856 and 51-43778 can be referred to.

Next, the present invention will be specifically described based on examples, but the present invention is not limited to these.

[0031]

【Example】

Example 1 A coating solution containing the color toning agents of the present invention (5), (6), and (7) and the conventional toning agent separately in the antihalation layer shown below was prepared, and a coating solution containing no coloring agent was prepared.

<Antihalation Layer> Water 800 cc Gelatin 80 g Carbon black dispersion 25 g Hydroquinone 20 g 1-Phenyl-3-pyrazolidone 2 g Formalin (10% solution) 1.2 cc Color toning agent 0.02 g Water to 1 liter. Moisture is 50cc / m ²
And

The above five kinds of coating liquids for the antihalation layer were separately coated on a polyethylene terephthalate film support which had been subjected to an undercoating treatment, and an average particle size of 0.3 μm was applied thereon.
1. Converted from silver chlorobromide (5 mol% of silver bromide) to 1.
An ortho-sensitized gelatin silver halide emulsion containing 5 g / m ² was coated to prepare a light-sensitive material.

On the other hand, an image-receiving layer comprising a gelatin-coated paper support and a hydrophilic colloid having a dry weight of 3 g / m ² was provided on one side of the support with gelatin containing nickel sulfide nuclei and carboxymethyl cellulose (4: 1). It was created.

The above four kinds of light-sensitive materials are respectively plate-making cameras ARTGRAPHICA manufactured by Dainippon Screen Co., Ltd.
In 601II, the image was taken at the same size using an original composed of a photograph in which characters and halftones were separated. The light-sensitive materials that had been photographed were overlaid on the respective image-receiving materials, passed through an ordinary developing machine having a developer for silver complex salt diffusion transfer having the following composition, and both materials were peeled off for 15 seconds after leaving the squeezing roller.

<Developer for silver complex salt diffusion transfer> Water 800 ml Tribasic sodium dodecahydrate 75 g Anhydrous sodium sulfite 40 g Potassium bromide 0.5 g Anhydrous sodium thiosulfate 20 g 1-Phenyl-5-mercaptotetrazole 70 mg Hydroxyethyl cellulose 3 g Water To 1 liter.

The color tone of the image thus obtained was evaluated. The results are shown in Table 1.

[0038]

[Table 1]

[0039]

As is apparent from Table 1, by using the silver complex salt diffusion transfer light-sensitive material of the present invention, it was possible to obtain a silver image having a desired tone of cold black tone.

Claims (1)

[Claims] 1. A silver complex emulsion diffusion transfer light-sensitive material having at least a silver halide emulsion layer and an antihalation layer as layers constituting a light-sensitive element, wherein a compound represented by the following chemical formula 1 or 2 is contained in the light-sensitive element constituting layer. A silver salt diffusion transfer light-sensitive material comprising at least one of: [Chemical 1] (In the formula, R ₁ and R ₂ represent a methyl or ethyl group.)