JP2907627B2 - Processing solution for silver complex salt diffusion transfer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing solution for silver complex salt diffusion transfer.

[0002]

2. Description of the Related Art In general, a silver complex salt diffusion transfer method comprises a silver halide emulsion layer coated as a photosensitive layer on a support, an image receiving layer containing physical development nuclei coated separately on the support, and a processing solution for the same. Consists of The principle of the silver complex salt diffusion transfer method is that silver halide is developed in an exposed portion of a photosensitive layer imagewise exposed by a processing solution or a developing agent in a photosensitive material to produce chemically developed silver. At the same time, the unexposed silver halide reacts with the silver halide solvent in the processing solution to form a soluble silver complex salt, which diffuses into the image receiving material. Deposits form a silver image.

[0003] The silver complex salt diffusion transfer method based on this principle is widely used for copying documents, as well as underlay materials during plate making operations. Important quality of the image receiving material used in the silver complex salt diffusion transfer method is high silver image density (reflection and transmission density), good color tone (reflection and transmission) (generally, blue-black tone is desired), and high diffusion transfer speed. And that the image receiving layer has sufficient film strength.

Further, it is necessary that the good quality of the positive material does not largely depend on the processing conditions (eg, time, temperature, degree of deterioration of the processing solution).

Further, when the processing solution is continuously used for a long time (hereinafter referred to as a running process), colored sludge (hereinafter referred to as sludge) is generated in the processing solution, which not only contaminates the solution, but also causes the surface of the photosensitive material and the developing material to be developed. There is a disadvantage that the sludge adheres to the apparatus and becomes dirty, so that the liquid must be frequently changed or filtered.

The cause of the sludge is that the silver halide in the light-sensitive material reacts with the silver halide solvent in the processing solution to form a soluble silver complex salt, and a part thereof is reduced in the processing solution to become a silver colloid, which is colored. It is. Some of them easily flocculate and sink, or most of them float in the liquid as blackish brown mud.
In particular, a treatment solution for diffusion transfer containing amino alcohol has a remarkable disadvantage.

Hitherto, it has been known that 1-phenyl-5-mercaptotetrazole, 2-thiazolidine-4-carboxylic acid, and acetylene glycol compounds described in JP-B-55-95947 prevent the generation of this sludge. It is thought that these compounds form stable salts with the silver halide dissolved in the processing solution and suppress the reduction to silver colloid. However, if the amount of addition increases and the amount of added sludge is sufficient to prevent sludge, the developing speed is extremely slowed, and the effect of preventing sludge itself is small.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver salt diffusion transfer method containing amino alcohol which prevents sludge formation for a long period of time without impairing the diffusion transfer characteristics and has excellent running stability. The purpose is to provide a transfer treatment liquid.

[0009]

Means for Solving the Problems The present inventors have conducted various studies on these points, and as a result, the objective was achieved by incorporating the compound represented by the following chemical formula 2 into a silver salt diffusion transfer treatment solution containing amino alcohol. It has been found that this is achieved, leading to the present invention.

[0010]

Embedded image

In the formula, R is an alkyl group or an aryl group, which may be substituted.

Examples of the substituent of the alkyl group or the aryl group include a sulfonyl group, a carboxyl group, an alkyl group, an alkoxyl group, and a halogen. Particularly, those having a sulfonyl group or a carboxyl group as a substituent are preferable.

Next, specific examples of the compound represented by Chemical formula 2 used in the present invention will be given, but it should not be construed that the invention is limited thereto.

[0014]

Embedded image

[0015]

Embedded image

[0016]

Embedded image

[0017]

Embedded image

[0018]

Embedded image

[0019]

Embedded image

[0020]

Embedded image

[0021]

Embedded image

[0022]

Embedded image

[0023]

Embedded image

[0024]

Embedded image

[0025]

Embedded image

[0026]

Embedded image

[0027]

Embedded image

[0028]

Embedded image

[0029]

Embedded image

The addition amount of the anti-sludge agent according to the present invention is 1
Although it can be changed between 0.001 g and 1.0 g per liter, usually 0.01 g to 0.1 g is preferable, and a sufficient sludge prevention effect can be obtained.
It hardly affects other photographic characteristics.

The processing solution for silver complex salt diffusion transfer according to the present invention can contain the following components. That is, a developing agent for developing the silver halide in the exposed portion, for example, hydroquinone and its derivatives, 1-phenyl-3-pyrazolidone and its derivatives, and silver halide solvents such as sodium thiosulfate, ammonium thiosulfate, and sodium thiocyanate , Potassium thiocyanate, etc., sodium sulfite as a preservative, potassium bromide as a development inhibitor, 1
Additives such as -phenyl-5-mercaptotetrazole, basic substances such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium tertiary phosphate, thickeners,
For example, it can contain carboxymethylcellulose, hydroxyethylcellulose, and the like.

The alkanolamine used in the silver complex salt diffusion transfer treatment solution in the present invention includes, for example, ethanolamine, diethanolamine, triethanolamine, diisopropanolamine, N-methylethanolamine, N-aminoethylethanolamine, N-aminoethylethanolamine, and the like. , N-
Diethylethanolamine, N, N-dimethylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, 3-aminopropanol, 1-amino-propan-2-ol, 4-aminobutanol,
5-amino-pentan-1-ol, 3,3′-iminodipropanol, N-ethyl-2,2′-iminodiethanol, 2-amino-2- (hydroxymethyl) propane-1,3-diol, 2 -Amino-2-methylpropane-1, 3-diol and the like. One of these can be used alone, or a plurality of them can be used in combination. The use amount of the alkanolamine is preferably in the range of 0.25 to 2 mol per liter of the treatment liquid (use liquid). Examples of the combined use of alkanolamines are disclosed in JP-A-61-73950, JP-A-61-73951, and JP-A-61-73951.
1-73953 and the like.

A fluorescent whitening agent can be used in the image receiving material to improve its whiteness. If the amount of the fluorescent whitening agent is too small, the effect of improving the white color is not sufficient, and if it is too large, a bluish color is added at a portion where the image density is high, so-called blooming (egg color) occurs, and the apparent image density is reduced. Causes a decline. Although the luminous efficiency of fluorescence varies depending on the type of fluorescent whitening agent, the type and concentration of oil used for emulsification, the coexistence of various quenching substances, and the coexistence of other ultraviolet absorbing substances, it cannot be expressed uniformly. 3mg-300m
Most preferably, it is used in the range of g / m ² .

The ratio of the high boiling oil used in the oil dispersion of the optical brightener is 50 ° C. to the high boiling oil of the optical brightener.
It is preferable that the amount is larger than the saturated dissolution amount in the above and 2.5 times or less. 50 ° C
When the amount is less than or equal to the saturated dissolution amount in (1) or more than 4.0, disadvantages such as poor running performance, a decrease in transfer density, and a decrease in reproducibility of fine lines occur.

On the other hand, the amount of the binder in the image receiving material is preferably 0.6 to 3.0 g / m ² , more preferably 1.0 to 2.0 g / m ^{2 in} consideration of coatability and the like.

The physical development nuclei used in the image receiving layer of the image receiving material according to the present invention include silver, gold, platinum, palladium,
Precious metals such as copper, cadmium, lead, cobalt and nickel or sulfides thereof, selenium compounds and the like can be used.

Examples of the binder for the image receiving material include gelatin, phthalated gelatin, acylated gelatin, phenylcarbamylated gelatin, carboxymethylcellulose, hydroxyethylcellulose, sodium alginate, polyvinyl alcohol, partially saponified polyvinyl alcohol, and polyvinyl alcohol. Heat-processed products with maleic acid copolymer (eg, styrene-maleic anhydride, ethylene maleic anhydride, etc.), polyacrylamide, poly-N-vinylpyrrolidone, latexes (eg, polyacrylate, polymethacrylic acid) ester,
Water-soluble polymer compounds such as polystyrene and polybutadiene (homo- or copolymers) can be used alone or in combination.

The image receiving material can be hardened with an appropriate hardener. Specific examples of the hardener include formaldehyde, aldehyde compounds such as glutaraldehyde,
Polyvalent ketone compounds such as diacetylcyclopentanedione, bis (2-chloroethylurea), 2-hydroxy-
4,6-dichloro-1,3,5 triazine, a compound having a reactive halogen as described in U.S. Pat. No. 3,288,775, divinyl sulfone, U.S. Pat.
Compounds having a reactive olefin as described in US Pat. No. 5,718, N-methylol compounds as described in U.S. Pat. No. 2,732,316, isocyanates as described in U.S. Pat. No. 3,103,437, U.S. Pat. 3,017,280
Nos. 2,983,611, carbodiimide-based compounds described in U.S. Pat. No. 3,100,704, and U.S. Pat. No. 3,091,537.
Epoxy compounds, halogenocarboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane, chromium alum, potassium alum,
There are inorganic hardeners such as zirconium sulfate, and these can be used alone or in combination of two or more.

The image receiving material may be a surfactant (for example, a natural surfactant such as saponin, a nonionic surfactant such as an alkylene oxide, glycerin, or glycidol), a higher alkylamine, a quaternary ammonium salt, pyridine or the like. Heterocycles, cationic surfactants such as sulfoniums, anionic surfactants containing acidic groups such as carboxylic acids, sulfonic acids, phosphoric acids, sulfate groups, phosphate groups, amino acids, aminosulfonic acids, amino alcohols Amphoteric surfactants such as sulfuric acid or phosphate esters, fluorine-based anions and amphoteric surfactants, etc.), matting agents,
Discoloration inhibitors, color toning agents (for example, 1-phenyl-5-mercaptotetrazole as a typical one, other color toning agents described in Photographic Silver Halide Diffusion Process, page 61, issued by Focal Press), and developing agents (for example, , Hydroquinone and its derivatives, 1-phenyl-3-pyrazolidone and its derivatives, etc.), and silver halide solvents (for example, sodium thiosulfate, ammonium thiosulfate, sodium thiocyanate,
Potassium thiocyanate, etc.). Further, an over layer may be provided on the image receiving layer, a neutralizing layer may be provided below the image receiving layer, and a subbing layer for improving adhesion to the support may be provided.

The silver halide emulsion used in the photosensitive layer of the silver complex salt diffusion transfer light-sensitive material of the present invention is preferably an emulsion mainly composed of silver chloride, but is not limited thereto. The emulsion used in the above may be any emulsion capable of developing and diffusing the silver complex salt in the exposed part and the unexposed part at the speed required for the diffusion transfer method. Silver bromide, silver iodide, Examples thereof include silver chloride, silver chlorobromide, silver iodobromide, silver chloroiodide, silver chloroiodobromide and mixtures thereof.

The silver halide emulsion can be sensitized in various ways when it is made or when it is coated. It may be chemically sensitized by methods well known in the art, for example by sodium thiosulfate, alkyl thioureas, or by gold compounds such as rhodan gold, gold chloride, or a combination of both. Further, spectral sensitization which is usually performed can be performed.

As the binder for the photosensitive layer, there can be used a polymer substance generally used for the production of a silver halide emulsion, for example, the binder described in the image receiving layer. The photosensitive layer can be hardened with an appropriate hardener described in the image receiving layer. Further, the photosensitive layer may contain additives generally used in silver halide photosensitive materials, such as surfactants, antifoggants, matting agents, fluorescent dyes, and developing agents (eg, hydroquinone and its derivatives, such as 1-phenyl-3- Pyrazolidone and its derivatives). If necessary, auxiliary layers such as an undercoat layer, an intermediate layer, a protective layer and a release layer may be provided in addition to the photosensitive layer.

The support used in the present invention may be any material such as a polyolefin resin film such as polyethylene and polypropylene and a paper coated therewith, and preferably has a roughened surface. Good. Examples of the surface roughening method include a solvent processing method, a foaming method, and a compression molding method using a roughened surface, and any of the surface roughening methods may be used. Roughness is desirably about 2 to about 20 μm in depth, which is the distance from the concave portion of the surface unevenness to the top, and about 5 to about 100 μm, in the size which is the distance from mountain to mountain. Since the roughened resin surface is hydrophobic as it is, it is general to perform some kind of hydrophilic treatment such as corona discharge treatment and undercoating treatment.

[0044]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto.

Example

<Treatment liquid>

The treatment liquid for diffusion transfer had the following composition. Water 800 ml Sodium hydroxide 4 g Anhydrous sodium sulfite 50 g Hydroquinone 12 g 1-Phenyl-3-pyrazolidone 3 g Potassium bromide 1 g Sodium thiosulfate 20 g Methyldiethanolamine 30 g Methylethanolamine 20 g Add water to make 1000 ml. 6.0 mg of the compound shown in Table 1 is added to this treatment solution.

<Preparation of photosensitive material>

As the photosensitive material, an undercoat layer containing carbon black was provided on a polyethylene laminated paper for preventing halation, and an ortho-sensitized silver chlorobromide (silver bromide) having an average particle diameter of 0.3 μm was provided thereon. 5 mol%) in terms of silver nitrate, and gelatin containing 1.5 g / m ² , 0.2 g / m ² of 1-phenyl-3-pyrazolidone and 0.7 g / m ² of hydroquinone, and 4 g / m ² gelatin. It was prepared with a silver halide emulsion layer.

<Preparation of image receiving material>

Nickel nitrate, silver nitrate and sodium sulfide were each reacted in equimolar amounts to produce physical development nuclei composed of nickel sulfide and silver sulfide in a 1% aqueous gelatin solution. On one side of a 110 g / m ² paper support coated on both sides with polyethylene, a gelatin image-receiving layer containing the above nucleus is provided so as to have a hydrophilic colloid dry weight of 0.9 g / m ² , and an image-receiving material comprising only an image-receiving layer It was created. The oil-soluble fluorescent whitening agent emulsified dispersion was added to 1.9 g / m ² .

On the other hand, an aqueous gelatin solution containing 1-phenyl-5-mercaptotetrazole was applied to a dry weight of hydrophilic colloid of 1.2 g / m ² to form an uppermost layer.

The light-sensitive material and the image-receiving material were each hardened with a hardener so as not to hinder the diffusion transfer processing.

The photosensitive material produced as described above is imagewise exposed, and the emulsion surface of the photosensitive material and the image receiving surface of the image receiving material are overlapped. After passing through a processor and leaving the squeezing roller, 30 seconds later, both materials were peeled off. The image receiving material was washed with water for 30 seconds and dried. The above operation was continuously performed so that each of the photosensitive material and the image receiving material was 1 m ² . The reflection density of the black part was measured with a Macbeth RD519 reflection densitometer.

Further, the test solution tested was observed one day later.
Table 1 shows the results.

[0056]

[Table 1]

[0057]

According to the examples 2 and 3, which contain the anti-sludge agent of the present invention in the processing liquid, no sludge is generated and the reflection density of the black portion is sufficiently high.

Claims (1)

(57) [Claims] 1. A silver complex salt diffusion transfer treatment solution comprising a compound represented by the following formula 1 in a silver salt diffusion transfer treatment solution containing an amino alcohol. Embedded image In the formula, R is an alkyl group or an aryl group, which may be substituted.