JPH0690485B2 - Image forming method by silver salt diffusion transfer - Google Patents

Description

TECHNICAL FIELD The present invention relates to an image forming method by silver salt diffusion transfer and a film unit used therefor.

(Prior Art) An image forming method by diffusion transfer using a silver salt such as silver halide is well known. The various methods will be described in detail. For example, a photosensitive silver halide emulsion layer that has been imagewise exposed is provided with a developer, a silver halide solvent and a film forming agent (thickener).
Treated with an alkaline aqueous solution containing, to reduce the exposed silver halide grains to silver with a developer, while the unexposed silver halide grains are converted to a transferable silver complex salt with a silver halide solvent. It consists of a silver precipitating agent-containing layer (image receiving layer) superposed on the emulsion layer, diffused and transferred by an invisibility, where a silver complex salt is reduced with a developer with the aid of a silver precipitating agent to obtain a silver image. .

In carrying out this method, for example, a light-sensitive element having a light-sensitive silver halide emulsion layer usually provided on a support, an image-receiving element and a developer having an image-receiving layer containing a silver precipitating agent on a support, a halogenated compound are used. A film unit is used which is a combination of processing elements consisting of a destructible container containing an aqueous alkali solution containing a silver solvent and a film forming agent. First, the emulsion layer of the light-sensitive element is imagewise exposed, and then the light-sensitive element and the image-receiving element are superposed so that the emulsion layer and the image-receiving layer of the image-receiving element face each other, while the processing element is destroyed to develop a viscous alkaline aqueous solution. As described above, a print having a desired image formed on the image-receiving layer can be obtained by allowing the image-receiving element to pass through a pair of rollers, leaving it for a predetermined time, and then peeling off the image-receiving element.

(Problems to be Solved by the Invention) One of the difficulties of this method is to make the color tone of the obtained image a pure black tone. Although there are many toning agents that lower the maximum density, there are few toning agents that make the color tone pure black without lowering it.

(Object of the Invention) An object of the present invention is to provide a novel image forming method by silver salt diffusion transfer.

Another object of the present invention is to provide a method for increasing the sensitivity without lowering the maximum density and obtaining a pure black image.

(Means for Solving the Problems) The above-mentioned object is to develop a photosensitive element containing an image-exposed photosensitive silver halide emulsion layer with an alkali processing composition in the presence of a silver halide solvent. Silver containing at least a part of unexposed silver halide in the emulsion layer as a transferable silver complex salt and transferring at least a part of the complex salt to a silver precipitating agent-containing image receiving layer to form an image on the image receiving layer. The image forming method by salt diffusion transfer can be achieved by at least one of the processing composition and the photosensitive element containing a compound represented by the following general formula (I).

In the formula, R ₀ may be the same or different and may be a hydrogen atom, a halogen atom (eg F, Cl, Br), an alkyl group, preferably an alkyl group having 1 to 14 carbon atoms (eg a methyl group, an ethyl group), a substituent Alkyl group, preferably substituted alkyl group having 1 to 14 carbon atoms in the alkyl portion, substituted or unsubstituted cycloalkyl group, preferably having 3 to 14 carbon atoms, alkoxy group, preferably having 1 to 14 carbon atoms, substituted alkoxy group Preferably, it has 1 to 14 carbon atoms (eg, methoxy group, ethoxy group), substituted or unsubstituted alkylsulfonyl group, preferably 1 to 14 carbon atoms, substituted or unsubstituted arylsulfonyl group, preferably 6 carbon atoms. 14, sulfamoyl groups (wherein the nitrogen atom of the sulfamoyl group is an alkyl group having 14 or less carbon atoms, a substituted alkyl group, a cycloalkyl group, a substituted cycloalkyl group). Group, aryl group, substituted aryl group, 5- to 7-membered nitrogen atom, oxygen atom, optionally substituted with a substituted or unsubstituted heterocyclic group containing at least one kind of sulfur atom, the nitrogen atom The above two substituents may be linked to each other to form a ring), an alkyl or aryl sulfonamide group (provided that the alkyl portion or the aryl portion may have a substituent. The nitrogen atom of the sulfonamide group) The atom is an alkyl group having 14 or less carbon atoms,
Substituted or unsubstituted heterocyclic group containing at least one of a substituted alkyl group, a cycloalkyl group, a substituted cycloalkyl group, an aryl group, a substituted aryl group, a 5- to 7-membered nitrogen atom, oxygen atom, and sulfur atom. May be replaced with. ), A carbamoyl group (wherein the nitrogen atom of the carbamoyl group is an alkyl group having 14 or less carbon atoms, a substituted alkyl group,
Cycloalkyl group, substituted cycloalkyl group, aryl group, substituted aryl group, 5- to 7-membered nitrogen atom, oxygen atom,
It may be substituted with a substituted or unsubstituted heterocyclic group containing at least one sulfur atom, and two positions on the nitrogen atom may be linked to each other to form a ring. ), A carboxamide group (wherein the carbon atom of the carbonamide group is an alkyl group having 14 or less carbon atoms, a substituted alkyl group, a cycloalkyl group, a substituted cycloalkyl group, an aryl group, a substituted aryl group, a 5- to 7-membered nitrogen atom, It may be substituted with a substituted or unsubstituted heterocyclic group containing at least one of oxygen atom and sulfur atom).
Heterocyclic group, preferably a substituted or unsubstituted heterocyclic group containing at least one of a 5- to 7-membered nitrogen atom, oxygen atom and sulfur atom, and a substituted or unsubstituted aryl group, preferably 14 or less carbon atoms , Acyl group, preferably carbon number
14 or less, substituted or unsubstituted alkoxycarbonyl group, preferably having 2 to 14 carbon atoms, substituted or unsubstituted acyloxy group, preferably having 2 to 14 carbon atoms, substituted or unsubstituted alkylthio group, preferably carbon A C 1-14 substituted or unsubstituted arylthio group, preferably a C 6-14 primary amino group or a salt thereof, a C 1-14 alkyl group or a C 6-14 aryl group. The substituted secondary or tertiary amino group or a salt thereof, provided that the alkyl group or the aryl group may have a substituent. Represents a nitro group, a hydroxy group, a carboxyl group, a sulfonic acid group, or a cyano group, R ₁ R ₂ is each a hydrogen atom, an alkyl group, preferably having 1 to 14 carbon atoms (eg, methyl group, ethyl group), substituted alkyl The group preferably represents an alkyl group having 1 to 14 carbon atoms (eg, methoxyethyl group, ethoxyethyl group, chloroethyl group, benzyl group) and aryl group (eg, phenyl group, naphthyl group).

m represents an integer of 1 to 4.

The compound represented by the general formula (I) may be represented by the following structural formula as a keto-enol tautomer.

The amount of the compound represented by the general formula (I) used in the present invention is preferably 5 × 10 ⁻⁶ to 1 × 10 ⁻² mol per 1 kg of the treating composition, and 1 × 10 ^{−5 to} 5 × 10 ^−3. mol is preferable, and
2 × 10 ^{−5 to} 5 × 10 ⁻⁴ are particularly preferable.

In the light-sensitive material element, 1 × 10 ⁻⁸ to 1 × 10 ⁻⁴ mol / m ² ) is preferable, and 1 × 10 ⁻⁷ to 1 × 10 ⁻⁵ mol / m ² ) is particularly preferable.

The compounds effective in the general formula (I) are exemplified below, but the present invention is not limited to these compounds.

Hereinafter, the present invention will be described in more detail.

In the image forming method and film unit of the present invention, the developer may be present in the light-sensitive element or the processing composition element. Preferably a developer is included in the processing composition. The developer is, for example, hydroquinone, tert-butylhydroquinone,
A benzene- or naphthalene-based organic compound having a hydroxy group at the para or ortho position is used.

Further, reductic acid as described in US Pat. No. 3,615,440 and α, β-ene diol as described in US Pat. No. 3,730,716 are preferably used. Further, hydroxylamine developers as described in US Pat. Nos. 3,287,125 and 3,293,034 are particularly preferably used.

The amount of the developer used is preferably 0.1 to 40 g, and most preferably 1 to 20 g per 100 g of the processing composition.

As the developer, a 1-aryl-3-pyrazolidinone compound or an alkyl-substituted p-aminophenol described in JP-B-49-13580 may be used in combination with the developer.

The silver halide solvent may be present in the processing element, the light sensitive element and / or the image receiving element. Among them, the processing element is the most preferable. U.S. Patents 2,857,274, 2,857,275 and 2,85
The cyclic compounds described in No. 7,276 are suitable, and among them, uracil, urasol, 6-methyluracil and the like are preferable examples.

Further, alkali metal thiosulfates, particularly sodium or potassium salts, are preferred, and U.S. Pat. Nos. 3,958,992 and 3,9
76,647, 4,009,167, 4,032,538, 4,046,56
No. 8, No. 4,047,954, No. 4,047,955, No. 4,107,176 and the disulfonylmethane compound of JP-A No. 47-330 and U.S. Pat. Compounds, etc. and U.S. Patent Nos. 4,251,617 and 4,2
67,254 and 4,267,256 aminothioethers can be selected. These can be used alone or in combination, and when two or more cyclic imide compounds or dihydroxypyrimidine compounds having a thioether group are used in combination, white crystals are deposited on the surface even if the prints are stored for a long time. There is an advantage that there is no.

Addition amount of silver halide solvent is 100g of alkaline processing composition
It is preferable to add 0.1 to 30 g, and most preferably 0.5 to 10 g.

When this is applied by distributing the processing liquid used in this invention as a thin layer between the overlaid photosensitive element and image receiving element, the processing liquid contains a polymeric film former, thickener or thickener. Is preferred. Hydroxyethyl cellulose and sodium carboxymethyl cellulose are particularly useful for this purpose and are included in the processing liquid in concentrations effective to provide suitable viscosities by known principles of diffusion transfer photography. The processing liquid may further contain other auxiliaries known in the silver salt diffusion transfer method, for example, antifoggants, toning agents, stabilizers and the like. In particular, an oxyethylamino compound,
For example, the inclusion of triethanolamine is useful for increasing the shelf life of processing solutions as described in US Pat. No. 3,619,185.

The processing liquid as described above is preferably contained in a destructible container to form a processing element. As for the destructible container and its material, any known material can be used, for example, U.S. Pat.No. 3,056,491,
3,056,492, 3,173,580, 3,750,907, 3,8
33,381, 4,303,750, 4,303,751 and the like.

The image receiving element in the present invention is coated on a support carrying an image receiving layer containing a silver precipitating agent, such as baryta paper, cellulose triacetate or polyesters. Such image-receiving elements are preferably prepared by coating a subbed support with a coating solution of a suitable cellulose ester, such as cellulose diacetate, in which a silver precipitating agent is dispersed. The obtained layer of cellulose ester is alkali-hydrolyzed to convert at least part of the depth of the cellulose ester into cellulose. In a particularly useful embodiment, the silver hydrolyzate layer and / or the underlying non-hydrolyzed lower layer cellulose ester, eg, the non-hydrolyzed portion of the cellulose ester layer containing cellulose diacetate, is silver. It contains one or more mercapto compounds suitable for improving the color tone, stability or other photographic properties of the transferred image. Such a mercapto compound is used by being diffused from the position where it is initially placed in the invisibility. This type of image receiving element is described in U.S. Pat. No. 3,607,269.

Specific examples of silver precipitants include heavy metals such as iron, lead, zinc, nickel, cadmium, tin, chromium, copper, cobalt, especially noble metals such as gold, silver, platinum and palladium. Other useful silver precipitants are the sulfides and selenides of precious metals, especially the sulfides of mercury, copper, aluminum, zinc, cadmium, cobalt, nickel, silver, lead, antimony, bismuth, cerium, magnesium, gold, platinum and palladium. And selenides of lead, zinc, antimony and nickel.

In particular, gold, platinum and palladium are preferably sulfides thereof.

Further, the image-receiving sheet preferably has an image stabilizing layer for improving the image storability, and a cationic polyelectrolyte is preferable as the stabilizer, and particularly JP-A-59-1669.
40, U.S. Patent 395899, JP-A-55-142339, JP-A-54-12602
7, the same 54-155835, the same 53-30328, the same 54-92274 water dispersion latex and U.S. Pat.
61, 3756814, the polyvinylpyridinium salt, the water-soluble quaternary ammonium salt polymer described in US Pat. No. 3,709,690, and the water-insoluble quaternary ammonium salt polymer described in US Pat.

Further, as the binder of the image stabilizing layer, cellulose acetate is preferable, and cellulose acetate having an acetylation degree of 40 to 49% is particularly preferable.

Further, it is preferable to provide an intermediate layer between the image receiving layer and the layer containing a toning agent or a stabilizer. Preferable examples of the intermediate layer include gum arabic, polyvinyl alcohol, polyacrylamide and the like.

A peeling layer is preferably provided on the surface of the image receiving layer in order to prevent the processing liquid from adhering to the surface of the image receiving layer during peeling after the development of the processing liquid. Preferable examples of such a release layer include gum arabic, hydroxyethyl cellulose, methyl cellulose, polyvinyl alcohol, polyacrylamide, sodium alginate, and US Pat.
Mention may be made of those described in 2,024, 3,820,999 and British Patent 1,360,653.

Further, it is preferable to provide an acidic polymer layer for neutralization between the image receiving layer and the support. Preferred acidic polymers include acrylic acid, maleic acid, methacrylic acid, itaconic acid, copolymers of unsaturated carboxylic acids such as crotonic acid,
Acidic cellulose derivatives and the like are included. Specific examples include butyl acrylate / acrylic acid copolymer, cellulose acetate hydrogen phthalate, ethyl methacrylate / methacrylic acid copolymer, and methyl methacrylate / methacrylic acid copolymer. In addition to these, polymers containing sulfonic acid groups such as polystyrene sulfonic acid and acetalized products of benzaldehyde sulfonic acid and polyvinyl alcohol are also useful.

In a particular embodiment of the present invention an image receiving layer may be incorporated in the light sensitive element described below. For example, on a polyethylene terephthalate sheet, an image receiving layer containing a silver precipitating agent in order, a light reflecting layer containing a white pigment such as titanium dioxide, a light shielding layer containing a light absorbing substance such as carbon black, and a photosensitive silver halide. The one provided with an emulsion layer is a preferred example. In such an embodiment, even if the photosensitive silver halide emulsion layer is not peeled off after the diffusion transfer process,
Since the back layer is shielded by the light reflecting layer, the image formed on the image receiving layer can be observed through the polyethylene terephthalate sheet.

Further, in the present invention, a light-sensitive element obtained by coating a light-sensitive silver halide emulsion on a support is preferably used.

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as the silver halide in the photosensitive silver halide emulsion used in the present invention. A preferred silver halide is silver iodobromide or silver iodochlorobromide containing 10 mol% or less of silver iodide. Particularly preferred is silver iodobromide containing 3 to 10 mol% silver iodide.

The average grain size of the silver halide grains in the photosensitive emulsion (the grain diameter in the case of spherical or spherical grains, the ridge length in the case of cubic grains, and the average based on the projected area) is not particularly limited. However, it is preferably 3 μm or less, more preferably 1.5 μm or less, and particularly preferably 0.8 to 1.
It is 2μ.

The particle size distribution may be narrow or wide.

The silver halide grains in the photosensitive emulsion may have an equiaxed crystal form such as a cube or an octahedron, or a heteromorphic crystal form such as a sphere or a plate, or a crystal thereof. It may have a complex shape. It may consist of a mixture of particles of different crystal forms.

The silver halide grains may be composed of different phases in the inside and the surface layer, or may be composed of a uniform phase. Further, it may be a particle in which a latent image is mainly formed on the surface or a particle in which a latent image is mainly formed inside the particle. Grains in which the latent image is mainly formed on the surface are preferred.

The thickness of the photosensitive emulsion layer is 0.5 to 8.0 µ, particularly 0.6 to 6.0 µ, and the coating amount of silver halide grains is 0.1 to 3 g / m ² , preferably 0.2 to 1.5 g / m ² .

The light-sensitive emulsion is prepared by a method usually used as a silver halide photographic emulsion, and chemical sensitization and spectral sensitization are carried out as necessary, and the emulsion is provided with an antifoggant, a stabilizer, a hardener, a coating aid, An antistatic agent or the like may be included. A vehicle such as gelatin is used for the emulsion.

The exposure for obtaining a photographic image may be performed using a usual method. That is, natural light (sunlight), tungsten light,
Any of various known light sources such as a fluorescent lamp, a mercury lamp, a xenon arc lamp, a carbon arc lamp, a xenon flash lamp, and a cathode ray tube flying spot can be used. The exposure time is not limited to 1/1000 second to 1 second which is usually used in cameras, but is shorter than 1/1000 second, for example, 1/10 ⁴ to 1/10 ⁶ second exposure using a xenon flash lamp or cathode ray tube. Or an exposure longer than 1 second can be used. If necessary, the spectral composition of the light used for exposure can be adjusted with a color filter. Laser light can also be used for the exposure. Also, electron beam, X-ray, γ
It may be exposed by light emitted from the phosphor excited by rays, α rays, or the like.

For the arrangement and combination of the respective elements for combining the light-sensitive element, the image-receiving element and the processing element as described above to form a film unit, for example, Neblettes, HANDBOOK OF PHOTOGRAPHY (HAND BOOK OF PHOTOGRAPHY)
AND REPROGRAPHY), 7th edition, pp. 282-285, and particularly preferred embodiments are described in detail in US Pat. No. 3,350,991, which can be referred to.

The present invention can be applied not only to the type in which the image receiving element and the photosensitive element are peeled off after developing the processing composition, but also to the type in which the film unit is integrally molded.

(Effect of the Invention) According to the present invention, when the compound represented by the general formula (I) is contained in at least one of the processing composition and the photosensitive element,
High sensitivity can be achieved without lowering the maximum density, a tone of pure black tone can be obtained, and secondarily, the gradation of the image can be hardened.

(Examples) Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Example 1 Photosensitive sheet Silver halide grains were formed by a single jet method, physically ripened by a usual method, desalted, and chemically ripened to obtain a silver iodobromide emulsion (iodide-containing 5.5 mol%). It was
The average diameter of the silver halide grains contained in this emulsion is 0.9.
It was micron. 1 kg of this emulsion contained 0.65 mol of silver halide. 1 kg of this emulsion was sampled in pots and dissolved in a constant temperature bath at 50 ° C.

Ortho sensitizing dye 3- {5-chloro-2- [2
-Ethyl-3- (3-ethyl-2-benzothiazolinylidene) propenyl] -3-benzoxazolio} propane-sulfonate, panchromatic sensitizing dye (4- [2-
[(3-Ethylbenzothiazoline- (2-ylidene)-
2-methyl-1-propenyl] -3-benzothiazolio} butane-sulfonate) and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene in 1% by weight aqueous solution 10
ml, 10 ml of a 1% by weight aqueous solution of 2-hydroxy-4,6-dichlorotriazine sodium salt, 10 ml of a 1% by weight aqueous solution of sodium dodecylbenzenesulfonate, and 0.1% of lipoic acid.
10% by weight of a methanol solution was added and mixed and stirred at 40 ° C. This complete emulsion was coated on a polyethylene terephthalate film base containing titanium dioxide as an undercoating agent so that the dry film thickness was 3 μm, and dried to obtain a sample. At the same time, a latex of polymethylmethacrylate (average size 3.5 μ) was added to the gelatin aqueous solution and applied so that the dry film thickness was 1 micron. The amount of silver applied is
It was 0.5 g / m ² .

Image-receiving sheet A solution of 18 g of cellulose acetate (54% acetylation) and 12 g of styrene-maleic anhydride copolymer dissolved in 270 ml of acetone and 30 ml of methanol was coated on polyethylene laminated paper at a thickness of 54 ml / m ² and dried. did. On top of this, mix the following compounds into cellulose acetate with a degree of acetylation of 46% and add 2g each.
The coating / drying was performed so as to be / m ² and 4 g / m ² .

x: y: z = 5: 47.5: 47.5 On top of this, 3,6-diphenyl-1,4-dimercapto-3
1 of H, 6H-2,3a, 5,6a-tetrazapentalene (0.05g / m ² )
Dry film thickness of 0% cellulose acetate acetone solution 10g
It was applied so as to be / m ² . Further, a 5% aqueous solution of polyacrylamide was mixed with an aqueous solution of dimethylolurea (5%) and acetic acid (50%) at concentrations of 5% and 1.25%, respectively, and coated at a coating thickness of 25 ml / m ² . On top of this, 3%
Acetone / methanol of cellulose acetate (9/1)
A solution in which the following silver precipitating agent was finely dispersed was applied to the solution.
1-phenyl-5-mercaptoimidazole was added to this coating solution so that the coating amount was 1.25 × 10 ^-6 mol / m ² . The dry film thickness was 0.8 μm. The following alkaline liquid was applied to this coated material at a rate of 18 ml / m ² , washed with water and dried to prepare an image receiving sheet.

Alkali liquid Potassium hydroxide (Purity 86%) 44.3g Water 200ml Methanol 800ml Treatment liquid Potassium hydroxide (85%) 260g Titanium dioxide 3g Uracil 45g 6-Methyluracil 45g Hydroxyethylcellulose 70g Zinc oxide 10g N, N-bismethoxyethylhydroxyl Amine 50g Triethanolamine 7g Tetrahydropyrimidinethione 0.4g Sodium 5-mercaptotetrazoylbenzenesulfonate 0.1g 2,4-Dimercaptopyrimidine 0.35g To this treatment solution was added the following compound 3 × 10 ^-4 mol and further water. After adding the above treatment solution to the total amount of 2 kg between the photosensitive sheet and the image receiving sheet, it was peeled after 30 seconds (25 ° C.). Table 1 shows the maximum and relative densities (D = 0.6) of the color tones at that time. The minimum concentration showed a value of 0.10. In the table, the gray scale is the value of γ in the horizontal portion of the characteristic curve, and is shown as a relative value when Comparative-1 is 100.

Example 2 The following compound (5 × 10 ⁻⁷ mol / m ²⁾ was added to the silver iodobromide emulsion layer of the photosensitive sheet shown in Example 1 to prepare a photosensitive sheet, and the processing solution was a formulation not containing this compound. The one prepared in 1. was used. Then, the same expansion processing as that of the first embodiment is carried out, and the result is shown in Table-2.

In addition, "-" in the table means that the maximum concentration is too low to make a comparison.

Claims (1)

[Claims] 1. A light-sensitive element containing an image-exposed light-sensitive silver halide emulsion layer is developed with an alkali processing composition in the presence of a silver halide solvent to produce an unexposed silver halide layer in the emulsion layer. At least a part of which is a transferable silver complex salt, and at least a part of the complex salt is transferred to a silver precipitating agent-containing image receiving layer to form an image on the image receiving layer. An image forming method by silver salt diffusion transfer, characterized in that at least one of the processing composition and the photosensitive element contains a compound represented by the following formula (I). In the formula, R ₀ may be the same or different, a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, a substituted or unsubstituted cycloalkyl group, an alkoxy group, a substituted alkoxy group, a substituted or unsubstituted alkylsulfonyl group, A substituted or unsubstituted arylsulfonyl group, a sulfamoyl group, an alkyl or aryl sulfonamide group, a carbamoyl group, a carbonamido group, a heterocyclic group, a substituted or unsubstituted aryl group, an acyl group, a substituted or unsubstituted alkoxycarbonyl group, A substituted or unsubstituted acyloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a primary amino group or a salt thereof, a secondary or tertiary amino group substituted with an alkyl group or an aryl group, or a salt thereof Salt, nitro group, hydroxy group, carboxyl group, sulfone It represents a group or a cyano group. R ₁ and R ₂ each represent a hydrogen atom, an alkyl group, a substituted alkyl group or an aryl group. m represents an integer of 1 to 4.