JPS6120035A - Image formation method for silver salt diffusion transferring - Google Patents

Abstract

PURPOSE:To obtain a superior silver image high in the max. density and to shorten image formation time by processing in the presence of a compd. represented by the formula shown here. CONSTITUTION:A photosensitive element including a silver halide photographic sensitive emulsion layer, and an image receiving element including a image receiving layer containing a silver precipitating agent are processed in the presence of a hydroxylamine silver halide developer and a silver halide solvent and in addition to both, a compd. represented by the formula in this image formation method for silver salt diffusion transfer. In the formula R1 is a 11-18C aliphatic hydrocarbon group having a one double bond, R2 is a 1-4C aliphatic hydrocarbon group, and cation M is H, an alkali metal or an org. amine cation. This compd. is contained in an amt. of 4X10<-4>-4X10<-1>mol per mol of silver halide.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for forming an image for silver salt diffusion transfer and a photosensitive element for silver salt diffusion transfer.

[Prior art]

Methods of forming images by diffusion transfer are well known. To specifically illustrate this method, an imagewise exposed silver halide photographic emulsion layer is treated with an alkaline aqueous solution containing a developing agent and a silver halide solvent, and the exposed silver halide grains are reduced to silver by the developing agent. On the other hand, the unexposed silver halide grains are converted into a transferable silver complex salt using a silver halide solvent, and the complex salt is diffused by imbibition into a silver precipitant-containing layer (image-receiving layer) overlaid with the emulsion layer. It consists of transferring and then reducing the silver complex salt with a developing agent with the help of a silver precipitant to obtain a silver image. When carrying out this method, usually a photosensitive material having a photosensitive silver halide emulsion layer on a support, an image receiving material having an image receiving layer containing a silver precipitant on a support, a developing agent, silver halide, etc. A film unit is used which combines a processing element consisting of a breakable container containing a viscous aqueous alkaline solution containing a solvent and a thickener. First, the emulsion layer of the light-sensitive material is exposed imagewise, and then the light-sensitive material and the image-receiving material are overlapped so that the car pattern emulsion layer and the image-receiving layer of the image-receiving material face each other, while the processing element is destroyed and a viscous alkaline aqueous solution is exposed. The image-receiving material is passed between a pair of rollers so as to be developed, and after being left for a predetermined period of time, the image-receiving material is peeled off from the photosensitive material, thereby obtaining a print in which a desired image is formed on the image-receiving layer.

Regarding the silver salt diffusion transfer method image receiving element, please refer to Tokuko Sho≠Tei-51.
No. 7j'7 discloses that an alkali-impermeable polymer material is impregnated with a silver precipitant material by vacuum evaporation, then dissolved in the solvent of the polymer material, coated on a support, and dried. Thereafter, an image-receiving material prepared by chemically treating the surface layer of the single polymer layer, such as hydrolysis, to make it permeable to alkali is described. Furthermore, Japanese Patent Publication No. Shoji-Miri≠l1 describes a method of embedding a silver precipitant during or after oxidizing cellulose ester F. According to this method, an image-receiving layer with high mechanical strength can be obtained. Further, US Pat. No. 3,471, No. 1 describes a method of forming an image-receiving layer by oxidizing a cellulose ester layer containing a silver precipitant in advance.

Silver halide developers with hydroxylamine as the developing agent used to develop silver halide grains produce silver transfer images that require little or no post-processing, especially when used in combination with a pan-receiving layer of regenerated cellulose. It has been found to be particularly useful. Particularly useful hydroxylamine silver halide developers are N-alkyl and N-furfoxylalkyl substituted hydroxyl anions. Many such hydroxylamines are
US Patent λ11727≠ No. 2t! 7 7! No., same λ
117λ7, 3217/λ1, 3217/coj, 3.22303≠, 33t22t/, and 37μ0/. Particularly effective and preferred hydroxylamine silver halide developer (%) (wherein R represents alkyl, alkoxyalkyl or alkoxyalkoxyalkyl, R2A is hydrogen,
alkyl, alkoxyalkyl, alkoxyalkoxyalkyl or alkenyl). Preferably the alkyl, alkoxy and alkenyl groups contain 1 to 3 carbons. As a particularly useful hydroxylamine silver halide developer, N・N-
Diethyl-hydroxylamine, N-N-bis-methoxyethyl-hydroxylamine and N-N-bis-
Ethoxyethyl-hydroxylamine can be mentioned.

Further, the above developer can be used in combination with the auxiliary developer such as a phenidone compound, a p-aminophenol compound, and ascorbic acid.

A diffusion transfer system using an image-receiving layer made of regenerated cellulose is disclosed in US Pat. No. J, 47/, -≠! As described in No. 1, the disadvantage is that the image forming time is longer than that of a system using an image-receiving layer made of colloidal silica.

On the other hand, depending on the type of photosensitive material for silver salt diffusion transfer, and especially on the additives contained in the photosensitive material, the maximum density of the silver image formed on the image-receiving layer may be low, a phenomenon that is not desirable for photographic images. occurs. For example, some surfactants reduce the maximum concentration, and some reduce the maximum concentration but also reduce sensitivity. Therefore, there is a need for a technique that does not reduce sensitivity or maximum density, and can shorten image forming time.

Surfactants are used for a variety of purposes in the field of photography, but here they are useful as coating aids, particularly in multilayer simultaneous coating, and to shorten the image formation time of silver salt diffusion transfer. Surfactant compounds that further increase maximum concentration are desired.

(Object of the Invention) An object of the present invention is to provide an image forming method for silver salt diffusion transfer, which can provide an excellent silver image with a high maximum density and which requires a short image forming time.

Another object of the present invention is to provide a photosensitive material capable of imparting a high maximum density and a low minimum density to an image-receiving layer by carrying out a silver salt diffusion transfer process.

Another object of the present invention is to provide a processing composition for complex salt diffusion transfer that provides excellent silver images.

The objects of the present invention are not limited to those described above, but will become clear from the description that follows.

The above objectives are achieved by the following image forming method.

A silver salt diffusion transfer image forming method in which a photosensitive element including a halogenated emulsion layer is treated with a processing composition, characterized in that the treatment is carried out in the presence of a compound represented by the following general formula (1). Image forming method for diffusion transfer.

RC0NCH2CH2803M L2 In the formula, R1ti represents an aliphatic carbon arsenic group, R2 represents a hydrogen atom or an aliphatic hydrocarbon group, and M represents a cation.

Furthermore, the above-mentioned object is achieved by a photosensitive element for silver salt diffusion transfer containing a silver halide photographic emulsion layer, which is characterized by containing a compound represented by general formula (1). Ru.

Furthermore, the above object is achieved by a processing composition containing a compound represented by general formula (1) for processing a light-sensitive element for silver salt diffusion transfer containing a silver halide photographic emulsion layer.

Preferred embodiments of the present invention are listed below.

Silver salt diffusion in which a light-sensitive element containing a silver halide photographic emulsion layer, an image-receiving element containing an image-receiving layer containing a silver precipitant, is treated with an alkaline processing composition in the presence of a hydroxylamine silver halide developer and a silver halide solvent. 1. A method for forming images for silver salt diffusion transfer, characterized in that processing is carried out in the presence of a compound represented by general formula (I).

Silver salt diffusion in which a light-sensitive element containing a silver halide photographic emulsion layer, an image-receiving element containing an image-receiving layer containing a silver precipitant, is treated with an alkaline processing composition in the presence of a hydroxylamine silver halide developer and a silver halide solvent. An image forming method for silver salt diffusion transfer, wherein the photosensitive material contains a compound represented by general formula (I).

Silver salt diffusion in which a light-sensitive element containing a silver halide photographic emulsion layer, an image-receiving element containing an image-receiving layer containing a silver precipitant, is treated with an alkaline processing composition in the presence of a hydroxylamine silver halide developer and a silver halide solvent. An image forming method for silver salt diffusion transfer, wherein the processing composition contains a compound represented by general formula (1).

A light-sensitive material containing a silver halide photographic emulsion layer and a protective layer on a support, and an image-receiving material containing an image-receiving layer containing a silver precipitant on another support, all containing a hydroxylamine silver halide developer and a silver halide solvent. In the image forming method for silver salt diffusion transfer, which is processed with an alkaline processing composition containing general formula (1)
An image forming method for silver salt diffusion transfer, characterized by processing in the presence of a compound represented by:

A photosensitive material containing a silver halide photographic emulsion layer and a protective layer on a support, and an image receiving material containing an image receiving layer containing a silver precipitant on another support are prepared using a hydroxylamine silver halide developer and a silver halide solvent. Including ah? - An image forming method for silver salt diffusion transfer in which the photosensitive material contains a compound represented by the general formula (1), in which the image forming method is processed with a caustic processing composition.

A photosensitive material containing a silver halide photographic emulsion layer and a protective layer on a support, and an image receiving material containing an image receiving layer containing a silver precipitant on another support are prepared using a hydroxylamine silver halide developer and a silver halide solvent. An image forming method for silver salt diffusion transfer which is processed with an alkaline processing composition comprising the steps of: adding a compound represented by general formula (1) to the depositing layer;

In a light-sensitive element for silver salt diffusion transfer containing a silver halide photographic emulsion layer, a preferred embodiment of a light-sensitive element for silver salt diffusion transfer characterized by containing a compound represented by general formula (1) will be mentioned.

A light-sensitive material for silver salt diffusion transfer comprising a silver halide photographic emulsion layer and a protective layer on a support, the light-sensitive material for silver salt diffusion transfer comprising a compound represented by general formula (I).

In a light-sensitive material for silver salt diffusion transfer comprising a halogenated scissors photographic emulsion layer and a protective layer on a support, the protective layer has the general formula (1).
A photosensitive material for silver salt diffusion transfer, characterized in that it contains a compound represented by:

The aliphatic hydrocarbon group represented by 几 in the general formula CI) preferably has 1 liter of carbon atoms.

More preferably, it is an aliphatic hydrocarbon group having a carbon number of 1/-/J' and one double bond.

Examples of R1 include undecyl, dodecyl, pentadecyl.
tadecy + ), hezotadecyl (heptad
ecyl).

The aliphatic hydrocarbon group represented by R2 is preferably one in which the number of carbon atoms is no≠. Examples of R20 include methyl, ethyl, furovir, methyl, cyclohexyl.

Suitable examples of cations represented by M include hydrogen, sodium, potassium, lithium, ammonium, or organic amine cations such as triethylamine, triethanolamine, morpholine, piperidine.

The compound represented by the general formula (1) is a British patent/101r2
No. 73, U.S. Patent J, 302, +73, 3. O
jj, tt No. 2 and tt No. 2,739. It is a compound known as rY1, etc., and its synthesis method is described in U.S. Patent No. 73,
It is described in tri No. 1.

The compound represented by the general formula (1) is contained in an amount of $X10' to 4tX10'' mopy, preferably Fio, ooi3 to 0.13 mole per 7 moles of silver rhodanide.

Next, examples of compounds used in the present invention are shown.

x C03(CH2)7CH=CH(CH2)7CO
NHCH,CI(2So3KIACH3(C1(2)3
C) I=01((CH2)3CONC)(2CH□80
．． Nas CH (CH) C0NCH, CH280
3Na3 2 l 1 2H5 7C1((CH)CONCH2CH2803NaCH3 f, C1(3(CH2), CD=Ct((C1(2
), C0NCJI2C) I2So3Na2H5 As the silver halide photographic emulsion contained in the light-sensitive element, a silver halide photographic emulsion conventionally known in the field of silver salt diffusion transfer method can be used.

In the photographic emulsion used in the present invention, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as the silver halide. The preferred silver halide is silver bromide, 1
Silver iodobromide or silver iodochlorobromide containing 0 molt or less silver iodide. Particularly preferred is iodine # from 3 molti to io molti! It contains all silver iodobromide.

Average grain sire of silver rhodanide grains in photographic emulsion 3
- The particle size (in the case of spherical or approximately spherical particles, the particle size is defined as the particle diameter, and in the case of cubic particles, the particle size is expressed as an average based on the projected area) is not particularly limited, but is preferably 3 μ or less. It is preferable that i, zμ or less, but particularly preferable is o,
r~/0.2μ or less.

The silver rhodide grains in the photographic emulsion may have a regular crystal structure such as a cube or an octahedron, or an irregular crystal structure such as a spherical shape or a plate shape.
It may have a regular) crystal form or a composite form of these crystal forms. - May consist of a mixture of particles of various crystal forms.

... Silver rhodanide grains may have different phases inside and on the surface, or may consist of a uniform phase.

Further, the particles may be particles in which a latent image is mainly formed on the surface, or may be particles in which a latent image is mainly formed inside the particles. Particles in which latent images are mainly formed on the surface are preferred.

The photographic emulsion used in the present invention is P, Chimie et Physique Photo by Glafkidea.
raphique-7 goo (published by Paul Monte 1, / 1967), G.
F.

Photographic Emuls by Duffin
ionChemistry (Ihe Focal
Press, 1944), V, 1no, Zelik
+Making and C by Nan et al.
oating Photographic Emuls
ion (published by 'I'he Focal Press, published by Hironoshi). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble...rodan salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. Good too.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

Soluble salts are usually removed from photographic emulsions after precipitation or physical ripening. For this purpose, the long-known Tardel water washing method, which involves gelatinization, may be used, or polyvalent anions may be removed. Inorganic salts (
e.g. sodium sulfate), anionic surfactants, anionic polymers (e.g. polystyrene sulfonic acid)
Alternatively, a sedimentation method (flocculation) using a gelatin derivative (eg, aliphatic acylated gelatin, aromatic acylated gelatin, etc.) may be used.

The process of removing soluble salts may be omitted.

Photographic emulsions do not undergo chemical sensitization, so-called pre-ripening (P
Although emulsions can also be used, chemical sensitization is usually used. For chemical sensitization, the Gla < 1 des, Duf n and Ze II i km
(or) 1. FrleserliGr
undlagen der Photographia
chenProzesse mjt S eyes berhal
ogenid-emulslonen (Akade
mischeVerlaggesellschaft,
The method described in /At) can be used.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminodorias. sol, benzotriazole, nitrobenzotriazole, mercaptotetrazole (especially l-phenyl-
! -mercaptotetrazole); mercaptopyrimidines; mercaptopyrimidines; thioketo compounds, such as oxadolinthione; azaindenes, even l 7- is triazaindenes, tetraazaindenes (especially ≠
-Hydroxy-substituted (/, J, 38.7) tetraazaindenes), pentaazaindenes, etc.; benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. Many compounds known as antifoggants or stabilizers can be added, such as lipoic acid.

For more detailed examples of these and how to use them, see, for example, US Patent No. 3. Rij$, $7μ issue, same 3
．． yr, z,? Those described in No. 4I7, Tokuko Shoyo 11λr, and Tokko No. 1 can be used.

The photographic material used in the present invention may contain a dispersion of a water-insoluble or poorly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability.

For example, alkyl (meth)acrylates, alkoxyalkyl (methacrylates, glycidyl (meth)acrylates, (meth)acrylamides, vinyl esters (e.g., acetate/r-acid), acrylonitrile, olefins, styrene, etc. alone or in combination, or these. and acrylic acid,
A polymer containing a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as a monomer component can be used.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material used in the present invention contains a compound other than the compound represented by general formula (1) for the purpose of coating aid, antistatic properties, improving slipperiness, emulsification dispersion, and preventing adhesion. It may also contain a number of surfactants.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or hapholyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), aliphatic esters of polyhydric alcohols, alkyl esters of sugars, etc. Ionic surfactant Nl +
Alkyl carboxylate, alkyl sulfonate, alkylbenzene, X/I/foonate, alkylnaphthalene sulfonate, alkyl sulfate, alkyl phosphate, sulfosuccinate, sulfoalkylpolyoxyethylene alkylphenyl ether Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, such as polyoxyethylene alkyl phosphates; amino acids, aminoalkaline sulfonic acids ,a? Ampholytic surfactants such as noalkyl sulfuric acid or phosphoric acid esters, alkyl betaines, ann oxides, etc.
Using cationic surfactants such as alkylamine salts, aliphatic or aromatic primary ammonium salts, complex μ-class ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles. I can do it.

The photographic emulsion used in the present invention may be spectrally sensitized with methine dyes and others. The sensitizing dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are cyanine dyes, merocyanine dyes, and dyes that map to complex merocyanine dyes.

In the present invention, it is preferable to use a combination of several sensitizing dyes as described in Japanese Patent Application No. 17-226304.

The silver halide emulsion used in the present invention contains Research Disclosure (Re5earchDisc) as a vehicle.
Losure) Volume 17j, 17tl13, page ko [Vehicles and vehicle-
J/-extenders The vehicles described in section J (12/7) can be used.

The silver halide emulsion layer is coated on the support together with other photographic layers if necessary. The application method is Research Disclosure Y.
) Volume 176, /744'J, 27-2 on page l'-
Coating and drying process
The method described in Dures J may be used. In addition, the support is Research Disclosure (Re5)
arch Disclosure) Volume 17≦,
/76443, the one described in "5upportsJ" by Kosa Sada can be used.

Silver halide photographic emulsions and other hydrophilic colloid layers may also contain antistatic agents, plasticizers, air antifoggants, and the like.

The photographic material used in the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaralium +2 +2-dehyde, etc.), L N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3- dihydroxydioxane, etc.),
Active vinyl compounds (/, 3.!-) lyacryloyl-hexahydro-5-) riazine, 113-vinylsulfonyl-copronomer, etc.), active halogen compounds (
2,4t-dichloro-t-hydroxy-8-toIJazinato), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), and the like can be used alone or in combination.

The photographic material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability.

For example, alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or these and acrylic acid, A polymer containing a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as a monomer component can be used.

The photographic material used in the present invention may contain a dye in the photographic emulsion layer and other hydrophilic colloid layers as a filter dye or for various purposes such as preventing irradiation, and may also contain an ultraviolet absorber. That's fine.

Preferably, a protective layer is provided on the silver halide emulsion layer. The protective layer is made of a hydrophilic polymer such as gelatin and may contain matting agents or lubricants such as silica and polymethyl methacrylate latex.

Exposure to obtain a photographic image may be carried out using a conventional method. i.e. natural light (sunlight), tungsten electric light,
Any of a variety of known light sources can be used, such as a fluorescent lamp, a water scissor lamp, a xenon arc lamp, a carbon arc lamp, a xenon flash lamp, a polar ray tube, and a flash spot. The exposure time is from 171,000 seconds normally used in cameras to 7
Exposure times shorter than 1/1000 seconds, such as 1/io using xenon flash lamps or cathode ray tubes.
Exposures of ~//106 seconds can be used, or exposures longer than 1 second can be used.

If necessary, the spectral composition of the light used for exposure can be adjusted using a color filter. Laser light can also be used for exposure. Alternatively, exposure may be performed using light emitted from a phosphor excited by electron beams, X-rays, r-rays, α-rays, or the like.

In the present invention, an image-receiving layer preferably made of regenerated cellulose containing a silver precipitant is used. The image receiving element including the image receiving layer will be specifically described below.

Image-receiving elements include supports carrying regenerated cellulose elms containing silver precipitants, such as baryta paper, polyethylene laminate paper, cellulose triacetate or polyesters. Such receiver elements are prepared by coating an optionally primed support with a coating solution of a suitable cellulose ester, such as cellulose diacetate-2, in which a silver precipitant is dispersed. be able to. The obtained cellulose ester layer is subjected to alkaline hydrolysis to convert at least a depthwise portion of the cellulose ester into cellulose. In a particularly useful embodiment, the unhydrolyzed portion of the cellulose ester layer containing the silver precipitant and/or the underlying unhydrolyzed cellulose ester, such as cellulose diacetate, is the silver transfer agent. They may include one or more mercapto compounds suitable for improving image tone, stability or other photographic properties. Such mercapto compounds are utilized during imbibition by diffusing from the position where they are initially placed.

In addition, if necessary, a layer of hydrolyzed retacellulose ester containing a silver precipitant and a lower layer of cellulose ester or partially hydrolyzed cellulose ester (!! may contain a mercapto compound as described in Section I). Another layer of hydrophilic polymer may be provided between the two. Co-polymers used in this hydrophilic polymer layer include, for example, gelatin, derivative gelatin (such as phthalated gelatin), sugars (such as starch, galactomannan, gum arabic, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, flurane, hydroxy and hydrophilic synthetic polymers (eg, polyacrylamide, polymethylacrylamide, poly-N-vinylpyrrolidone, co-hydroxyethyl methacrylate, etc.).

Furthermore, an alkali neutralizing agent layer may be provided if necessary. For example, in this alkali neutralizing agent layer,
The polymer acids described in 27 and the like are used.

Examples of suitable 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 radium. Other useful silver precipitants are sulfides and selenides of precious metals, especially mercury, copper, aluminum, bent lead,
Can drill cadmium, cobalt, nickel, silver, lead, antimony, bismuth, cerium and magnesium sulfides, and lead, zinc, antimony and nickel selenides. The function of materials such as silver precipitants in the Kushi transfer method is described, for example, in Nidwin H. Rand et al., US Pat. No. 277, tlt.

The image receiving element may contain various additives, such as hardeners, fluorescent brighteners, coating aids, if desired.

As the developing agent used in the present invention, it is preferable to use the above-mentioned hydroxylamine developer. A phenidone compound is used in combination as an auxiliary developer.

The silver halide solvent used in the present invention may be an alkali metal thiosulfate, such as sodium thiosulfate or potassium thiosulfate, preferably as described in U.S. Pat.
1!7λ74', the same one! 7ko7j and 31!
7. Cyclic imides of the type described in detail in No. 7, such as uracil, tsuzazole, j-methyl-uracil, and the like.

The treatment composition contains an alkali, preferably an alkali metal hydroxide, such as sodium hydroxide or potassium hydroxide. If applied by distributing the processing composition as a thin layer between a superimposed photosensitive element and an image receiving element, the processing composition may contain polymeric film formers, thickeners or thickeners. It is preferable that it contains an agent.

Hydroxyethylcellulose and sodium carboxymethylcellulose are particularly useful for this purpose and are included in the processing composition in concentrations effective to provide the appropriate viscosity according to the known principles of diffusion-roll photography.

The processing composition may further contain other auxiliaries known in the silver transfer process, such as antifogging agents, toning agents, etc.
gents), stabilizers, etc. may be included. Mercapto compounds, indazole compounds, indazole compounds, triazole compounds, etc. are useful as antifoggants and color toning agents, and are particularly described in US Patent No. 314,541. No. 37
J412J, El, 172μ73, British Patent Application No. 2/Co/31 and West German Patent Application (OLS) 11
Compounds described in No. 011341 and the like are effective. The inclusion of stabilizers, particularly oxidation compounds such as triethanolamine, may also increase the shelf life of the treatment composition, as described in U.S. Pat. It has been found to be useful for

The layer structure of the photosensitive material for silver salt diffusion transfer used in the present invention is preferably as follows.

The support has a subbing layer on both sides of a polyethylene terephthalate film containing titanium dioxide. One side has a silver halide photographic emulsion layer and a protective layer thereon. The other side has a carbon black layer and a protective layer thereon. Those with

A support having subbing layers on both sides of a polyethylene terephthalate film containing titanium dioxide or carbon black, a titanium dioxide layer on one side, a silver halide layer on the support,
Furthermore, it has a protective layer on top and a carbon black layer on the other side.

A polyethylene terephthalate film support with subbing layers on both sides, a silver halide photographic emulsion layer on one side, a protective layer thereon, and a carbon black or colored dye layer on the other side.

The support has a subbing layer on both sides of a polyethylene terephthalate film containing carbon black or a colored dye, and has a silver halide photographic emulsion layer on one side and a protective layer on the other side, and a protective layer on the other side. Those with j-.

A polyethylene terephthalate film containing carbon black or colored dye is provided with an undercoat layer, on which is a silver halide photographic emulsion layer, and further on which is a protective layer.

The opposite side of the silver halide photographic emulsion layer is carbon black,
It may have a pack layer that does not contain colored dye.

A film made by adhering a polyethylene terephthalate film containing titanium dioxide and a polyethylene terephthalate film containing carbon black has an undercoat I- on both sides.A silver halide photographic emulsion layer is placed on one side of the support, and a protective layer is placed on the support. and a carbon black layer on the other side.

A laminate support with a polyethylene layer containing titanium dioxide on one side and a polyethylene layer on the other side of paper containing carbon black is provided with subbing layers on both sides, a silver halide photographic emulsion layer on one side, and a protective layer on top of it. One layer has one layer, and the other side has 4 layers of force to bomb blanc.

Undercoat layers are provided on both sides of a laminate support having a polyethylene layer containing titanium dioxide on one side of paper containing carbon black and a polyethylene layer on the other side, and a titanium dioxide layer, a silver halide photographic emulsion layer, One has a protective layer, and the other has a carbon black layer.

Undercoat layers are provided on both sides of a laminate support having polyethylene J- on both sides of the paper, which has a carbon black layer, a silver halide photographic emulsion layer, and a protective layer in this order, and a carbon black layer on the other side ( Functions and Effects of the Invention) The configuration of the present invention, that is, the image forming method for silver salt diffusion transfer of the present invention provides the effect that the image forming time is short. In particular, by using a photosensitive material containing the compound represented by the general formula (I), a silver image having a large maximum density and a small minimum density can be formed on the image-receiving layer. Among the anionic surfactants known as coating aids, it is surprising that the above effect can be obtained with the compound belonging to the general formula N) used in the present invention, although the mechanism of action is unknown. be. In particular, by adding the above-mentioned specific compounds to the protective layer of the photosensitive material, the effect is even more remarkable. It goes without saying that the compound represented by general formula (1) itself acts as a coating aid, and other surfactants of general formula (1) may be used as coating aids in addition to the compound of general formula (t). It is preferable to add it to the protective layer in an amount of, for example, 1/30 to 3 (by weight) of the compound.

(Example) Example 1 Silver halide grains were formed by a double jet method, physically ripened and desalted by a conventional method, and further chemically ripened to obtain a silver iodobromide emulsion (iodine content A, jmolti). Ta. The average diameter of the silver rodanide grains contained in this emulsion is /
It was 1 micron.

This emulsion was dissolved at uo 0c and added to J-[t-chloroco[λ-
0.02% by weight methanol solution of ethyl-5-(3-ethyl-λ-penzothiazolinylidene)propenyl]-3-benzoxasilyl primary propane sulfonate 200
@l+≠-(J-(J-ethylbenzothiazoline-coylidene-λ-methyl-7-propenyl]-3-penzothiasolio)pronosulfonate 0.02 t-
Methanol solution 00. tIII-hydroxy-1-methyl-/, J, Jm, 1 weight aqueous solution of 7-chitrazaindene 100ml + lipoic acid/weight ratio methanol solution/
0. 410 ml of a ≠wt% aqueous solution of ll-cohydroxy/J-bisvinylsulfonylzolonogne + additional 0. Convert an aqueous dispersion of ethyl acrylate polymer with a size of Orμ to the amount of polymer! oy was added.

This emulsion was coated simultaneously with a gelatin retention layer containing a matte-3≠- forming agent of polymethyl methacrylate and a surfactant as shown in Table 1. The amount of surfactant added is 0.03 mole F) per mole of silver halide. The amount of silver applied was 0 per 7m, and 9 per toy.

The support used was a polyethylene terephthalate film containing titanium dioxide that was undercoated and coated with a carbon black layer on the opposite side of the emulsion layer for the purpose of blocking light.

The photosensitive layer sheet thus prepared was overlapped with an image-receiving layer sheet prepared as described below, and the following processing composition was spread in the meantime to a thickness of 0.0 .mu.mm for diffusion transfer development to obtain a positive image.

Cellulose acetate (degree of acetylation: 1j) -1,44f and 3,bu-diphenyl- on polyethylene laminated paper
/, Kujimercapto-Jt (, jH-co, Ja, j,
Ja-tetrazabentalene 0゜j4fl acetone 17ml and methanol II! , 1 is applied to a thickness of j OHl/m and dried. On top of this, add 2μ2 of gum arabic, 27ml of water and 42ml of methanol.
Dissolve in 7 liters of mixed solution, and then add formalin (concentration 6 liters)
Add 6 ml, coat and dry at a thickness of 27°/ml/m2. Furthermore, cellulose acetate/7. ≠v
acetone t! It was dissolved in a mixture of 3 ml and 2 liters of methanol and 1 ton of methanol, and coated and dried to a thickness of 111/m''.

An alkaline solution containing nickel sulfide as a silver precipitant was added onto the coated material prepared by K as described above. An image-receiving sheet was prepared by coating and drying to a thickness of ml/m'', then washing with water and drying.The composition of the alkaline solution used for coating is as follows.

The silver precipitant contained in the alkaline solution, that is, nickel sulfide, was prepared by reacting -0% nickel nitrate aqueous solution and -0% sodium sulfide aqueous solution in glycerin with thorough stirring.

The composition of the treatment liquid is as follows.

Potassium hydroxide (≠θ%KO) I Aqueous solution J23CC Titanium dioxide 32 Hydroxyethyl cellulose 722 Zinc oxide
2.769N,N-bis-methoxyethylhydroxyamine 7jf triethanolamine solution (water J, triethanolamine to J part, J part) /7. /G1 Tetrahydropyrimidinethione o,tyco,l-dimercaptopyrimidine
0,319 Uracil TaO
The reflection density of the positive image sample obtained by the 3V diffusion transfer process was measured using a TCD type self-recording densitometer manufactured by Fuji Film Co., Ltd., and the sensitivity of 37 degrees was calculated from the exposure amount to obtain an optical density of 0.4. . Sensitivity was expressed as a relative value with ioo being the peeling time of sample A/20 seconds and 30 seconds, respectively.

As is clear from Table 1, Sunsol A/X, 2, J, and 4' containing the surfactant of the present invention had a high maximum density at a 20-second islemo exfoliation time and a short image forming time.

Comparative sample shop! The maximum concentration was low for both peeling times of 20 seconds and 30 seconds. In addition, although the maximum concentration of samples mA and 7 was equivalent to that of samples A/-g, the relative sensitivity was low.

-3! - Surfactants a and bSc in Table 1 are compounds with the following structural formulas.

a CH0OCH80aNa C6H1300CH2 Example 2 The same process as in Example 1 was performed except that the following image-receiving sheet was used, and the results shown in Table 1 were obtained.

Image receiving sheet A solution of cellulose acetate c acetate (flsaqb)try and styrene-maleic anhydride copolymer/29 dissolved in 270 ml of acetone and 30 ml of methanol was placed on a polyethylene laminate paper with a thickness of 141H7/-g O- m2. It was coated and dried. On top of this, J, 7-diphenyl-11 μm dimercapto-3H, 4H-j, Ja,
j, Oojri of Aa-tetrazabentalene? The dry film thickness of cellulose acetate acetone solution is j f / m
It was applied so that it became 2. Furthermore, a dimethylol urea (j%) aqueous solution and acetic acid (jO%) were added to and mixed with a 5% aqueous solution of polyacrylamide at a concentration of j%, /, 26%, respectively, and coj Hl / ? It was coated with a coating thickness of F1. Further, on top of this, a solution containing finely dispersed sulfide/hair radium in an acetone/methanol solution of cellulose acetate was applied.

This coating solution contained /-phenyl-j-mercazotoimidazole to give a fermentation rate of 2j x 10' mol/m2. The dry film thickness was O0rμm. This coated material was coated with the following alkaline solution at a ratio of 11,127 m 2 , washed with water and dried to produce an image-receiving sheet. The above sulfurized radium dispersion is of cellulose acetate!
A methanol solution of 7 x 10 mol of sodium sulfide and 7 x 10 mol of salt -4/ = reaction mixture was prepared by adding a methanol solution of sodium radium to a 3% acetone/methanol mixed solution and stirring well.

As is clear from Table 2, samples A/, , 2, J, and 4Z containing the surfactant of the present invention had a high maximum density at a peeling time of 20 seconds and a short image forming time. Comparative sample JkLj has a peeling time of 10 seconds,
The maximum concentration was low for both 30 seconds. Also sample A4.7
The maximum concentration was the same as that of A/-4<, but the relative sensitivity was low and 9.

Example 3 A photosensitive layer sheet was prepared in the same manner as in Example 3, except that sodium alkylbenzenesulfonate having an alkyl group having 13 carbon atoms was used as a surfactant in the gelatin protective layer, and a photosensitive layer sheet was prepared in the same manner as in Example 3. Using the image-receiving layer sheet prepared in the following manner, development processing was performed using a processing solution prepared as described below to obtain a diffusion transfer image on the image-receiving layer sheet.

A surfactant of 0°007 was added to the treatment solution of Example 1 as shown in Table 3.
mol (per 7jy of N,N-bis-methoxyethylhydroxyamine) was added, and the amount of water added was adjusted to make the total amount the same as the treatment solution of Example 1.

As is clear from Table 3, Samples A/, A, and 3 containing the surfactant of the present invention all had high maximum densities and short image forming times at both 20 and 30 seconds peeling times. Comparative sample, +11114' peeling time 20
The maximum concentration was low for both seconds and 30 seconds.

Patent applicant: Fuji Photo Film Co., Ltd. -P6- −256=

Claims (1)

[Scope of Claims] An image forming method for silver salt diffusion transfer in which a photosensitive element containing a silver halide photographic emulsion layer is treated with a processing composition in the presence of a compound represented by the following general formula (I). An image forming method for silver salt diffusion transfer, characterized by: (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 represents an aliphatic hydrocarbon group, R_2 represents a hydrogen atom or an aliphatic hydrocarbon group, and M represents a cation.