JPH04159546A - Image forming method by silver salt diffusion transfer - Google Patents

Abstract

PURPOSE:To prevent a processing liquid from sticking to an image receiving element even in peeling after long-time by incorporating a polymer expressed by specific formula into the layers of a photosensitive element at 0.2 to 30wt.% in total of the total weight of a hydrophilic binder and further incorporating a polymer film forming agent into a processing element. CONSTITUTION:The polymer expressed by formula I is incorporated into >=1 layers inclusive of the uppermost layer of the photosensitive element at 0.2 to 30wt.% in total of the total weight of the hydrophilic binder and further, the polymer film forming agent or thickener is incorporated into the processing element. In the formula I, A denotes a monomer unit polymerizing a substd. ethylenic unsatd. monomer having an anionic functional group; B denotes a monomer unit copolymerizing a copolymerizable substd. ethylenic unsatd. monomer; (x), (y) denote the molar per cent of the respective components; (x) attains 5 to 100 value and (y) 0 to 95. The processing liquid is prevented from sticking onto the image plane of the image receiving member in this way in spite of a change in the peeling time and further, the silver images which are highly resistant to sticking of the traces of finger prints, etc., are obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an image forming method by silver salt diffusion transfer and a film unit used therein.

(Prior Art) The diffusion transfer method is currently well known in the art, and its details will be omitted. For more information, please contact A. Lott (A, R.
ott), E-wipe (H, eyede), “Photography Schiff Silver Halide Diffusion Processes (PhotographlcSllv)
er Hallde Diffuslon Proce
sses)”, published by Focal Press (Foca
Press, 1972); J, Sturge, VW Walworth (
v, walworth), nee sietsubu (^, Sh
epp), “Imaging Processes and Materials; Neblett 8th Edition (Imag1ng Proc
Essesana Materials: Nebl
ette's Eighth p, attton)",
Published by Van Nostrand Reinhold (Van N
o5trand Re1nhold, 1989),
Chapter e, Instant photogra
phy and RelatedReprograph
lc Processes); G-9 Heist (G
.

Hatst), ``Modern Photographic Processing (Moclern Photography)
c ProcesslngVOl, 2), published by John Willey and Sons.
And 5onss 1979) %Chapter (Ch
apter) 8% Defusion Transfer (
Dlffuslon Transfer) and others.

This diffusion transfer method allows the production of many types of photographic materials and is described in detail in the bottom section above. For example, a photosensitive element in which a silver halide emulsion is coated on a support and an image receiving element in which an image receiving layer containing silver precipitation nuclei is coated on another support are superimposed, and a developing agent and a silver halide solvent are used. It is known that a transferred image can be obtained by spreading a processing element comprising a highly viscous alkaline processing composition containing between two said elements.

(Problem to be Solved by the Invention) In the above configuration, after exposing the photosensitive element, the photosensitive element is overlapped with the image receiving element, the processing element is developed in the meantime, and when it is peeled off after a certain period of time, a transferred image is obtained on the image receiving element. . The image-receiving element usually has a peeling layer on its surface, and after the development process, part of the layer loses its film-forming ability due to alkali and dissolves, and in the peeling operation, the part adheres to the photosensitive element side with the processing solution and is removed. and a portion remaining on the image receiving element side. If this peeling operation is done within the specified time, there will be no problem.
However, if the peeling layer is peeled off after a longer period of time has elapsed, the peeling layer will completely dissolve in the processing liquid and disappear, so that the processing liquid may adhere to the image receiving element.

As a peel-improving technology, Japanese Patent Publication No. 63-3300 discloses a diffusion transfer photographic film unit in which a non-photosensitive granular material is contained in the emulsion layer or hydrophilic layer (other than the image-receiving layer) directly adjacent to the release layer. Disclosed. Also, JP-A-59
No. 229555 discloses a technique of adding a release agent to a release layer.

Furthermore, in Japanese Patent Publication No. 63-155934, it is stated that the number of carbon atoms is 7 to 8.
A copolymer comprising a repeating unit derived from a substituted ethylenically unsaturated monomer having at least one alkyl group of A release layer is disclosed that comprises a coalescent layer and a layer containing a cellulose ester. However, although the above techniques can improve short-term releasability, they have not been able to improve long-term releasability.

(Object of the Invention) An object of the present invention is to provide a method that prevents a processing liquid from adhering to an image receiving element even after a long period of time has elapsed.

A further object of the present invention is to provide a method for preventing screen stains due to fingerprints and the like.

(Means for Solving the Problems) The above object is to develop a light-sensitive element containing an image-exposed light-sensitive silver halide emulsion layer using an alkaline processing element containing a silver halide solvent to remove the emulsion layer. An image forming method comprising converting at least a portion of the unexposed silver halide into a transferable silver complex salt, transferring at least a portion of the complex salt to an image receiving element including an image receiving layer containing silver precipitation nuclei, and forming an image on the image receiving element. In one or more layers of the photosensitive element, including the top layer,
Contains a total of 0.2 to 30% by weight of the polymer represented by general formula (I) based on the total amount of the hydrophilic binder, and further contains a polymer film forming agent or thickener in the processing element. This was achieved by an image forming method using silver salt diffusion transfer, which is characterized by the following.

General formula (I) +A + Represents a polymerized monomer unit. x1y represents the mole percentage of each component, X takes a value of 5 to 100, and y takes a value of 0 to 95.

The polymer of general formula (I) will be explained in more detail below.

At least one kind of anionic functional group represented by A includes -COOH group, -8O3H group, -802H group, -0
PO3H2 group (or its monoalkyl ester group)
, -0SO3H group, etc. These anionic groups may be in the form of their salts, for example, alkali metal salts (such as Na salts), ammonium salts (salts with ammonia, methylamine, dimethylamine, etc.), and especially alkali metal salts. It is preferable that it is in the form of

Examples of substituted ethylenically unsaturated monomers having such anionic functional groups are shown below in non-dissociated form, but are not limited thereto.

CH.

CIl,=C11 C00C11t(:H,0COCHffiCI1.C0
0II, Hs C)It-CCl1t=CI(cL-CI1CH*=lj1 In the present invention, two or more types of substituted ethylenically unsaturated monomer units having at least one type of anionic group represented by A may be included. .

Examples of substituted ethylenically unsaturated monomers in B are ethylene, propylene, 1-butene, isobutyne, styrene,
α-methylstyrene, vinyl ketone, substituted monoethylenically unsaturated esters of aliphatic acids (vinyl acetate, allyl acetate, etc.), esters or amides of substituted ethylenically unsaturated monocarboxylic or dicarboxylic acids (methyl methacrylate, ethyl methacrylate, n- butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, n-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl methacrylate, acrylamide, N-methyl acrylamide, etc.)
Substituted monoethylenically unsaturated compounds (acrylonitrile, N
-vinylpyrrolidone, etc.), or dienes (butadiene, isoprene, etc.), among which acrylamide, hydroxyethyl methacrylate, methyl methacrylate, N-vinylpyrrolidone, etc. are particularly preferred. B may contain two or more types of the above monomer units.

x and y represent the mole percentage of each component, and X is 5 to 1001
Preferably 20-100, particularly preferably 50-100
takes the value of y has a value of 0 to 95, preferably 0 to 80, particularly preferably 0 to 50.

The solution concentration of the polymer represented by the general formula (I) can be varied in various ways taking into consideration the solubility in the coating liquid or the influence on photographic properties, but in particular, the concentration of the polymer in an alkaline aqueous solution (for example, 10
% potassium hydroxide aqueous solution) or water/methanol =
It is preferable that 5% by weight or more is dissolved in at least one of 10010 to 50150 (volume ratio).

Examples of polymers having at least one type of repeating unit having at least one type of anionic functional group in the present invention are shown below, but the present invention is not limited thereto. The quantitative ratios in the compounds represent molar percentage ratios.

Example (I) 1,000 cozco + Cθ0K (3)　　　　　　(:H.

+CHjC-)- 0OK (4) Co.

lls Clix: y-50: 50 cases (6)
CIl, C0(IK -(-CIlIC+- 0OK x:y=30:10 x:y=10:90 z:y:zWealth 5.0':2515 I1(ION CH.

The above polymer used in the present invention is added to one or more layers including the top layer (hydrophilic binder-containing layer) of the photosensitive element, and the total amount thereof is based on the total amount of the hydrophilic binder in the photosensitive element. It is preferably 0.5 to 20%, particularly preferably 1 to 15%.

The hydrophilic binder used in the photosensitive element of the present invention includes:
Although gelatin is advantageously used, other hydrophilic binders can also be used.

For example, proteins (gelatin derivatives, graft polymers of gelatin and other polymers, albumin, casein, etc.), cellulose derivatives (hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, etc.), sugars (sodium alginate, starch derivatives, etc.), Synthetic hydrophilic polymers other than general formula (I) (single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc.) can be used.

Examples of gelatin include lime-treated gelatin, acid-treated gelatin, Bull, Soc, Sc1. Photo, Japan
Enzyme-treated gelatin as described in No. 16°P, 30 (I9661) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used.

Gelatin derivatives are obtained by reacting gelatin with acid halides, acid anhydrides, isocyanates, bromoacetic acids, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkylene oxides, epoxy compounds, etc. things are used. Specific examples include U.S. Pat.
No. 5, same No. 3,186,846, same No. 3. ．． 312,5
53, British Patent No. 861,414, British Patent No. 1,033,1
No. 89, No. 1,005,784, Special Publication No. 42-268
It is described in No. 45 etc.

As the gelatin graft polymer, a gelatin grafted with a single or copolymer of a vinyl monomer such as acrylic acid, methacrylic acid, acrylic ester, acrylamide, acrylonitrile, or styrene can be used.

Specific examples include U.S. Pat. No. 2,763,625, U.S. Pat.
It is described in No. 831,767, No. 2,956,884, etc.

The image-receiving element of the present invention is coated on a support carrying an image-receiving layer containing silver precipitation nuclei, such as baryta paper, polyethylene laminate paper, cellulose pentose or a polyester compound.

Such image receiving elements are preferably made by coating an optionally subbed support with a coating solution of a suitable cellulose ester, such as cellulose diacetate, in which silver precipitation nuclei are dispersed. The obtained cellulose ester layer is subjected to alkaline hydrolysis to convert at least a portion of the cellulose ester in the depth direction into cellulose.

In particularly useful embodiments, the unhydrolyzed portions of the cellulose ester layer containing the silver precipitate core layer and/or the underlying unhydrolyzed cellulose ester, e.g. cellulose diacetate, are Contains one or more mercapto compounds suitable for improving image tone, stability or other photographic properties.

Such a mercapto compound is utilized during invivision by diffusing from the position where it is initially placed. A receiving element of this type is described in US Pat. No. 3,711.283.

As the mercapto compound, Japanese Patent Application Publication No. 49-120634, Japanese Patent Publication No. 56-44418, British Patent No. 1.276.9
No. 61, Japanese Patent Publication No. 56-21140, Japanese Patent Publication No. 59-23
Compounds described in No. 1537 and JP-A-60-122939 are preferred.

Specific examples of silver precipitation nuclei include heavy metals such as iron-lead, zinc, nickel, cadmium, tin, chromium, copper, cobalt, as well as noble metals such as gold, silver, platinum and palladium. Other useful silver precipitation nuclei are sulfides and selenides of heavy and precious metals, especially mercury, copper, aluminum, zinc, cadmium, cobalt, nickel, silver, lead, antimony, bismuth, cerium, magnesium, gold, platinum, and Mention may be made of palladium sulfides and selenides. In particular, gold, platinum, palladium, or their sulfides are preferred.

Further, it is preferable to provide a neutralizing acidic polymer layer (alkali neutralization layer) between the unsaponified layer (timing layer) and the support.

The alkali neutralizing layer used in the present invention includes, for example, U.S. Pat.
, 594, 164, etc. are used. A preferred polymeric acid is maleic anhydride copolymer (
(e.g., styrene-maleic anhydride copolymer, methyl vinyl ether-maleic anhydride copolymer, ethylene-maleic anhydride copolymer, etc.) and -(meth)acrylic acid (co)polymer (e.g., acrylic acid-alkyl acrylate copolymers, acrylic acid-alkyl methacrylate copolymers, methacrylic acid-alkyl acrylate copolymers, methacrylic acid-alkyl methacrylate copolymers, etc.).

In addition, polymers containing sulfonic acid such as polyethylene sulfonic acid and an acetal of benzaldehyde sulfonic acid and polyvinyl alcohol are also useful.

Further, the neutralization layer may contain a mercapto compound used in the timing layer. Further, for the purpose of improving membrane physical properties, these polymer acids may be mixed with a hydrolyzable alkali-impermeable polymer (the above-mentioned cellulose ester is particularly preferred) or an alkali-permeable polymer.

Further, it is preferable that the image receiving element has an image stabilizing layer for improving image storage stability, and a cationic polymer electrolyte is preferable as the stabilizing agent.
No. 166940, U.S. Pat. 548,56
No. 4, No. 3,148,061, No. 3.756°814
Polyvinylpyridinium salt described in US Pat. No. 3,7
Preferred as the cationic polyelectrolyte are the water-soluble quaternary ammonium salt polymers described in US Pat. No. 09,690 or the water-insoluble quaternary ammonium salt polymers described in US Pat.

Further, as the binder for the image stabilizing layer, cellulose acetate is preferable, and cellulose diacetate having a degree of acetylation of 40 to 49% is particularly preferable. This image stabilizing layer is preferably provided between the above-mentioned neutralizing layer and timing layer.

The timing layer also contains acid polymers (for example, methyl vinyl ether ξ
A copolymer of maleic anhydride or a copolymer of methyl vinyl ether and maleic anhydride half ester) can be included.

In addition, the timing layer and neutralization layer contain white pigments (e.g., titanium dioxide, silicon dioxide, kaolin, zinc dioxide, barium sulfate) to prevent light from penetrating into the sheet from the cross-sectional direction (light piping). ) can be included.

Additionally, an intermediate layer may be provided between the image receiving layer and the timing layer. Hydrophilic polymers such as gum arabic, polyvinyl alcohol, and polyacrylamide are preferably used as the intermediate layer.

Further, it is preferable to provide a peeling layer on the surface of the image-receiving layer in order to prevent the treatment liquid from adhering to the surface of the image-receiving layer during peeling after the treatment liquid is developed. Preferred examples of such a release layer include gum arabic, hydroxyethyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, polyacrylamide, sodium alginate, and US Pat. Nos. 3,772,024 and 3. 820.
Mention may be made of those described in No. 999 and British Patent No. 1,360,653.

As a method of light blocking, a light blocking agent (for example,
methods of incorporating carbon black or organic black pigments,
The above light shielding agent is applied to the back side of the support, and on top of that,
It is preferable to apply white pigments (for example, titanium dioxide, silicon dioxide, kaolin, zinc dioxide, barium sulfate) for whitening.

Further, for the purpose of improving curl and brittleness, a moisture absorbent such as glycerin or a film quality improving agent such as polyethyl acrylate latex may be included.

Moreover, it is preferable to provide a protective layer on the uppermost layer thereof. The protective layer can contain a matting agent to improve adhesion or provide writability.

Gelatin, cellulose ester, polyvinyl alcohol, etc. are used as the binder for the above-mentioned light-shielding layer and protective layer.

In the present invention, a photosensitive silver halide emulsion layer is formed on one side of a support having undercoat layers on both sides of a polyethylene terephthalate film containing titanium dioxide or carbon black.
A photosensitive element having a protective layer thereon, a carbon black layer on the other side, and a protective layer thereon is preferably used.

In addition to the above layer structure, the support has an undercoat layer on both sides of a polyethylene terephthalate film containing titanium dioxide or carbon black, a titanium dioxide layer on one side, a photosensitive silver halide emulsion layer on top of that, and a protective layer on top of that. A photosensitive element is preferably used in which a carbon black layer is provided on the other side, and a protective layer is provided on the carbon black layer on the other side.

Moreover, a colored dye can be used in place of or in addition to the above-mentioned carbon black. Further, when polyethylene terephthalate contains carbon black and/or colored dye, it is not necessary to provide a layer of carbon black and/or colored dye on one side. Furthermore, the titanium dioxide may be replaced with other white pigments.

As the support, in addition to the above-mentioned polyester compound, polyethylene-laminated paper, baryta paper, and pentose acid cellulose are used.

The silver halide emulsion used in the photosensitive element of the present invention contains at least 0.5 mol % of silver iodide. Here, "at least 0.5 mol% of silver iodide" means that the content of silver iodide in the total silver halide is 0.5 mol% or more,
Therefore, the silver halide emulsion may contain pure silver chloride, silver chlorobromide, pure silver bromide, or pure silver iodide grains, but silver iodobromide or silver chloroiodobromide grains account for 90% of the total silver halide. The above is preferable, and it is more preferable that it consists only of silver iodobromide or silver chloroiodobromide grains.

The silver iodide content in silver iodobromide or silver chloroiodobromide is preferably 0.5 to 8 mol%, more preferably 1 to 5 mol%. In order to shorten the image forming time, the silver iodide content is preferably 3 mol % or less.

The average size of the silver halide grains (represented by the diameter when the projected area is approximated as a circle) is not particularly limited, but is preferably 4 μm or less, more preferably 3 μm or less, and particularly preferably 0.2 to 2 μm.

The particle size distribution may be narrow or wide.

The silver halide grains in the silver halide emulsion may have an equiaxed crystal shape such as a cube or an octahedron, or may have an irregular crystal shape such as a spherical shape or a tabular shape, or may have an irregular crystal shape such as a spherical shape or a tabular shape. It may also have a compound shape.

Regarding the halogen composition distribution of silver halide grains, there are grains with a so-called uniform structure in which the composition is the same throughout the grain, a core inside the grain and a shell surrounding it [-layer or multiple layers]. Particles with a so-called laminated structure that have different compositions, or structures that have parts with different compositions in a non-layered manner inside or on the particle surface (if they are on the particle surface, parts of different compositions are bonded on the edges, corners, or faces of the particle) It is possible to appropriately select and use particles with a structure such as In order to obtain high sensitivity, it is more advantageous to use one of the latter than particles with a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When silver halide grains have the above-mentioned structure, the boundary between different halogen compositions may be a clear boundary or an unclear boundary where a mixed crystal is formed. It may also have continuous structural changes.

The silver halide grains may be grains in which the latent image is mainly formed on the surface, grains in which the latent image is mainly formed inside the grain, or in which the latent image is not localized in any of them. It's okay. Particularly preferred are particles in which latent images are mainly formed on the surface.

The thickness of the silver halide emulsion layer is 0.5 to 8.0 μm, especially 0.6 to 6.0 μm, and the coating amount of silver halide grains is 0.1 to 3 g/J in terms of silver amount, preferably 0. .2～
It is 1.5g/+J.

The photosensitive silver halide emulsion layer is formed by the manufacturing process of photographic materials,
Various compounds can be contained for the purpose of preventing fogging during storage or photographic processing and stabilizing photographic performance.

These compounds include azoles (e.g., benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, nitrobenzotriazoles, benzotriazoles), mercaptopyrimidines, mercaptotriazines, thioketo compounds, azaindenes (e.g., triazaindenes, tetrazaindenes, pentaazaindenes), Well-known antifoggants and stabilizers such as benzenesulfonic acids, benzenesulfinic acids, benzenesulfonic acid amides, and α-riboic acid are preferably used. Representative examples include 1-phenyl-2-mercaptotetrazole, 4-hydroxy-6-methyl-1°3.
3g, 7-tetrazaindene, 2-mercaptobenzothiazole, 5-carboxybutyl-1,2-dithiolane, etc.

For more detailed examples of these and how to use them, for example, those described in US Pat. No. 3,982.947 and Japanese Patent Publication No. 52-28660 can be used.

Further, a spectral sensitizer can be added to the silver halide emulsion layer of the present invention. The sensitizing dyes used are preferably cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxanol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes.

Also, JP-A-59-114533, JP-A No. 61-16333
As described in No. 4, multiple sensitizing dyes can be used in combination.

The photosensitive elements of the present invention can include inorganic or organic hardeners. For example, chromium salts (chromium alum, chromium acetate, etc.), alta-humans (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxy Dioxane, etc.), active vinyl compounds (I,3,5-1-lyacryloyl-hexahydro-5-) riazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), etc., may be used alone or in combination. I can do it.

Coating aids may be used in the silver halide emulsion layer and other hydrophilic colloid layers of the photosensitive element of the invention.

As a coating aid, Research Disclosure (Re
Search Disclosure) Volume 176, 1
rcoat of 7643.26 pages (I978, 12 issue)
The compounds described in the section of ing alds J and the compounds described in JP-A-61-20035 can be used.

The silver halide emulsion layer and other hydrophilic colloid layers of the photosensitive element of the present invention contain, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, for the purpose of increasing sensitivity, increasing contrast, or promoting development.
It may also contain compounds such as thioether compounds, thiomorpholines, quaternary ammonium compounds, urethane derivatives, urea derivatives, imidazole derivatives, and 8-pyrazolidones.

Examples of such compounds include U.S. Pat.
No. 2, No. 2,423,549, No. 2,716.062
Compounds described in No. 3,617,280, No. 3772.021, No. 3,808,003, etc. can be used.

The silver halide emulsion layer and other hydrophilic colloid layers of the light-sensitive element of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylates, alkoxyalkyl (meth)acrylates, glycidyl (meth)acrylamide, vinyl esters (e.g. vinyl acetate), acrylonitrile, olefins, styrene, etc. alone or in combination, or together with acrylic acid,
A polymer containing a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, styrene sulfonic acid, etc. as a monomer component can be used.

The silver halide emulsion layer used in the photosensitive element of the present invention may be composed of a plurality of silver halide emulsion layers. Furthermore, a protective layer can be provided on the silver halide emulsion layer. This protective layer may be the same as or different from the top layer in the present invention. The uppermost layer may contain a matting agent or a slipping agent such as polymethyl methacrylate latex or silica as described in JP-A-61-47946 and JP-A-61-75338.

In the photosensitive element of the present invention, dyes and ultraviolet absorbers may be contained in the silver halide emulsion layer and other hydrophilic colloid layers for the purpose of filtering or preventing irradiation.

In addition, the photosensitive element of the present invention includes antistatic agents, plasticizers,
Air antifoggants may be included.

Polymeric film formers or thickeners included in the treatment elements of the present invention include cellulose derivatives such as carboxymethyl cellulose, ethyl cellulose, hydroxyethyl cellulose, methyl cellulose, hydroxypropyl cellulose, vinyl polymers such as polyvinyl alcohol, polyacrylic acid, etc. or acrylic acid polymers such as polymethacrylic acid, or inorganic polymers such as water glass. Among these, hydroxyethyl cellulose and carboxymethyl cellulose are particularly preferred.

In addition to the above, the processing elements used in the present invention include a developing agent, a silver halide solvent, an alkali agent, and a toning agent (To
Depending on the purpose, a developing agent and/or a silver halide solvent may also be included in the light-sensitive element and/or the image-receiving element.

The developing agent used in the present invention is a benzene derivative in which at least two hydroxyl groups and/or amino groups are substituted at the ortho or para position of the benzene nucleus (e.g., hydroquinone, amitol, metol, glycine, p-aminophenol, pyrogallol) and hydroxylamines, especially primary aliphatic N-substituted, secondary aliphatic N-substituted, aromatic N-substituted or β-hydroxylamines, which are soluble in aqueous alkali;
For example, hydroxylamine, N-methylhydroxylamine, N-ethylhydroxylamine, U.S. Pat.
857,276 and N-alkoxyalkyl substituted hydroxylamines as described in U.S. Pat. No. 3,293,034.

Hydroxylamine derivatives having a tetrahydrofurfuryl group described in JP-A-49-88521 may also be used.

Also, West German Patent Application (OLS) No. 2,009,054,
Amyl reductones described in US Patent Nos. 2,009,055 and 2,009°078, and US Pat.
Heterocyclic amyl reductones described in US Pat. No. 8,425 are also used.

Tetraalkyl reductin acids described in US Pat. No. 3,615,440 can also be used.

Phenidone, p-aminophenol and ascorbic acid can be used in combination with the above-mentioned developing agent as an auxiliary developing agent, and phenidone is preferably used in combination.

The silver halide solvents used in this invention include conventional fixing agents (e.g., sodium thiosulfate, sodium thiocyanate, ammonium thiosulfate, and those described in the above-mentioned U.S. Pat. No. 2,543.181) and cyclic fixers. Combinations of imides and nitrogen bases, such as pulpyrate or uracil and ammonia or amines, and combinations such as those described in U.S. Pat. No. 2,857,274 are used. .1-bissulfonyl alkanes and their derivatives are also known and can be used as silver halide solvents in the present invention.

The alkali used in the present invention preferably contains an alkali metal hydroxide, such as sodium hydroxide or potassium hydroxide.

As the color toning agent used in the present invention, U.S. Patent No. 3.23
-6; Tetrahydropyrimidinethione compounds described in JP-A No. 642, mercaptotriazole compounds described in JP-A-59-195236, water-soluble mercapto compounds described in JP-A-61-241749, JP-A-61-241750, and JP-A-61-241751 Or JP-A-63-24
The phenylmercaptoimidazole compound described in No. 1546 can be used. Among them, tetrahydropyrimidinethione, 3-mercapto-4,5-dimethyltriazole, 3-(5-mercaptotetrazolyl)
Sodium benzenesulfonate and 1-phenylmercaptoimidazole are preferred.

The processing composition may further contain other auxiliaries known in the silver salt diffusion transfer process, such as antifoggants, stabilizers, and the like.

(Example) Below, the present invention will be explained in further detail by giving examples and comparative examples.

Example 1 1. Preparation of image-receiving element An image-receiving element was prepared by sequentially depositing the following layers on a polyethylene laminate paper support. The numbers in brackets indicate the coating amount in g/i.
This is shown in .

(I) Neutralization layer Cellulose acetate (degree of acetylation 55%) [6,0], Methyl vinyl ether-maleic anhydride copolymer [4,0], Uvitex OB (trade name of Ciba Geigy) ) [0,04] , 1-(4-benzylcarbamoylphenyl)-2゜3-dihydroxyimidazole-2-thione [0゜25] (2) Image stabilizing layer Cellulose acetate (degree of acetylation 46%) [4, OF, the following compound [2,0] (3) Timing layer cellulose acetate (acetylation degree 55%) [8,0] (4) Image receiving layer cellulose acetate (acetylation degree 55%) [2,0] , palladium sulfide [7,5X10-'), 1-(4-hexylcarbamoylphenyl)-2,8-dihydroimidazole-2-thione [1,0XIO-2] (5) Saponification of sodium hydroxide 12g and glycerin 24g saponified from the surface with a mixture of 280 ml of methanol and
Washed with water.

(6) Peeling layer Butyl methacrylate-acrylic acid copolymer (molar ratio 15:85) [0,1] (7) Back layer A light shielding layer, a white layer and a protective layer were coated on the back side of the above support.

(7-1) Light-shielding layer Carbon black [4,0], gelatin [8°0], polyacrylate particles (average diameter 0.05μIl) [O9
2] (7-2) White layer titanium dioxide [6,0], gelatin [0,7] (7-3
) Protective layer polymethyl methacrylate particles (average diameter 0゜05μ
m) [o, 2, Gelatin [1,6, 2, Preparation of photosensitive element A photosensitive element was prepared by coating the following layers on a support (polyethylene terephthalate). The numerical value in [ ] indicates the coating amount in g/J.

(I) First photosensitive layer Silver iodobromide with an average grain size of 1.1 μm (Agl content 6°5 mol%) [silver equivalent 0.05], silver iodobromide with an average grain size of 0.6 μm (Agl content 6 .0 mol%) [silver equivalent 0.05], 4
-Hydroxy-6-methyl-1,3,3a,7-tetrazaindene [2,4X10-3], sensitizing dye A below
[6,7X10-', the following sensitizing dye B [6,7X1
0-5], the following sensitizing dye C [2,2X10"], gelatin [1,7] (2) second photosensitive layer silver iodobromide with an average grain size of 1.1 μm (Agl content 6.5 mol%) [Silver equivalent 0.51], 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene [0,01],
The following sensitizing dye A [3,5x10-'], the following sensitizing dye B [3,5x10-''], the following sensitizing dye C [1,2
X10-1], gelatin [3,1 (C) (B) (C) (3) Protective layer gelatin [0,7], polymethyl methacrylate particles (
Average diameter 4.7 μm) [0,1] (4) Back layer (4-1)! Light layer carbon black [4,0], gelatin [2°0] (4-2) Protective layer gelatin [0,7], polymethyl methacrylate particles (
Average diameter: 0.05 μm) [0,1] The above photosensitive element (I
Photosensitive elements (IB) to (I
J) was produced. Regarding the type and amount of polymer added,
It is shown in Table 1.

Table 3: Preparation of Treatment Solution and Bod Preparation Since the treatment solution is oxidized by air, it was prepared in a nitrogen stream. After preparation, multiple cleavable containers (bods)
Each piece was filled with 0.7 g of treatment liquid to form a treatment element.

Titanium dioxide -------5g Potassium hydroxide ---280g Uracil
----------90g Tetrahydropyrimidinethione---0,2g 2.4-dimercaptopyrimidine---0,2g 3-(5-mercaptotitrazolyl)benzenesulfone -0.2g Zinc nitrate 9H20---40g Triethanolamine -1-6g Hydroxyethylcellulose---45g N,N-bis(methoxyethyl)hydroxylamine (I7% aqueous solution) --220g 4-Methyl-4-hydroxymethyl-1-phenyl-3-pyrazolinone ---------0.2g H2O----1300m 1 4, development treatment The above image-receiving element, photosensitive element ( For samples combining IA) to (IJ) and processing elements, the liquid thickness was 35μ at 25℃.
The image-receiving elements that were developed at 35°C and then peeled off at 10, 20, and 30 minutes after being developed at The adhesion of the above treatment liquid was evaluated. Evaluation,
It was expressed as the area ratio (%) of the treatment liquid attached per five screens of 9.5 cm x 7.2 cm.

The results are shown in Table 2.

Table 2 As is clear from Table 2, the photosensitive element (IB) of the present invention
The screen of the image-receiving element combined with ~(IJ) remained free of treatment liquid for a longer period of time compared to the screen of the image-receiving element combined with Comparative Example (IA). Furthermore, in the present invention, better results were obtained when the polymer was added to the lower layer rather than only to the uppermost layer.

Example-2 Samples combined in the same manner as in Example-1 were heated at 15°C-60
After 10 minutes, fingerprints were pressed onto the screen of the image receiving element in several places. Surface turbidity was visually evaluated. As a result, the screen of the image receiving element combined with the photosensitive elements (IB) to (IJ) of the present invention had far fewer fingerprint marks and turbidity than the screen of the image receiving element combined with the comparative example (IA). .

Example 3 A photosensitive element was prepared by coating the following layers on a support (polyethylene terephthalate). The numbers in [ ] indicate the coating amount in g/F.

(I) Colloidal silver layer with an average grain size of 0.01 μm, colloidal silver [0,002], gelatin [0,9] (2) Photosensitive layer: silver iodobromide with an average grain size of 1.1 μm (AgI content: 1°5 mol) %) [Silver equivalent 0.50], average particle size 0. 7 μm silver iodobromide (AgI content 1.5 mol%) [0.05 pieces in terms of silver,
4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene [0,013, sensitizing dye A [,3,2x
10"], sensitizing dye B [8,2x10-'], sensitizing dye C [1,2x10-'], gelatin [3,9] (3) Protective layer gelatin [0,71, polymethyl methacrylate particles (
Average diameter: 4.7 μm) [0,1] (4) Back layer (4-1) Light shielding layer carbon black [4,0], gelatin [2°0] (4-2) Protective layer gelatin [0,7] , polymethyl methacrylate particles [
0,11 Photosensitive elements (3B) to (3D) were prepared by using the above photosensitive element as (3A) and adding the polymer shown in the present invention to layer (I), layer (2), and layer (3). The types and amounts of polymers added are shown in Table 3.

The third surface photosensitive elements (3A) to (3D) were combined with the image receiving element and processing element of Example-1, and the same development and peeling treatment as in Example-1 was performed. The results are shown in Table 4.

As is clear from Table 4, the photosensitive element (3B) of the present invention
The screen of the image-receiving element combined with (3D) has the following characteristics compared to the screen of the image-receiving element combined with comparative example (3A).
The treatment liquid did not adhere for a longer period of time.

(Effects of the Invention) According to the present invention, even if the peeling time changes from a short time of less than 1 minute to a long time of 20 minutes or more, the processing liquid will not adhere to the screen of the image receiving element, and fingerprint marks will remain. It is possible to obtain silver images that are resistant to stains.

Patent applicant: Fuji Photo Film Co., Ltd.

Claims (1)

Claims: A light-sensitive element containing an imagewise exposed light-sensitive silver halide emulsion layer is developed using an alkaline processing element containing a silver halide solvent to remove at least the unexposed silver halide of the emulsion layer. An image forming method in which a part of the complex salt is a transferable silver complex salt, and at least a part of the complex salt is transferred to an image receiving element including an image receiving layer containing silver precipitated nuclei to form an image on the image receiving element, the uppermost layer of the photosensitive element. 0.2 to 30% by weight of the polymer represented by the general formula (I) based on the total amount of the hydrophilic binder in one or more layers containing the polymer. An image forming method by silver salt diffusion transfer characterized by containing a film forming agent or a thickening agent. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Here, A represents a monomer unit obtained by polymerizing a substituted ethylenically unsaturated monomer having an anionic functional group, and B represents a copolymerizable substituted ethylenically unsaturated monomer. represents a monomer unit copolymerized with A. x and y represent the mole percentage of each component, x takes a value of 5 to 100, and y takes a value of 0 to 95.