JP2879625B2 - Image receiving element for silver salt diffusion transfer method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image receiving element used in an image forming method by silver salt diffusion transfer.

[0002]

2. Description of the Related Art The diffusion transfer method is currently well known in the art, and the details thereof will be omitted. For more information, see A.Rott and E.Weyde, "Photographic Silver Halide Diffusion P
Rocesses), Focal Press (1972); J. Sturge, V. Walworth and A. Shepp, Image Processing and Materials: Neblet 8th Edition. (Imaging Processes and
Materials: Neblette's Eighth Edition) "
Van Nostrand Reinhol
d) Published by the company (1989), Chapter 6, "Instant Photos and Related Methods for Processing Replicated Photos (Instant
photography and Related Reprographic Processe
s) "; G. Haist," Modern Photo Processing,
Volume 2 (Modern Photographic Processing Vol.2) "
John Wiley and S
ons) published by the company (1979), Chapter 8 (Chapter 8),
It is described in "Diffusion Transfer" and the like. With this diffusion transfer method, many types of photographic materials can be prepared, and are described in detail in the above-mentioned publication. 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 overlapped, and a developing agent and a silver halide solvent are used. It is known that a transferred image can be obtained by developing a processing element comprising a high-viscosity alkaline processing composition containing A method using regenerated cellulose as a binder for an image receiving layer is known. That is, Japanese Patent Publication No. 46-4394.
No. 4 describes a method for preparing an image receiving element by dispersing silver precipitation nuclei in acetylcellulose, coating the dispersion on a support, and hydrolyzing and regenerating the acetylcellulose. JP-B-51-49411 discloses a method in which a cellulose ester layer is provided on a paper support, and a cellulose precipitant is hydrolyzed at the same time as or after the cellulose ester layer is hydrolyzed with an alkaline hydrolyzing solution. It describes an image-receiving material made by incorporating it into a cellulose ester layer, that is, a regenerated cellulose layer. However, the silver image formed on the image receiving element thus obtained tends to have a metallic luster on the surface, and when observed with reflected light, the specular reflectance increases particularly in a high-density portion, so that the image becomes a reverse image, and the image is inverted. Significantly degrades quality.
This is a phenomenon that occurs because the transferred silver is concentrated and deposited only on the very surface of the image receiving layer, and this can be confirmed by observing the cross section of the image receiving layer having a metallic luster with an electron microscope.

[0003]

In order to improve the metallic luster, it is important to include only a necessary amount of a compound having an effective phenomenon suppressing action in the image receiving layer. If the content is too small, silver precipitates are concentrated on the surface of the image receiving layer, thereby giving rise to metallic luster. Conversely, if the content is too large, the color tone becomes too cold and the maximum density (Dmax) is large. To decline. In order to improve the metallic luster, it is also important to control the saponification reaction of the cellulose ester. If the region having a high free OH group ratio (saponified) is too shallow, the active silver precipitant concentrates on the surface of the image receiving layer, so that the metallic luster tends to appear. Conversely, if the region having a high free OH group ratio is too deep, the diffusion of the image stabilizer added to the lower neutralizing layer and the neutralization timing layer increases, Dmax decreases, and the addition to the image receiving layer increases. The diffused compound also diffuses, and the effect of preventing metallic luster decreases. Therefore, in order to prevent metallic luster, it is important to define three conditions of the type and content of the compound to be contained in the image receiving layer and the distribution of the free OH group ratio of the image receiving layer, and to simultaneously satisfy these conditions.

An object of the present invention is to provide an image receiving element for a silver salt diffusion transfer method, which defines conditions for preventing metallic luster and does not exhibit metallic luster even in a high density part.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to develop a photosensitive element containing an image-exposed photosensitive silver halide emulsion layer using an alkaline processing element containing a silver halide solvent. An unexposed silver halide as a transferable complex salt, and transferring at least a portion of the complex salt to an image receiving element including a silver precipitate nucleus-containing image receiving layer to form an image on the image receiving element. After coating a cellulose ester containing silver precipitation nuclei on a support, the free OH group ratio of the image receiving layer made of regenerated cellulose obtained by saponifying with an alkaline solution is from 0.5 to 3.0 μm from the surface. The area is 40% or more, and the image-receiving layer contains at least one compound selected from the group consisting of compounds represented by formula (I) in an amount of 1 × 10 ^{−5 to} 6 × 10 ⁻⁵ mol per 1 cm ^3. Characterized by It was achieved by the image-receiving element for salt diffusion transfer process. General formula (I)

[0006]

Embedded image

In the formula, R represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 25 carbon atoms, or a substituted or unsubstituted aryl group. The substituted or unsubstituted alkyl group or the substituted or unsubstituted alkenyl group preferably has 4 to 15 carbon atoms, particularly preferably 5 to 10 carbon atoms. L represents a divalent linking group, particularly preferably an ether group, a thioether group, a carboxamide group, or a substituted or unsubstituted phenylene group. Z represents an atomic group necessary for forming a 5- or 6-membered ring. As such a heterocyclic ring, a diazole ring, a triazole ring, a tetrazole ring, a thiazole ring, a thiadiazole ring, and a thiatriazole ring are preferable. M represents a hydrogen atom or an alkali metal atom. n
Represents 0 or 1. Compounds effective in the general formula (I) are exemplified below, but the present invention is not limited to these compounds.

[0008]

Embedded image

The amount of the compound represented by the general formula (I) is
Preferably 1cm^Three1.5 × 10 ^-Five~ 5.5 × 10^-Five
mol.

The synthesis of the compounds of the present invention can be carried out by known methods.
It can be synthesized by the synthesis method described in No. 231537. The compound of the general formula (I) of the present invention is contained in the image receiving layer by mixing it with a coating solution when a cellulose ester as a binder of the image receiving layer is applied. Or JP-A-61-285
As described in No. 452, after forming a regenerated cellulose layer containing silver precipitation nuclei, the compound is dissolved in a suitable solvent such as methanol, ethanol, acetone, diacetone alcohol, methyl ethyl ketone, water alone or in a mixed solvent. Then, it is usually applied by a known method, or mixed with a coating solution at the time of applying a release layer and / or a neutralization timing layer and / or a neutralization layer and / or other auxiliary layers. May be contained in the image receiving layer.

The amount of the compound of the present invention which is effective for improving the metallic luster can not be generally specified because it greatly varies depending on the coating method and coating conditions. Therefore, it is appropriate to define the content in the image receiving layer after the completion of the image receiving element. Further, the saponification state of the cellulose ester in the image receiving layer, which is one of the important factors for improving the metallic luster, varies greatly depending on the application method and application conditions of the alkali saponification solution, and general prescriptions cannot be prescribed. It is appropriate that the saponification state of the cellulose ester of the image receiving layer effective for improving the metallic luster be determined by the values of the free OH group ratio and the depth. As the saponification formulation, alkali / H ₂ O, alkali / methanol and the like are generally used, and an alkali / methanol formulation containing glycerin for controlling the saponification depth is preferable.

The content of the compound of the present invention in the image receiving layer and the degree of saponification can be measured by the following methods. That is, a micro-infrared absorption spectrum is measured on a sample of a section having a thickness of 1 to 3 μm, which is formed by obliquely cutting the image receiving element at an angle as low as possible using a microtome. The measurement of the microscopic infrared absorption spectrum is described in "FT-1R seen from a chart" published by Kodansha (1990). From the characteristic absorption spectrum intensity of the compound of the present invention, the content of the compound can be determined using a calibration curve prepared in advance. Further, the free OH group ratio of the cellulose ester at an arbitrary depth can be determined from the intensity ratio of the specific absorption of the carbonyl group and the specific absorption of the ether bond of the cellulose skeleton.

The image receiving element according to the present invention comprises a support carrying an image receiving layer containing silver precipitation nuclei, for example, baryta paper,
Coated on polyethylene laminated paper, cellulose triacetate or polyester compounds. The image receiving element of the present invention may contain the compound of the present invention or other mercapto compounds to improve the color tone, stability or other photographic performance of the silver transfer image. Examples of the mercapto compound used include JP-A-49-120634 and JP-B-56-120.
No. 44418, British Patent 1,276,961, JP-B-56-21140, JP-A-59-231537, 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, and the like.
There are copper, cobalt and also noble metals such as gold, silver, platinum and palladium. Other useful silver precipitation nuclei are sulfides and selenides of heavy and noble metals, especially mercury, copper, aluminum, zinc, cadmium, cobalt, nickel, silver,
Lead, antimony, bismuth, cerium, magnesium,
Mention may be made of sulfides and selenides of gold, platinum and palladium. In particular, gold, platinum, palladium or their sulfides are preferred.

The thickness of the cellulose ester layer before the saponification treatment determines the neutralization timing time. The appropriate thickness of the cellulose ester layer varies depending on the degree of acetylation, the components of the processing solution, and the like, but is generally preferably 4 μm to 8 μm, and particularly preferably 4.5 μm.
μm to 7 μm are preferred.

It is preferable to provide a neutralizing acidic polymer layer (alkali neutralized layer) between the unsaponified layer (timing layer) of the cellulose ester after the saponification treatment and the support. For example, a polymer acid described in U.S. Pat. No. 3,594,164 is used. Preferred polymer acids are maleic anhydride copolymers (eg, styrene-maleic anhydride copolymer, methyl vinyl ether-maleic anhydride copolymer, ethylene-maleic anhydride copolymer, etc.) and (meth) acrylic acid (Co) polymers (eg,
Acrylic acid-alkyl acrylate copolymer, acrylic acid-alkyl methacrylate copolymer, methacrylic acid-alkyl acrylate copolymer, methacrylic acid-
Alkyl methacrylate copolymer). In addition, polymers containing sulfonic acids such as polyethylene sulfonic acid and acetalized products of benzaldehyde sulfonic acid and polyvinyl alcohol are also useful. Further, the neutralization layer may contain a mercapto compound used in the timing layer. For the purpose of improving the physical properties of the membrane, these polymer acids may be mixed with a hydrolyzable alkali-impermeable polymer (particularly the above-mentioned cellulose ester is preferred) or an alkali-permeable polymer.

The image receiving element preferably has an image stabilizing layer for improving image storability, and a cationic polymer electrolyte is preferable as the stabilizing agent. US Patent 3,958,9
No. 95, JP-A-55-142339 and JP-A-54-126
Nos. 027, 54-155835 and 53-3032
No. 8, the water-dispersed latex described in US Pat.
548,564, 3,148,061, 3,7
No. 56,814, a polyvinylpyridinium salt, a water-soluble quaternary ammonium salt polymer described in U.S. Pat. No. 3,709,690, or U.S. Pat. No. 3,898,088.
The water-insoluble quaternary ammonium salt polymer described in (1) is preferred as the cationic polyelectrolyte. As the binder for the image stabilizing layer, cellulose acetate is preferred, and cellulose diacetate having an acetylation degree of 40 to 49% is particularly preferred.
This image stabilizing layer is preferably provided between the neutralizing layer and the timing layer.

Further, the timing layer is provided with an acid polymer (for example, methyl vinyl ether and methyl vinyl ether) for the purpose of preventing the timing time from being lengthened by a change in the cellulose ester during long-term storage or shortening the timing time. Copolymer of maleic anhydride or copolymer of methyl vinyl ether and half ester of maleic anhydride)
Can be included.

Further, a white pigment (for example, titanium dioxide, silicon dioxide, kaolin, zinc dioxide) is added to the timing layer and the neutralizing layer in order to prevent light from penetrating from the cross-sectional direction of the sheet to the inside (light piping). , Barium sulfate).

Further, in the timing layer and the neutralizing layer,
A plasticizer may be included for the purpose of improving curl and brittleness. As the plasticizer, a known compound can be used.

An intermediate layer may be provided between the image receiving layer and the timing layer. As the intermediate layer, a hydrophilic polymer such as gum arabic, polyvinyl alcohol, and polyacrylamide can be used.

It is preferable to provide a release layer 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 at the time of release after the development of the processing liquid. Preferred as such a release layer are, in addition to gum arabic, hydroxyethylcellulose, carboxymethylcellulose, polyvinyl alcohol, polyacrylamide and sodium alginate, U.S. Pat. Nos. 3,772,024, 3,820,999 and British Patent 1,360,65
No. 3 can be mentioned. In order to increase the whiteness at the time of observation, in any layer of the image receiving element,
Uvitex OB (trade name of Ciba-Geigy), White Fluor (Whitefluo)
r) Benzoxazoles such as PSN (trade name of Sumitomo Chemical Co., Ltd.), white fluor (Whiteflu)
or) It is preferable to include a coumarin-based fluorescent whitening agent such as B (trade name of Sumitomo Chemical Co., Ltd.).

As a light-shielding method, a method of including a light-shielding agent (for example, carbon black or organic black pigment) in the paper of the support or a method of applying the light-shielding agent on the back surface of the support, and further, It is preferable to apply a white pigment (for example, titanium dioxide, silicon dioxide, kaolin, zinc dioxide, barium sulfate) for whitening. It is preferable to provide a protective layer on the uppermost layer. In the protective layer,
A matting agent can be included to improve the adhesiveness or to provide writing.

As a binder for the light-shielding layer and the protective layer, gelatin, cellulose ester, polyvinyl alcohol and the like are used.

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

In addition to the above-mentioned layer constitution, a support having 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 the titanium dioxide layer, and A photosensitive element in which a protective layer is provided on the other side and a carbon black layer is provided on the other side, and a protective layer is provided thereon is preferably used. A colored dye may be used instead of or in addition to the above-described carbon black.
When polyethylene terephthalate contains carbon black and / or a colored dye, it is not necessary to provide a layer of carbon black and / or a colored dye on one surface. Further, the titanium dioxide may be replaced with another white pigment.

As the support, in addition to the polyester compound, paper laminated with polyethylene, baryta paper, and cellulose triacetate are used.

The silver halide emulsion grains used in the present invention may be any of silver bromide, silver chloride, silver chlorobromide, silver iodobromide, silver chloroiodobromide and silver iodochloride. Silver iodobromide or silver chloroiodobromide having a silver halide content of 1 to 10 mol%. When used for shortening the processing time, the average silver iodide content is preferably from 1.0 to 3.0 mol%, more preferably from 1.5 to 3.0 mol%. Furthermore, it is preferable to change the silver iodide content inside and on the surface of the grains. The higher the silver iodide content inside and the lower the silver iodide content near the surface, the higher the sensitivity and the faster the dissolution rate, and thus the faster the completion of the transferred image. The silver chloride content may be arbitrarily set, but is preferably 1 mol% or less from the viewpoint of sensitivity and fog.

The effect of silver iodobromide formed on the surface after chemical sensitization is a very effective means for achieving higher sensitivity without slowing down the dissolution rate. The silver iodobromide to be formed preferably has a silver amount of 3 to 8%. If the amount of silver is too small or too large in the range of the present invention, the feeling becomes low and the effect cannot be exhibited. The silver iodide content of silver iodobromide on the surface is preferably 2 to 4 mol%. If the silver iodide content is too high, the dissolution rate will be slow and the completion of the transferred image will be slow. Examples of a method for forming silver iodobromide include a method of adding silver ions and a halogen ion after chemical sensitization, a method of adding a fine grain emulsion of silver iodobromide and recrystallization on host grains by Ostwald ripening, and a method of forming silver bromoiodide. There is a method in which a fine grain emulsion of silver iodide and an aqueous solution of potassium iodide are added and Ostwald ripening is performed to recrystallize on host grains.

Regarding the halogen composition distribution of the silver halide grains of the present invention, including those described above, grains having a so-called uniform structure having the same composition in any part of the grains, a core (nucleus) inside the grains and surrounding the grains. A particle having a so-called laminated structure having a different composition from a shell (one or more layers) or a structure having a non-layered portion having a different composition inside or on the surface of the particle (when the particle is on the particle surface, the edge of the particle, Particles having a structure in which portions having different compositions are joined on corners or surfaces) can be appropriately selected and used. In order to obtain high sensitivity, it is advantageous to use one of the latter two particles rather than particles having a uniform structure, and this is also preferable from the viewpoint of pressure resistance. When the silver halide grains have the above-described structure, the boundary portion having a different halogen composition may be a clear boundary or an unclear boundary where a mixed crystal is formed. May have a continuous structural change.

The silver halide grains of the present invention may be grains in which a latent image is mainly formed on the surface or grains in which a latent image is mainly formed inside the grains. Also need not be localized. In particular, particles that form a latent image at the position showing the highest sensitivity under the following conditions are preferable. [Conditions for Confirming Latent Image Position—A silver halide emulsion was coated on a polyethylene terephthalate film so as to have a silver amount of 1 g / m ² , and a sample having a gelatin protective layer thereon was exposed. 0.3g /
Develop with the processing solution of No. 1 at 20 ° C. for 20 minutes. ]

The silver halide grains of the present invention may be those having an equiaxed crystal form such as cubic or octahedral, those having an irregular crystal form such as spherical or tabular, or those having these crystal forms. Any of those having a composite shape may be used. The average size of the silver halide grains of the present invention (expressed as a diameter approximated to a sphere) 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.

Emulsions used in the present invention are prepared by using Graphite (PG
Lafkides), "Chemistry and Physics in Photography (Chimie et Phisiq)
ue Photographique) ", Paul Monell
tel) (1967); Duffin (GF Duffin)
Author, Photographic Emulsion Chem
istry) ”, published by Focal press (1
966); Celikman et al. (VLZelikman et al)
Author, "Making and Coating P
hotographic Emulsions ", Focal Press (Fo)
cal Press) (1964). That is, any method such as an acidic method, a neutral method, and an ammonia method may be used, and the method of reacting a soluble silver salt and a soluble halide is a single-sided mixing method, a double-mixing method, or a combination thereof. May be used. A method of forming particles in an atmosphere containing excess silver ions (so-called reverse mixing method) can also be used. As one type of the double jet method, a method of keeping pAg constant in a liquid phase in which silver halide is formed, that is, a controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained. Further, as a method for obtaining tabular silver halide having a nearly uniform grain size, for example, US Pat.
7,354 technology can be used.

The silver halide emulsion used in the present invention comprises iron,
In addition to iridium salts or complex salts, various polyvalent metal ion compounds can be introduced during the process of emulsion grain formation or physical ripening. Examples of the compound to be used include salts of cadmium, zinc, lead, thallium and the like, and salts or complex salts of ruthenium, rhodium, palladium, osmium and platinum of Group VIII of the periodic table. In particular, a group VIII element can be preferably used. The addition amount of these compounds may vary widely depending on the purpose, but is preferably from 10 ^-9 to 10 based on 1 mol of silver halide.
^-4 mol is preferred.

The chemical sensitization used in the silver halide emulsion of the present invention is described in the above-mentioned books by Glafkides, Duffin and Zelikman or edited by H. Frieser, "Halogenation". The basics of the silver photographic process (DieGrundlagen der Photograph
ischen Prozesse mit Silberhalogeniden), Akademisch
e Verlagsgesellschaft) (1968). That is, compounds containing sulfur that can react with active gelatin or silver (eg, thiosulfates, thioureas, mercapto compounds, rhodanines)
Sulfur sensitization method using noble metal compounds (for example, gold complex salts, platinum, iridium, palladium, etc.
Noble metal sensitization using complex group VIII metal; reduction sensitization using a reducing substance (eg, stannous salt, amines, hydrazine derivative, formamidine sulfinic acid, silane compound) alone or in combination Can be used.

As the spectral sensitizer used in the silver halide emulsion of the present invention, cyanine dyes, merocyanine dyes,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxanol dyes are preferred. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. A specific example is
Hemer (FM Hamer), "Heterocyclie Compounds-Cyan
in Dyes and Related Compounds), published by John Wiley and Sons (196)
4 years). Other US Patent 2,49
No. 3,748, No. 2,519,001, No. 2,97
7,229, 3,480,434 and 3,67
No. 2,897, No. 3,703,377, No. 2,68
8,545, 2,912,329, 3,39
7,060, 3,615,635, 3,62
8,964, British Patent 1,195,302,
242,588, 1,293,862, West German Patent Application (OLS) 2,030,326, 2,121,
No. 780, Japanese Patent Publication No. 43-4936, No. 44-1403
No. 0, No. 43-10773, U.S. Pat.
No. 64, 3,522,052, 3,527,64
No. 1, 3,615,613, 3,615,632
No. 3,617,295 and 3,635,721
No. 3,694,217, British Patent 1,137,5
Spectral sensitizers described in JP-A Nos. 80, 1,216, 203 and the like can also be used. The spectral sensitizer is disclosed in
As described in 114533 and 61-163335, a plurality of combinations can be used.

The thickness of the photosensitive element of the present invention is 0.5 to 8.0.
[mu] m, in particular 1.0～6.0Myuemu, the coating amount of silver halide grains, 0.1 to 3.0 g / m ² as silver amount is preferably 0.2 to 2.0 g / m ² .

In the photosensitive silver halide emulsion layer of the present invention,
Various compounds can be contained for the purpose of preventing fog during the production process, storage, or photographic processing of the photographic material and stabilizing photographic performance. These compounds include azoles (eg, benzothiazolium salts,
Nitroimidazoles, nitrobenzimidazoles,
Chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, nitrobenzotriazoles, benzotriazoles), mercaptopyrimidines, mercaptotriazines, Well-known antifoggants such as thioketo compounds, azaindenes (eg, triazaindenes, tetrazaindenes, pentaazaindenes), benzenesulfonic acids, benzenesulfinic acids, benzenesulfonic acid amides, α-lipoic acid and the like Agents and stabilizers are preferably used. Representative examples include 1-phenyl-2-mercaptotetrazole,
4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, 2-mercaptobenzothiazole, 5-
And carboxybutyl-1,2-dithiolane. For more detailed examples of these and methods of using them, see, for example, US Pat. No. 3,982,947,
What was described in 2-28660 can be used.

The photosensitive element of the present invention can contain an inorganic or organic hardener. For example, chromium salts (chrom alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea,
Methylol dimethylhydantoin, dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, etc.), mucohalic acids (mucochloric acid, mucophenoxycyclolic acid) And the like can be used alone or in combination. Coating aids can be used in the silver halide emulsion layer and other hydrophilic colloid layers of the light-sensitive element of the present invention. As a coating aid, Research Disclos
ure) Volume 176, 17643, p. 26 (1978.12
Compounds described in "Coating aids" of JP-A-61-20035 can be used.

In the silver halide emulsion layer and other hydrophilic colloid layers of the light-sensitive element of the present invention, for example, a polyalkylene oxide or a derivative thereof such as an ether, ester, or amine is used for the purpose of increasing sensitivity, increasing contrast, or promoting development. , Thioether compounds, thiomorpholines,
It may contain compounds such as quaternary ammonium compounds, urethane derivatives, urea derivatives, imidazole derivatives, and 3-pyrazolidones. Examples of such compounds include U.S. Pat. Nos. 2,400,532 and 2,423,549,
Compounds described in JP-A Nos. 2,716,062, 3,617,280, 3,772,021, and 3,808,003 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 hardly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene alone or in combination, or acrylic acid, methacrylic acid, A polymer having a combination of α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, styrene sulfonic acid and the like as a monomer component can be used.

The light-sensitive element of the present invention may comprise a plurality of silver halide emulsion layers. Further, a protective layer can be provided on the silver halide emulsion layer. This protective layer is made of a hydrophilic polymer such as gelatin.
Matting agents or sliding agents such as polymethyl methacrylate latex and silica as described in JP-A-47946 and JP-A-61-75338 can be contained.

In the light-sensitive element of the present invention, a dye or an ultraviolet absorber may be contained in the silver halide emulsion layer and other hydrophilic colloid layers for the purpose of, for example, preventing a filter or irradiation.

In addition, the light-sensitive element of the present invention may contain an antistatic agent, a plasticizer, and an air antifoggant.

As the hydrophilic binder used in the photosensitive element of the present invention, it is advantageous to use gelatin, but 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.) and Synthetic hydrophilic polymers (polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-
A single or copolymer such as vinylpyrrolidone, polyacrylamide, polyvinylimidazole and polyvinylpyrazole) can be used. As gelatin,
In addition to lime-processed gelatin, acid-processed gelatin and Photographic Society of Japan (Bull. Soc. Sci. Phot. Japan), No. 16, p. 30
Enzyme-treated gelatin as described in (1966) may be used, and hydrolysates or enzymatic degradation products of gelatin can also be used. Gelatin derivatives are obtained by reacting gelatin with acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinylsulfonamides, maleimide compounds, polyalkylene oxides, epoxy compounds and the like. Things are used. A specific example is disclosed in US Pat. No. 2,614,92.
No. 8, 3,132,945, 3,186,846
No. 3,312,553, British Patent 861,414
Nos. 1,033,189 and 1,005,784
And JP-B-42-26845.
As the gelatin / graft polymer, those obtained by grafting a homopolymer or a copolymer of a vinyl monomer such as acrylic acid, methacrylic acid, an acrylate, acrylamide, acrylonitrile, styrene, etc. onto gelatin can be used. A specific example is described in US Pat.
No. 3,625, No. 2,831,767, No. 2,95
No. 6,884.

The above-mentioned photosensitive silver halide emulsion layer, protective layer, carbon black layer and the like usually contain a hydrophilic binder such as gelatin.

Processing elements used in the present invention include a developing agent, a silver halide solvent, an alkali agent and a toning agent (Toni).
ng agents), but depending on the purpose, a developing agent and / or a silver halide solvent are added to the photosensitive element and / or
Alternatively, it can be included in the image receiving element.

The developing agent used in the present invention is a benzene derivative having at least two hydroxyl groups and / or amino groups substituted at the ortho or para position of the benzene nucleus (for example, hydroquinone, amidol, methol, glycine, p-type). Aminophenol, pyrogallol)
And hydroxylamines, especially primary aliphatic N-substituted, secondary aliphatic N-substituted, aromatic N-substituted or β
Hydroxylamines, which are soluble in aqueous alkalis, such as hydroxylamine, N-methylhydroxylamine, N-ethylhydroxylamine,
US Pat. No. 2,857,276 and N described in US Pat. No. 3,293,034.
-Alkoxyalkyl-substituted hydroxylamines. Further, a hydroxylamine derivative having a tetrahydrofurfuryl group described in JP-A-49-88521 can also be used. In addition, West German patent application (OLS)
Aminoreductones described in 2,009,054, 2,009,055, and 2,009,078, and heterocyclic aminoreductones described in US Pat. No. 4,128,425 are also used. Can be Further, a tetraalkyl reductic acid described in U.S. Pat. No. 3,615,440 can also be used.

Phenidones, p-aminophenols and ascorbic acid can be used in combination with the above-mentioned developing agents as auxiliary developing agents, and it is preferable to use phenidones in combination.

The silver halide solvent used in the present invention includes a conventional fixing agent (for example, sodium thiosulfate, sodium thiocyanate, ammonium thiosulfate and those described in the aforementioned US Pat. No. 2,543,181). , A combination of a cyclic imide and a nitrogen base (for example, a combination of barbiturate or uracil and ammonia or an amine, and a combination as described in US Pat. No. 2,857,274). Can be Also, 1,1-bissulfonylalkanes and derivatives thereof are known and can be used as the silver halide solvent of the present invention.

The treatment composition contains a hydroxide of an alkali, preferably an alkali metal, such as sodium hydroxide or potassium hydroxide. If the processing composition is to be developed as a thin layer between a superimposed photosensitive element and an image receiving element, the processing element preferably contains a polymeric film former or thickener.

As the polymer film forming agent or thickening agent contained in the processing element, carboxymethyl cellulose,
Cellulose derivatives such as ethylcellulose, hydroxyethylcellulose, methylcellulose and hydroxypropylcellulose, vinyl polymers such as polyvinyl alcohol, acrylic polymers such as polyacrylic acid and polymethacrylic acid, and inorganic polymers such as water glass are used. Of these, hydroxyethyl cellulose and carboxymethyl cellulose are particularly preferred. These are included in the processing composition in a concentration effective to provide the appropriate viscosity by known techniques of diffusion transfer photography.

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

[0054]

The present invention will be described below in more detail with reference to examples and comparative examples.

Embodiment 1

1. Production of Image Receiving Element The following layers were sequentially provided on a polyethylene laminate paper support to produce an image receiving element (1-A). The numerical value in [] indicates the coating amount before saponification and washing with g / m ² . (1) Neutralization layer Cellulose acetate (55% acetylation degree) [6.0], methyl vinyl ether-maleic anhydride copolymer [4.0], Uvitex OB (trade name of Ciba Geigy) [ 0.04], 1- (4-hexylcarbamoylphenyl) -2,3-dihydroxyimidazole-2
-Thion [0.25] (2) Image stabilizing layer Cellulose acetate (acetylation degree 46%) [4.0], polymer [2.0] shown below

[0057]

Embedded image

(3) Timing layer Cellulose acetate (55% acetylation degree) [8.0] (4) Image receiving layer Cellulose acetate (55% acetylation degree) [2.0], palladium sulfide [7.5 × 10 ^-4 ], 1- (4-hexylcarbamoylphenyl) -2,3-dihydroimidazole-2
-Thion [1 × 10 ^-2 ]

(5) Saponification The surface was saponified with a mixture of 12 g of sodium hydroxide, 24 g of glycerin and 280 ml of methanol, and washed with water. (6) Release 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 applied to the back surface of the support. (7-1) Light-shielding layer Carbon black [4.0], gelatin [8.0] (7-2) White layer titanium dioxide [6.0], gelatin [0.7] (7-3) Protective layer poly Methyl methacrylate particles (average diameter 0.05μ
m) [0.2], gelatin [1.6]

An image receiving element similar to 1-A was prepared except that the 1- (4-hexylcarbamoylphenyl) -2,3-dihydroimidazole-2-thione in the image receiving layer was changed as shown in Table 1.

[0061]

[Table 1]

[0062] 2. Preparation of photosensitive element The following layers were coated on a support (polyethylene terephthalate) to prepare a photosensitive element. The numerical value in [] indicates the coating amount in g / m ² . (1) Colloidal silver layer Colloidal silver [0.002] and gelatin [0.9] having an average particle size of 0.01 μm (2) Photosensitive layer Silver iodobromide emulsion having an average particle size of 1.1 μm (AgI content 3.0)
Mol% core-shell type structure) [0.55 silver equivalent], 4-
Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene [0.01], the following sensitizing dye (A),
(B) and (C) were calculated as [3.2 × 10 ⁻⁴ ] and [3.2 ×
10 ^-4 ] and [1.2 × 10 ^-4 ], gelatin [3.
9]

[0063]

Embedded image

(3) Protective layer Gelatin [0.7], 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 (average diameter 0.05 µm) [0.1]

3. Preparation of treatment liquid and preparation of pod The treatment liquid was oxidized by air, so it was prepared in a nitrogen stream. After the preparation according to the following formulation, 0.7 g of the processing liquid was filled in each of a plurality of cleavable containers (pods) to obtain a processing element.

Titanium dioxide 5 g Potassium hydroxide 280 g Uracil 90 g Sodium thiosulfate (anhydrous) 1.0 g Tetrahydropyrimidinethione 0.2 g 2,4-dimercaptopyrimidine 0.2 g 3- (5-mercaptotetrazolyl) benzenesulfonic acid sodium 0.2g potassium iodide 0.3g zinc nitrate · 9H ₂ O 40 g triethanolamine 6g hydroxyethylcellulose 45 g N, N-bis (methoxyethyl) hydroxylamine 250 g (17% aq) 4-methyl-4-hydroxymethyl - 1-phenyl-3-pyrazolidinone 3.0 g H ₂ O 1266 ml

[0067] 4. Development Processing and Measurement The sample obtained by combining the image receiving element, the photosensitive element and the processing element was exposed to continuous tone in 1/10 second,
After developing at 5 ° C. to a liquid thickness of 35 μm, the metallic gloss of the image receiving element peeled off in 5 minutes was visually judged. on the other hand,
Separately, the unprocessed image receiving element is cut with a microtome at a cutting angle of about 2
The sample prepared by cutting at a degree was measured with a microscopic infrared spectrophotometer to analyze the distribution of the saponification degree of the cellulose ester in the image receiving layer and to quantify the compound of the present invention in the image receiving layer. Table 2 shows the results.

[0068]

[Table 2]

As is clear from Table 2, even if the degree of saponification of the cellulose ester as the binder in the image receiving layer is almost the same, if the content of the compound of the present invention in the image receiving layer is not appropriate, the metallic luster is reduced. And the color tone becomes abnormal, and the quality of the transferred image is significantly reduced.

Example 2 In Example 1, the amount of 1- (4-hexylcarbamoylphenyl) -2,3-dihydroimidazole-2-thione added to the image receiving layer of the image receiving element and the content of the saponification solution were shown. Except for the point changed as in Example 3, the development and peeling treatment and the analysis of the image receiving element were performed in the same manner as in Example 1. Table 4 shows the results.

[0071]

[Table 3]

[0072]

[Table 4]

As is clear from Table 4, even in an image-receiving element containing the same amount of the compound of the present invention in the image-receiving layer, if the degree of saponification of the cellulose ester as the binder in the image-receiving layer is not appropriate, the metallic luster is high. It can be seen that the density of the transferred image is lowered and the quality of the transferred image is significantly reduced.

Example 3 In Example 1, 1- (4-hexylcarbamoylphenyl) -2,3-dihydroimidazole-2-thione in the image receiving layer of the image receiving element was replaced with the same amount of the compound shown in Table 5 Except for this point, the development and peeling treatment and the analysis of the image receiving element were performed in the same manner as in Example 1. Table 5 shows the results.

[0075]

[Table 5]

As is clear from Table 5, the compounds of the present invention have an effect of preventing metallic luster.

[0077]

According to the present invention, it is possible to obtain a good transferred image having no metallic luster even in a high density portion.

Claims (1)

(57) [Claims] A photosensitive element containing a photosensitive silver halide emulsion layer that has been image-exposed is developed using an alkaline processing element containing a silver halide solvent to form at least one of the unexposed silver halide in the emulsion layer. Part of the complex is a transferable complex salt, and at least a part of the complex salt is transferred to an image receiving element including an image receiving layer containing a silver precipitate nucleus, whereby an image is formed on the image receiving element. The free OH group ratio of the image receiving layer composed of regenerated cellulose obtained by applying a cellulose ester containing the solution and then saponifying with an alkaline solution is 40% or more in a region from the surface to 0.5 to 3.0 μm, and At least one compound selected from the group of compounds represented by formula (I) is added to the image receiving layer in an amount of 1 × 10 ³ per 1 cm ^3.
An image receiving element for a silver salt diffusion transfer method, comprising ^{-5 to} 6 × 10 ^-5 mol. General formula (I) In the formula, R represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 25 carbon atoms, or a substituted or unsubstituted aryl group. L represents a divalent linking group. Z represents an atomic group necessary for forming a 5- or 6-membered ring. M represents a hydrogen atom or an alkali metal atom. n represents 0 or 1.