JPH0545826A - Image receiving element for silver salt diffusion transfer process - Google Patents

Abstract

PURPOSE:To obtain the image receiving element for the silver salt diffusion transfer process not exhibiting metallic luster even in high density part by regulating the free hydroxyl ratio of the image receiving layer and conditions for preventing the metallic luster and incorporating a specified compound in the image receiving layer. CONSTITUTION:A support is coated with cellulose ester containing silver precipitation nuclei, and then coated with the image receiving layer made of regenerated cellulose obtained by saponifying with an alkaline solution, and the free hydroxyl ratio of the layer is regulated to >=40 96% in the region of 0.5-3.0mum apart from the surface of the layer, and the layer contains at least one of the compounds represented by formula I in which R is H, 1-25C alkyl, such alkenyl, or aryl; L is a divalent bonding group; Z is an atomic group necessary to form a 5-or 6-membered ring; M is II or an H or alkali metal atom; and n is 0 or 1.

Description

Detailed Description of the Invention

[0001]

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]

Diffusion transfer methods are currently well known in the art and will not be described in detail. For more details, see A. Rott and E. Weyde, “Photographic Silver Halide Diffusion P
rocesses ", published by Focal Press (1972); by J. Sturge, V. Walworth and A. Shepp," Image Processing and Materials: Nebulette 8th Edition ". (Imaging Processes and
Materials: Neblette's Eighth Edition) ", van
Van Nostrand Reinhol
d) Published (1989) Chapter 6 (Chapter 6), "Instant Photographs and Related Duplicate Photograph Processing Methods (Instant
photography and Related Reprographic Processe
s) ”; by G. Haist,“ Modern Photo Processing,
Volume 2 (Modern Photographic Processing Vol.2) ",
John Wiley and S
ons) (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 made and are described in detail in the aforementioned textbooks. For example, a light-sensitive 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 superposed, and a developing agent and a silver halide solvent are superposed. It is known that a transfer image can be obtained by spreading a processing element consisting of a highly viscous alkaline processing composition containing, between said two elements. A method of using regenerated cellulose as a binder of an image receiving layer is known. That is, Japanese Patent Publication No. 46-4394
No. 4 describes a method of preparing an image-receiving element by dispersing silver precipitation nuclei in acetyl cellulose, coating the support on a support, and then hydrolyzing and reproducing the acetyl cellulose. Further, in JP-B-51-49411, a layer of cellulose ester is provided on a paper support, and the silver precipitating agent is hydrolyzed at the same time as or after the cellulose ester layer is hydrolyzed with an alkaline hydrolyzing solution. An image-receiving material produced by incorporating a cellulose ester layer, that is, a regenerated cellulose layer, is described. 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 becomes high, especially in a high-density portion, so that an inverted image results. It significantly deteriorates the quality.
This is a phenomenon that occurs because the transferred silver concentrates and deposits only on the very surface of the image receiving layer, and its appearance can be confirmed by observing the cross section of the image receiving layer having 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 low, silver precipitation concentrates on the surface of the image-receiving layer, resulting in a metallic luster. On the contrary, if the content is too high, the color tone becomes too cold and the maximum density (Dmax) becomes large. Fall to. It is also important to control the saponification reaction of the cellulose ester in order to improve the metallic luster. If the area having a high percentage of free OH groups (saponified) is too shallow, the active silver precipitating agent concentrates on the surface of the image receiving layer, so that a metallic luster is likely to appear. On the other hand, if the region having a high free OH group ratio is too deep, the diffusion of the image stabilizer added to the lower neutralization layer and the neutralization timing layer will increase and Dmax will decrease, and at the same time, it will be added to the image receiving layer. The compound also diffuses and the effect of preventing metallic luster is reduced. Therefore, in order to prevent metallic luster, it is important to define three conditions of the kind and content of the compound contained in the image receiving layer and the distribution of the free OH group ratio of the image receiving layer, and satisfy these conditions at the same time.

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 portion.

[0005]

The foregoing objects have been achieved by developing a light-sensitive element containing an image-exposed light-sensitive silver halide emulsion layer with an alkaline processing element containing a silver halide solvent to obtain the emulsion layer. In the image forming method, at least a part of the unexposed silver halide as a transferable complex salt is used, and at least a part of the complex salt is transferred to an image receiving element including a silver precipitation 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 and then saponifying with an alkaline solution, the image-receiving layer made of regenerated cellulose has a free OH group ratio of 0.5 to 3.0 μm from the surface. In an area of 40% or more, and the image-receiving layer contains 1 × 10 ^{−5 to} 6 × 10 ⁻⁵ mol per cm ³ of at least one compound selected from the group of compounds represented by formula (I). Characterized by It was achieved by the image-receiving element for salt diffusion transfer process. General formula (I)

[0006]

[Chemical 2]

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 5 to 10 carbon atoms. L represents a divalent linking group, and is 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 heterocycle, 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. The compounds effective in the general formula (I) are exemplified below, but the present invention is not limited to these compounds.

[0008]

[Chemical 3]

The addition amount of the compound represented by the general formula (I) is
Preferably 1 cm³1.5 × 10 per ^-Five~ 5.5 x 10^-Five
mol.

The compounds of the present invention can be synthesized by known methods, but some compounds are disclosed in JP-A-59-
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 with the coating liquid when the cellulose ester which is the binder of the image receiving layer is applied. Alternatively, JP-A-61-285
No. 452, the regenerated cellulose layer containing silver precipitation nuclei is prepared and then 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 coated by a known method, or is mixed with a coating solution at the time of coating the release layer and / or the neutralization timing layer and / or the neutralization layer and / or other auxiliary layer. , May be contained in the image receiving layer.

The coating amount of the compound of the present invention, which is effective for improving the metallic luster, greatly varies depending on the coating method and coating conditions, and therefore cannot be generally specified. Therefore, it is appropriate to specify the content in the image receiving layer after completion of the image receiving element. Further, the saponification state of the cellulose ester in the image receiving layer, which is an important factor for improving the metallic luster, greatly changes depending on the application method and application conditions of the alkali saponification solution, and cannot be generally specified by the formulation. The saponification state of the cellulose ester of the image receiving layer, which is effective for improving the metallic luster, is appropriately defined by the free OH group ratio and the depth value. As the saponification recipe, alkali / H ₂ O, alkali / methanol, etc. are generally used, but an alkali / methanol recipe containing glycerin for adjusting the saponification depth is preferred.

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, the microscopic infrared absorption spectrum is measured for a sample having a thickness of 1 to 3 μm, which is prepared by cutting the image receiving element obliquely at a low angle using a microtome. 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 ratio of the free OH groups of the cellulose ester at an arbitrary depth can be obtained from the intensity ratio of the intrinsic absorption of the carbonyl group and the intrinsic absorption of the ether bond of the cellulose skeleton.

The image-receiving element in the present invention is a support carrying an image-receiving layer containing silver precipitation nuclei, for example, baryta paper,
It is coated on polyethylene laminated paper, cellulose triacetate or polyester compounds. The image receiving element of the invention may contain a compound of the invention or another mercapto compound to improve the color tone, stability or other photographic performance of the silver transferred image. Examples of the mercapto compound used include JP-A-49-120634 and JP-B-56-
The compounds described in JP-A-44418, British Patent 1,276,961, JP-B-56-21140, JP-A-59-231537 and JP-A-60-122939 are preferable.

Specific examples of silver precipitation nuclei include heavy metals such as iron, lead, zinc, nickel, cadmium, tin, chromium,
There are copper, cobalt as well as precious 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 gold, platinum, and palladium sulfides and selenides. Particularly, gold, platinum, palladium and their sulfides are preferable.

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 treatment liquid, etc., but is generally preferably 4 μm to 8 μm, particularly 4.5.
μm to 7 μm is preferable.

Further, it is preferable to provide an acidic polymer layer for neutralization (alkali neutralization layer) between the unsaponified layer of cellulose ester (timing layer) after the saponification treatment and the support. For example, the polymer acids described in U.S. Pat. No. 3,594,164 are used. Preferred polymer acids include maleic anhydride copolymers (for example, styrene-maleic anhydride copolymers, methyl vinyl ether-maleic anhydride copolymers, ethylene-maleic anhydride copolymers) 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 copolymers). In addition, polymers containing sulfonic acid such as polyethylene sulfonic acid and acetalized product 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 non-permeable polymer (particularly the above-mentioned cellulose ester is preferable) or an alkali-permeable polymer.

Further, the image receiving element preferably has an image stabilizing layer for improving the image storability, and a cationic polyelectrolyte is preferable as the stabilizing agent, particularly JP-A-59-166940. US Patent 3,958,9
95, JP-A-55-142339, JP-A-54-126.
No. 027, No. 54-155835, No. 53-3032.
Water-dispersed latex described in US Pat.
548,564, 3,148,061, 3,7
Polyvinylpyridinium salt described in US Pat. No. 56,814, water-soluble quaternary ammonium salt polymer described in US Pat. No. 3,709,690 or US Pat. No. 3,898,088.
The water-insoluble quaternary ammonium salt polymer described in No. 1 is preferable as the cationic polyelectrolyte. In addition, as the binder of the image stabilizing layer, cellulose acetate is preferable, and cellulose diacetate having an acetylation degree of 40 to 49% is particularly preferable.
This image stabilizing layer is preferably provided between the neutralizing layer and the timing layer.

The timing layer has an acid polymer (for example, methyl vinyl ether) for the purpose of preventing the timing time from becoming long due to the change of cellulose ester when it is stored for a long period of time or shortening the timing time. Maleic anhydride copolymer or methyl vinyl ether and maleic anhydride half ester copolymer)
Can be included.

Further, a white pigment (for example, titanium dioxide, silicon dioxide, kaolin, zinc dioxide) is added to the timing layer and the neutralization layer for the purpose of preventing light from penetrating from the cross-sectional direction of the sheet to the inside (light piping). , Barium sulphate).

Furthermore, in the timing layer and the neutralization layer,
A plasticizer may be included for the purpose of improving curl and brittleness. Well-known compounds can be used as the plasticizer.

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 or polyacrylamide can be used.

Further, a peeling layer is preferably provided on the surface of the image receiving layer in order to prevent the processing liquid from adhering to the surface of the image receiving layer during peeling after developing the processing liquid. Preferable examples of such a release layer include gum arabic, hydroxyethyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, polyacrylamide and sodium alginate, as well as US Pat. Nos. 3,772,024, 3,820,999 and British Patent. 1,360,65
The thing described in No. 3 can be mentioned.

As a method of shading, a method of incorporating a shading agent (for example, carbon black or an organic black pigment) in the paper of the support, or coating the above-mentioned shading 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. Further, it is preferable to provide a protective layer on these uppermost layers. The protective layer is
A matting agent may be included to improve the adhesiveness and to provide the writing property.

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

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

In addition to the above-mentioned layer structure, a titanium dioxide 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 photosensitive silver halide emulsion layer is formed thereon. A photosensitive element having a protective layer provided on the other side, a carbon black layer on the other side, and a protective layer provided thereon is preferably used. A colored dye may be used instead of the carbon black or in addition to the carbon black.
When the 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 above 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, but preferably the average iodide. 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 1.0 to 3.0 mol%, more preferably 1.5 to 3.0 mol%. Further, it is preferable to change the silver iodide content inside and on the surface of the grain. The higher the internal silver iodide content 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 set arbitrarily, but from the viewpoint of sensitivity and fog, 1 mol% or less is preferable.

The effect of silver iodobromide formed on the surface after chemical sensitization is a very effective means of achieving higher sensitivity without slowing the dissolution rate. The silver iodobromide formed is preferably 3 to 8% in terms of silver amount. If the amount of silver is too small or too large, the sensitivity is lowered 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 becomes slow and the completion of the transferred image becomes slow. As a method of forming silver iodobromide, 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 recrystallizing it on the host grains by Ostwald ripening and an odor There is a method in which a silver halide fine grain emulsion and an aqueous potassium iodide solution are added and recrystallized on the host grains by Ostwald ripening.

Regarding the halogen composition distribution of the silver halide grain of the present invention, including what has been described above, a grain having a so-called uniform structure having the same composition in any portion of the grain, a core (nucleus) inside the grain and surrounding it. Particles having a so-called laminated structure having a different composition from that of a shell (a single layer or a plurality of layers) or a structure having a non-layered portion having a different composition (in the case of being on the particle surface, the edge of the particle, It is possible to appropriately select and use particles having a structure in which portions having different compositions are bonded to a corner or a surface. In order to obtain high sensitivity, it is advantageous to use either of the latter two particles rather than the particles having a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When the silver halide grains have the structure as described above, the boundary portion having different halogen composition may be a clear boundary or an unclear boundary forming a mixed crystal. It may have a continuous structural change.

The silver halide grain of the present invention may be a grain in which a latent image is mainly formed on the surface or may be a grain in which a latent image is mainly formed, and the latent image is formed on any of them. Does not have to 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 that the silver amount was 1 g / m ² , and a sample having a gelatin protective layer thereon was exposed, and then MAA-1 + hypo 0 0.3 g /
Development is carried out for 20 minutes at 20 ° C. with the processing liquid of No. 1. ]

The silver halide grains of the present invention are those having an equiaxed crystal form such as a cube and octahedron, those having an irregular crystal form such as a sphere and a tabular form, or a crystal form of these. Any one having a complex shape may be used. The average size of the silver halide grains of the present invention (represented by the diameter when 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.

The emulsion used in the present invention is a graphide (PG
Lafkides), "The Chemistry and Physics of Photography (Chimie et Phisiq
ue Photographique) ”, Paul Montel
Published by tel) (1967); GF Duffin
Written by "Photographic Emulsion Chem
istry) ", published by Focal press (1
966); Zelikman et al.
Author, “Making and Coating P
hotographic Emulsions) ", Focal Press (Fo
cal Press) (1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a format for reacting a soluble silver salt and a soluble halogen salt, any method such as a one-sided mixing method, a simultaneous mixing method, and a combination thereof may be used. You may use. It is also possible to use a method of forming particles in an atmosphere in which silver ions are excessive (so-called reverse mixing method). As one form of the simultaneous mixing method, a method of keeping pAg constant in a liquid phase in which silver halide is produced, 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 substantially uniform grain size can be obtained. Further, as a method for obtaining a tabular silver halide having a substantially uniform grain size, for example, US Pat.
The technology of No. 7,354 can be used.

The silver halide emulsion used in the present invention is iron,
In addition to the salt or complex salt of iridium, various polyvalent metal ion compounds can be introduced in the process of emulsion grain formation or physical ripening. Examples of the compound used include salts such as cadmium, zinc, lead and thallium, or salts or complex salts such as ruthenium, rhodium, palladium, osmium and platinum of Group VIII of the periodic table. In particular, Group VIII elements can be preferably used. The amount of these compounds added varies over a wide range depending on the purpose, but is 10 ^-9 to 10 ^-10 mol per mol of silver halide.
^-4 mol is preferred.

The chemical sensitization used in the silver halide emulsion of the present invention is described in "Glafkides", "Duffin" and "Zelikman" or in "Halogenation" by Freezer (H. Frieser). The basics of the silver photography process (DieGrundlagen der Photograph
ischen Prozesse mit Silberhalogeniden) ", Academiche Fairlarks Gezelshaft (Akademisch
e Verlagsgesellschaft) (1968) can be used. That is, compounds containing sulfur capable of reacting with active gelatin or silver (eg, thiosulfates, thioureas, mercapto compounds, rhodanins)
Sulfur sensitization method using a noble metal compound (eg, gold complex salt, platinum, iridium, palladium, etc.
A noble metal sensitization method using a Group VIII metal complex salt); a reduction sensitization method using a reducing substance (eg, stannous salt, amines, hydrazine derivative, formamidinesulfinic acid, silane compound) alone or in combination Can be used.

The spectral sensitizer used in the silver halide emulsion of the present invention includes cyanine dyes, merocyanine dyes,
Preference is given to 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. A specific example is
FM Hamer, “Heterocyclie Compounds-Cyan
in Dyes and Related Compounds ”, published by John Wiley and Sons (196
4 years). Others, US Patent 2,49
3,748, 2,519,001, 2,97
7,229, 3,480,434, 3,67
2,897, 3,703,377, 2,68
8,545, 2,912,329, 3,39
No. 7,060, No. 3,615, 635, No. 3,62
8,964, British Patents 1,195,302, 1,
242,588, 1,293,862, West German Patent Application (OLS) 2,030,326, 2,121,
No. 780, Japanese Examined Patent Publication No. 43-4936, No. 44-1403
0, 43-10773, U.S. Pat. No. 3,511,6
No. 64, No. 3,522, 052, No. 3,527, 64
No. 1, No. 3,615, 613, No. 3, 615, 632
No. 3,617,295, No. 3,635,721
No. 3,694,217, British Patent 1,137,5
The spectral sensitizers described in No. 80, No. 1,216,203 and the like can also be used. The spectral sensitizer is disclosed in JP-A-59-
As described in Nos. 114533 and 61-163335, a plurality of them can be used in combination.

The photosensitive element of the present invention has a thickness of 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 ..

The light-sensitive silver halide emulsion layer of the present invention comprises
Various compounds can be incorporated for the purpose of preventing fogging and stabilizing photographic performance during the manufacturing process of photographic materials, during storage, or during photographic processing. These compounds include azoles (for example, benzothiazolium salt,
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, etc. Agents and stabilizers are preferably used. As a typical example, 1-phenyl-2-mercaptotetrazole,
4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, 2-mercaptobenzothiazole, 5-
Carboxybutyl-1,2-dithiolane and the like. For more detailed specific examples of these and methods for using them, see, for example, US Pat.
Those described in 2-28660 can be used.

The light-sensitive element of the present invention may contain an inorganic or organic hardener. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea,
Methyloldimethylhydantoin etc.), dioxane derivative (2,3-dihydroxydioxane etc.), active vinyl compound (1,3,5-triacryloyl-hexahydro-s-triazine etc.), mucohalogenic acids (mucochloric acid, mucophenoxycycloric acid) Etc.) and the like can be used alone or in combination. A coating aid 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) 176, 17643, p. 26 (1978.12)
The compounds described in the section "Coating aids" of the issue) or the compounds described in JP-A-61-20035 can be used.

The silver halide emulsion layer and other hydrophilic colloid layers of the light-sensitive element of the present invention include, for example, polyalkylene oxide or its derivatives such as ethers, esters and amines for the purpose of increasing sensitivity, increasing contrast or promoting development. , Thioether compounds, thiomorpholines,
Compounds such as quaternary ammonium compounds, urethane derivatives, urea derivatives, imidazole derivatives and 3-pyrazolidones may be included. Examples of such compounds include U.S. Pat. Nos. 2,400,532, 2,423,549,
The compounds described in 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 sparingly 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, etc., alone or in combination, or with these, acrylic acid, methacrylic acid, A polymer having a monomer component of a combination of α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, styrenesulfonic acid and the like can be used.

The silver halide emulsion layer used in the light-sensitive element of the present invention may be composed of a plurality of 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 and is disclosed in JP-A-61-161.
A matting agent or a slipping agent such as polymethylmethacrylate latex or silica as described in No. 47946 and No. 61-75338 can be included.

The light-sensitive element of the present invention may contain a dye or an ultraviolet absorber in the silver halide emulsion layer and other hydrophilic colloid layers for the purpose of filtering or preventing 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.), saccharides (sodium alginate, starch derivatives, etc.) and Synthetic hydrophilic polymer (polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-
It is possible to use vinylpyrrolidone, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, or other homopolymers or copolymers. As for gelatin,
In addition to lime-processed gelatin, acid-processed gelatin and the Journal of the Photographic Society of Japan (Bull.Soc.Sci.Phot.Japan), No. 16, P.P. Thirty
The enzyme-treated gelatin as described in (1966) may be used, and a hydrolyzed product or an enzymatically decomposed product of gelatin may also be used. Gelatin derivatives can be obtained by reacting gelatin with acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkylene oxides, epoxy compounds, etc. Things are used. Specific examples thereof include US Pat. No. 2,614,92.
No.8, No.3,132,945, No.3,186,846
No. 3,312,553, British Patent 861,414
Issue 1,033,189, Issue 1,005,784
And Japanese Examined Patent Publication No. 2626845.
As the gelatin / graft polymer, it is possible to use one obtained by grafting a single or copolymer of vinylic monomers such as acrylic acid, methacrylic acid, acrylic acid ester, acrylamide, acrylonitrile and styrene to gelatin. A specific example is US Pat.
3,625, 2,831,767, 2,95
6, 884 and the like.

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

The processing elements used in this invention include developing agents, silver halide solvents, alkaline agents and toning agents (Toni.
ng agents) are included in the photosensitive element and / or a developing agent and / or a silver halide solvent depending on the purpose.
Alternatively, it may be included in 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 (eg, hydroquinone, amidole, methol, 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, such as hydroxylamine, N-methylhydroxylamine, N-ethylhydroxylamine,
Those described in US Pat. No. 2,857,276 and N described in US Pat. No. 3,293,034
-Alkoxyalkyl substituted hydroxylamines are included. Further, a hydroxylamine derivative having a tetrahydrofurfuryl group described in JP-A-49-88521 can also be used. Also, West German patent application (OLS)
Amino reductones described in Nos. 2,009,054, 2,009,055 and 2,009,078 and heterocyclic amino reductones described in US Pat. No. 4,128,425 are also used. Be done. Moreover, the tetraalkyl reductic acid described in US Pat. No. 3,615,440 can also be used.

Phenidones, p-aminophenols and ascorbic acid can be used in combination with the above 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 above-mentioned US Pat. No. 2,543,181). , A combination of a cyclic imide and a nitrogen base (for example, a combination of barbiturate or uracil with ammonia or an amine, and a combination as described in US Pat. No. 2,857,274) and the like are used. Be done. Further, 1,1-bissulfonylalkane and its derivative are known and can be used as the silver halide solvent of the present invention.

The treatment composition contains alkalis, preferably alkali metal hydroxides such as sodium hydroxide or potassium hydroxide. When the processing composition is developed as a thin layer between the overlaid light-sensitive element and the image-receiving element, the processing element preferably contains a polymeric film former or thickener.

Polymeric film formers or thickeners included in the processing element include carboxymethyl cellulose,
Cellulose derivatives such as ethyl cellulose, hydroxyethyl cellulose, methyl cellulose and hydroxypropyl cellulose, vinyl polymers such as polyvinyl alcohol, acrylic acid 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 preferable. These are included in the processing composition in a concentration effective to provide the proper viscosity by the well known technique 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]

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

Example 1

1. Preparation of image-receiving element An image-receiving element (1-A) was prepared by providing the following layers in order on a support polyethylene laminated paper. Numerical values in [] indicate the coating amount in g / m ² . (1) Neutralization layer Cellulose acetate (acetation degree 55%) [6.0], methyl vinyl ether-maleic anhydride copolymer [4.0], Uvietx 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], the following polymer [2.0]

[0057]

[Chemical 4]

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

(5) Saponification Saponification was carried out from the surface with a liquid prepared by mixing 12 g of sodium hydroxide, 24 g of glycerin and 280 ml of methanol, and washed with water. (6) Release layer Butylmethacrylate-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 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 1- (4-hexylcarbamoylphenyl) -2,3-dihydroimidazole-2-thione in the image receiving layer was changed as shown in Table 1.

[0061]

[Table 1]

2. Preparation of Photosensitive Element A photosensitive element was prepared by coating the following layers on a support (polyethylene terephthalate). Numerical values in [] indicate 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 of 3.0)
Mol% core / shell type structure) [silver conversion 0.55], 4-
Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene [0.01], sensitizing dye (A) below,
(B) and (C) are respectively [3.2 × 10 ⁻⁴ ], [3.2 ×
10 ^-4 ], and [1.2 × 10 ^-4 ], gelatin [3.
9]

[0063]

[Chemical 5]

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

3. Preparation of treatment liquid and pod formation Since the treatment liquid is oxidized by air, it was prepared in a nitrogen stream. After prepared by the following formulation, a plurality of cleavable containers (pods) were filled with 0.7 g of the treatment liquid to prepare a treatment 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

4. Development processing The sample in which the image receiving element, the photosensitive element and the processing element were combined was exposed to continuous gradation for 1/10 second, and 2
After development treatment so that the liquid thickness would be 35 μm at 5 ° C., the metallic gloss of the image-receiving element peeled off in 5 minutes was visually judged. next,
A sample prepared by cutting the untreated image receiving element with a microtome at a cutting angle of about 2 degrees was measured with a microscopic infrared spectrophotometer,
The saponification degree distribution of cellulose ester in the image receiving layer was analyzed and the compound of the present invention in the image receiving layer was quantified. The results are shown in Table 2.

[0068]

[Table 2]

As is clear from Table 2, even if the degree of saponification of the cellulose ester which is the binder of 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 proper, the metallic luster is obtained. It can be seen that the quality of the transferred image is remarkably deteriorated due to the display or abnormal color tone.

Example 2 In Example 1, the amount of 1- (4-hexylcarbamoylphenyl) -2,3-dihydroimidazol-2-thione added to the image-receiving layer of the image-receiving element and the content of the saponification solution are shown. The development and peeling process and the analysis of the image receiving element were performed in the same manner as in Example 1 except that the changes were made as described in Example 3. The results are shown in Table 4.

[0071]

[Table 3]

[0072]

[Table 4]

As is clear from Table 4, even if the image-receiving element contains the compound of the present invention in the same amount in the image-receiving layer, if the saponification degree of the cellulose ester serving as the binder of the image-receiving layer is not appropriate, the metallic luster is obtained. It is understood that the quality of the transferred image is remarkably deteriorated due to the occurrence of a decrease in the density.

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 by the compound in the same amount as shown in Table 5. The development and peeling process and the analysis of the image receiving element were performed in the same manner as in Example 1 except for the points described above. The results are shown in Table 5.

[0075]

[Table 5]

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

[0077]

According to the present invention, it is possible to obtain a good transferred image without metallic luster even in a high density portion.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] October 2, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Correction content]

[Chemical 1] 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.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0006

[Correction method] Change

[Correction content]

[0006]

[Chemical 2]

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0012

[Correction method] Change

[Correction content]

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, the microscopic infrared absorption spectrum is measured for a sample having a thickness of 1 to 3 μm, which is prepared by cutting the image receiving element obliquely at a low angle using a microtome. The measurement of the microscopic infrared absorption spectrum is described in "FT-1R in 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 ratio of the free OH groups of the cellulose ester at an arbitrary depth can be obtained from the intensity ratio of the intrinsic absorption of the carbonyl group and the intrinsic absorption of the ether bond of the cellulose skeleton.

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0022

[Correction method] Change

[Correction content]

Further, a peeling layer is preferably provided on the surface of the image receiving layer in order to prevent the processing liquid from adhering to the surface of the image receiving layer during peeling after developing the processing liquid. Preferable examples of such a release layer include gum arabic, hydroxyethyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, polyacrylamide and sodium alginate, as well as US Pat. Nos. 3,772,024, 3,820,999 and British Patent. 1,360,65
The thing described in No. 3 can be mentioned. To enhance the whiteness during observation, either layer of the image receiving element,
Uvitex OB (trade name of Ciba Geigy), White Fluor (Whitefluo)
r) Benzoxazole type such as PSN (trade name of Sumitomo Chemical Co., Ltd.), White Fluor (Whiteflu
or) a coumarin-based fluorescent whitening agent such as B (trade name of Sumitomo Chemical Co., Ltd.).

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0056

[Correction method] Change

[Correction content]

1. Preparation of image-receiving element An image-receiving element (1-A) was prepared by providing the following layers in order on a support polyethylene laminated paper. The numerical value in [] indicates the coating amount before saponification and washing with water in g / m ² . (1) Neutralization layer Cellulose acetate (acetation degree 55%) [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], the following polymer [2.0]

[Procedure Amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0067

[Correction method] Change

[Correction content]

4. Development processing and measurement The sample in which the image receiving element, the photosensitive element and the processing element were combined was exposed to continuous gradation for 1/10 seconds, and 2
After development treatment so that the liquid thickness would be 35 μm at 5 ° C., the metallic gloss of the image-receiving element peeled off in 5 minutes was visually judged. on the other hand,
Separately, the untreated image receiving element is cut with a microtome at a cutting angle of about 2
The sample prepared by cutting with a microscopic degree was measured with a microscopic infrared spectrophotometer to analyze the saponification degree distribution of cellulose ester in the image receiving layer and quantify the compound of the present invention in the image receiving layer. The results are shown in Table 2.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0071

[Correction method] Change

[Correction content]

[0071]

[Table 3]

[Procedure Amendment 8]

[Document name to be amended] Statement

[Name of item to be corrected] 0072

[Correction method] Change

[Correction content]

[0072]

[Table 4]

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0075

[Correction method] Change

[Correction content]

[0075]

[Table 5]

Claims (1)

[Claims] 1. A photosensitive element containing an imagewise exposed light sensitive silver halide emulsion layer is developed with an alkaline processing element containing a silver halide solvent to provide at least one of the unexposed silver halide layers in the emulsion layer. Part is a transferable complex salt, and at least a part of the complex salt is transferred to an image receiving element including a silver precipitation nucleus-containing image receiving layer to form an image on the image receiving element. The free OH group ratio of the image-receiving layer made of regenerated cellulose obtained by saponification with an alkaline solution after coating with a containing cellulose ester is 40% or more in a region from the surface to 0.5 to 3.0 μm, and In the image-receiving layer, at least one compound selected from the group of compounds represented by formula (I) is added at 1 × 10 ⁻⁵ per cm ^3.
An image-receiving element for silver salt diffusion transfer method, characterized in that the content is up 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.